阅读说明：本技术 气相色谱分析方法及气相色谱分析系统 (Gas chromatography method and gas chromatography system ) 是由 芝本繁明 于 2021-05-07 设计创作，主要内容包括：本发明的课题为将通过水的电解而生成的氢气及氧气有效率地应用于气相色谱分析中的气相色谱分析方法及气相色谱分析系统。气相色谱分析方法包括：使用载体气体,将样品气体导入至分离管柱(4)而将所述样品气体中的成分分离的步骤；以及将经过所述分离管柱(4)的样品气体导入至检测器(6)来检测所述样品气体中的成分的步骤,并且所述检测步骤包括：将通过水的电解而生成的氢气及氧气各别地取出；以及将所取出的氢气及氧气的流量分别进行控制,作为检测器气体而分别向所述检测器供给。(The subject of the invention is a gas chromatography method and a gas chromatography system for efficiently applying hydrogen and oxygen generated by water electrolysis to gas chromatography. The gas chromatographic analysis method comprises the following steps: a step of introducing a sample gas into a separation column (4) using a carrier gas to separate components in the sample gas; and a step of introducing the sample gas passing through the separation column (4) to a detector (6) to detect a component in the sample gas, and the detecting step includes: separately taking out hydrogen and oxygen generated by the electrolysis of water; and controlling the flow rates of the extracted hydrogen gas and the extracted oxygen gas, respectively, and supplying the hydrogen gas and the oxygen gas as detector gases to the detectors, respectively.)

1. A gas chromatography method, comprising:

a step of introducing a sample gas into a separation column using a carrier gas to separate components in the sample gas; and

a step of introducing the sample gas passed through the separation column to a detector to detect a component in the sample gas, and

the step of detecting comprises:

separately taking out hydrogen and oxygen generated by the electrolysis of water;

the flow rates of the extracted hydrogen gas and oxygen gas are controlled separately, and the hydrogen gas and oxygen gas are supplied to the detector as detector gases.

2. The gas chromatographic analysis method of claim 1, wherein

The step of detecting includes adjusting a ratio of hydrogen to oxygen introduced to the detector to a ratio suitable for the detector.

3. The gas chromatographic analysis method according to claim 2, wherein

The step of separating comprises supplying hydrogen generated by electrolysis of water as the carrier gas upstream of the separation column; and is

In the step of detecting, the flow rates of the hydrogen gas and the oxygen gas are controlled so that the ratio of the total flow rate of the hydrogen gas introduced into the detector as the detector gas and the hydrogen gas introduced into the detector as the carrier gas to the flow rate of the oxygen gas introduced into the detector becomes a ratio suitable for the detector.

4. A gas chromatography system, comprising:

a separation column for separating components in the sample gas;

a detector fluidly connected downstream of the separation column for detecting components separated by the separation column;

a gas generator configured to generate hydrogen gas and oxygen gas by electrolysis of water, and to separately take out the generated hydrogen gas and oxygen gas;

a first flow passage for guiding the hydrogen gas generated in the gas generator to the detector as a detector gas;

a second flow path for guiding oxygen generated in the gas generator to the detector as a detector gas; and

and a detector gas flow rate adjusting unit that adjusts a flow rate of the hydrogen gas introduced into the detector through the first flow channel and a flow rate of the oxygen gas introduced into the detector through the second flow channel.

5. The gas chromatography system of claim 4, further comprising:

and a controller configured to control the detector gas flow rate adjuster to adjust a ratio of a flow rate of the hydrogen gas to a flow rate of the oxygen gas introduced into the detector to a ratio suitable for the detector.

6. The gas chromatography system of claim 5, further comprising:

a third flow path for guiding the hydrogen gas generated in the gas generator as a carrier gas to the upstream of the separation column; and

a carrier gas flow rate adjusting unit that adjusts a flow rate of the hydrogen gas introduced as the carrier gas into the detector, and adjusts the hydrogen gas flow rate

The control unit is configured to: and a detector gas flow rate adjusting unit configured to control the detector gas flow rate adjusting unit and the carrier gas flow rate adjusting unit to adjust a ratio of a total flow rate of the hydrogen gas introduced into the detector as the detector gas and the hydrogen gas introduced into the detector as the carrier gas to a flow rate of the oxygen gas introduced into the detector to a ratio suitable for the detector.

7. The gas chromatography system of claim 5, comprising:

an information storage unit that stores information relating to a correlation between a type of the detector and a ratio of a flow rate of hydrogen gas to a flow rate of oxygen gas suitable for the type; and is

The control unit is configured to: the type of the detector is identified based on information input by a user or information obtained from the detector, a ratio of hydrogen to oxygen suitable for the type of the detector is calculated from the information storage unit, and the calculated ratio of hydrogen to oxygen is used as a ratio suitable for the detector.

8. The gas chromatography system of claim 6, comprising:

an information storage unit that stores information relating to a correlation between a type of the detector and a ratio of a flow rate of hydrogen gas to a flow rate of oxygen gas suitable for the type; and is

The control unit is configured to: the type of the detector is identified based on information input by a user or information obtained from the detector, a ratio of hydrogen to oxygen suitable for the type of the detector is calculated from the information storage unit, and the calculated ratio of hydrogen to oxygen is used as a ratio suitable for the detector.

9. The gas chromatography system of any of claims 4-8, wherein

The separation column is a capillary column.

Technical Field

The invention relates to a gas chromatography method and a gas chromatography system.

Background

In the gas chromatography, a Flame Ionization Detector (FID), a Flame Photometric Detector (FPD), a Flame Thermionic Detector (FTD), a Thermal Conductivity Detector (TCD), or the like can be used as the Detector.

However, in a detector such as FID, hydrogen gas needs to be supplied to the detector. A hydrogen gas cylinder is generally used as a supply source of hydrogen gas, but in order to avoid the danger of the hydrogen gas cylinder, it has been proposed to generate hydrogen gas by using a water electrolysis device and use the generated hydrogen gas as a working gas for FID (see patent document 1).

[ Prior art documents ]

[ patent document ]

[ patent document 1] US2002/054832A1

Disclosure of Invention

[ problems to be solved by the invention ]

The system described in patent document 1 cannot sufficiently use hydrogen gas and oxygen gas generated by an electrolysis device using water.

The purpose of the present invention is to efficiently apply hydrogen and oxygen generated by electrolysis of water to gas chromatography.

[ means for solving problems ]

The gas chromatography analysis method of the present invention comprises: a step of introducing a sample gas into a separation column using a carrier gas to separate components in the sample gas; and a step of introducing the sample gas passing through the separation column to a detector to detect a component in the sample gas, the step of detecting including: separately taking out hydrogen and oxygen generated by the electrolysis of water; and controlling the flow rate of each of the extracted hydrogen gas and oxygen gas, and supplying the respective gas to the detector as detector gases.

The gas chromatography system of the present invention comprises: a separation column for separating components in the sample gas; a detector fluidly connected downstream of the separation column for detecting components separated by the separation column; a gas generator configured to generate hydrogen gas and oxygen gas by electrolysis of water, and to separately take out the generated hydrogen gas and oxygen gas; a first flow passage for guiding the hydrogen gas generated in the gas generator to the detector as a detector gas; a second flow path for guiding oxygen generated in the gas generator to the detector as a detector gas; and a detector gas flow rate adjustment unit that adjusts the flow rate of hydrogen gas introduced into the detector through the first flow channel and the flow rate of oxygen gas introduced into the detector through the second flow channel.

That is, in the gas chromatography method and system of the present invention, the hydrogen gas and the oxygen gas generated by the electrolysis of water are separately taken out, and the hydrogen gas and the oxygen gas are introduced as the detector gas to the detector while controlling the flow rates of the hydrogen gas and the oxygen gas, respectively. This makes it possible to control the ratio of the hydrogen gas and the oxygen gas introduced into the detector to a desired value. The ideal ratio of the hydrogen gas and the oxygen gas introduced into the detector differs depending on the type of the detector, but in the present invention, the ratio of the hydrogen gas and the oxygen gas introduced into the detector can be controlled to a desired value, and thus, the present invention can be applied to a plurality of types of detectors. On the other hand, in the method of introducing the mixed gas of hydrogen and oxygen generated by the electrolysis of water to the detector as described in patent document 1, the ratio of hydrogen to oxygen introduced to the detector is constant, and it cannot be adapted to various types of detectors.

[ Effect of the invention ]

In the gas chromatography method of the present invention, the hydrogen gas and the oxygen gas generated by the electrolysis of water are separately taken out, and the respective flow rates of the taken-out hydrogen gas and oxygen gas are controlled to supply the hydrogen gas and oxygen gas to the detector as the detector gas, respectively, so that the hydrogen gas and oxygen gas generated by the electrolysis of water can be efficiently used for the gas chromatography.

In the gas chromatography system of the present invention, the gas chromatography system is configured such that: hydrogen and oxygen gases are generated by the electrolysis of water and are separately taken out, and the hydrogen and oxygen gases taken out are introduced as detector gases to the detector while adjusting the flow rates of the hydrogen and oxygen gases, respectively.

Drawings

Fig. 1 is a schematic configuration diagram showing an embodiment of a gas chromatography system.

Fig. 2 is a cross-sectional view schematically showing an example of the structure of the detector according to the embodiment.

Fig. 3 is a flowchart showing an example of the operation of the embodiment.

Fig. 4 is a schematic diagram schematically showing the principle of gas generation in the gas generator of the embodiment.

[ description of symbols ]

2: syringe with a needle

4: separation tubular column

6: detector

8: tubular column oven

10: gas generator

12: control device

13. 14, 16, 18: flow passage

20：AFC

22：APC

24: control unit

26: information storage unit

Detailed Description

Hereinafter, an embodiment of the gas chromatography method and system according to the present invention will be described with reference to the drawings.

As shown in fig. 1, the gas chromatography system of this embodiment includes: an injector 2, a separation column 4, a detector 6, a column oven 8, a gas generator 10, a control device 12, an Advanced Flow Controller (AFC) 20, and an Advanced Pressure Controller (APC).

The separation column 4 is, for example, a capillary tube coated or filled with a separation medium for separating components in the sample gas. The inlet end of the separation column 4 is fluidly connected to the injector 2 and the outlet end is fluidly connected to the detector 6. The separation column 4 is housed in a column oven 8 in which the temperature of the internal space is adjusted to a set temperature.

The injector 2 generates a sample gas, and introduces the generated sample gas into the separation column 4 by using a carrier gas. In this embodiment, hydrogen gas generated in the gas generator 10 is used as the carrier gas.

The detector 6 is arranged to detect components in the sample gas passing through the separation column 4. The detector 6 can use any of FID, FPD, FTD, TCD. When the detector 6 is any one of the FID, FPD, and FTD, the hydrogen gas and the oxygen gas generated in the gas generator 10 are supplied to the detector 6 as a detector gas. In addition, when the detector 6 is TCD, only the hydrogen gas generated in the gas generator 10 is supplied to the detector 6 as the detector gas (that is, the flow rate of the oxygen gas introduced into the detector 6 is adjusted to zero).

The gas generator 10 is configured to: hydrogen and oxygen are generated by electrolysis of water, and the generated hydrogen and oxygen can be taken out separately. Fig. 4 schematically shows the gas generation principle in the gas generator 10. In the gas generator 10, an anode electrode and a cathode electrode are provided with an ion exchange membrane interposed therebetween, and a dc voltage is applied between the anode electrode and the cathode electrode, whereby the following formula is applied to the anode electrode side

2H₂O－4e＝O₂+4H⁺

Oxygen is generated by the electrolytic reaction of (1), and at the cathode electrode side, oxygen is generated by the following formula

4H⁺+4e＝2H₂

To generate oxygen. The gas generator 10 is configured to be able to separately take out oxygen gas generated in the anode electrode and hydrogen gas generated in the cathode electrode. Furthermore, an electrolysis apparatus configured to be able to separately take out hydrogen and oxygen generated by electrolysis of water is known (for example, see japanese patent laid-open nos. 2020 and 066796 and 2018 and 178231).

The gas generator 10 includes a hydrogen outlet and an oxygen outlet, and the flow path 13 is connected to the hydrogen outlet and the flow path 18 is connected to the oxygen outlet. The flow channel 13 branches into a flow channel 14 leading to the injector 2 and a flow channel 16 leading to the detector 6. Flow channel 18 leads to detector 6. The flow passage 16 constitutes a first flow passage for guiding the hydrogen gas generated in the gas generator 10 to the detector 6 as a detector gas. The flow channel 18 constitutes a second flow channel for guiding the oxygen gas generated in the gas generator 10 to the detector 6 as a detector gas. The flow channel 14 constitutes a third flow channel for guiding the hydrogen gas generated in the gas generator 10 as a carrier gas to the upstream of the separation column 4.

The AFC20 is used to control the total flow rate of hydrogen gas introduced into the injector 2, the inlet pressure of the separation column 4, the flow rate of the split flow discharge port, and the flow rate of the purge discharge port, respectively, at the time of analysis. The flow rate obtained by subtracting the flow rate of the split discharge port and the flow rate of the flushing discharge port from the total flow rate of the hydrogen gas introduced into the injector 2 becomes the flow rate of the hydrogen gas introduced as the carrier gas into the detector 6 via the separation column 4. That is, AFC20 realizes a carrier gas flow rate adjusting portion for adjusting the flow rate of hydrogen gas introduced as a carrier gas to detector 6.

The APC 22 is used to adjust the flow rate of hydrogen flowing through the flow passage 16 and the flow rate of oxygen flowing through the flow passage 18, respectively. That is, the APC 22 realizes a detector gas flow rate adjustment unit for adjusting the flow rate of each of the hydrogen gas and the oxygen gas introduced into the detector 6 as the detector gas. The detector gas flow rate adjustment unit does not need to be implemented by a flow rate adjuster such as one APC 22, and the flow rate of the hydrogen gas flowing through the flow path 16 and the flow rate of the oxygen gas flowing through the flow path 18 may be adjusted by different flow rate adjusters.

Here, the structure of the detector 6 will be described by taking FID as an example.

In the case where the detector 6 is an FID, as shown in fig. 2, a nozzle 102 for generating a hydrogen flame is provided in an inner space of a unit 100 of the detector 6. The pipe 104 forming the outlet portion of the separation column 4 passes through the inside of the nozzle 102. A pipe 108 forming a part of the flow channel 16 is fluidly connected to the nozzle 102, and the hydrogen gas generated in the gas generator 10 is introduced as a detector gas into a gap between the outer peripheral surface of the pipe 104 and the inner surface of the nozzle 102. The hydrogen gas introduced into the nozzle 102 as the detector gas joins the carrier gas from the separation column 4 at the tip of the nozzle 102, and is discharged from the tip of the nozzle 102.

The pipe 110 forming a part of the flow passage 18 leads to the internal space of the cell 100, and the oxygen gas generated in the gas generator 10 is introduced as the detector gas into the internal space of the cell 100. The oxygen gas introduced into the internal space of the unit 100 is used as a combustion-supporting gas for combusting the hydrogen gas discharged from the tip of the nozzle 102, thereby forming a hydrogen flame at the tip of the nozzle 102. The pipe 110 is connected to the inside of the nozzle 2, and hydrogen and oxygen may be mixed in the inside of the nozzle 2.

Returning to fig. 1, the description of the analysis system is continued.

The control device 12 has a function of controlling the operation of the gas generator 10, the AFC20, and the APC 22, and is realized by an electronic circuit including at least a Central Processing Unit (CPU) and a data storage device. The control device 12 includes a control unit 24 and an information storage unit 26. The control unit 24 is a function realized by the CPU executing a program, and the information storage unit 26 is a function realized by a storage area that is a part of the data storage device.

The control unit 24 is configured to: the operations of the AFC20 and the APC 22 are controlled not only to operate the gas generator 10 so as to obtain the amounts of hydrogen and oxygen necessary for analysis, but also to adapt the ratio of the flow rate of hydrogen to the flow rate of oxygen introduced to the detector 6.

The ratio of the flow rates of hydrogen and oxygen required for the detector 6 to operate normally differs depending on the type of the detector 6 (FID, FPD, etc.). The information storage unit 26 stores information on the flow rate ratio of hydrogen gas and oxygen gas suitable for various detectors. In addition, as another embodiment, the detector 6 itself may hold information on the ratio of hydrogen to oxygen suitable for the detector 6.

An example of the operation of the gas chromatography system realized by the control unit 24 will be described with reference to the flowcharts of fig. 1 and 3.

First, the control unit 24 determines which type of detector 6 is based on information input by the user or information read from the detector 6, and calculates the ratio of the flow rates of hydrogen gas and oxygen gas suitable for the type of detector 6 from the information stored in the information storage unit 26 (step 101). Then, the control unit 24 calculates the ratio of the total flow rate of the hydrogen gas introduced as the carrier gas into the detector 6 through the separation column 4 and the hydrogen gas introduced as the detector gas into the detector 6 through the flow path 16 to the flow rate of the oxygen gas introduced into the detector 6 through the flow path 18, and sets the ratio to the respective flow rates of the hydrogen gas and the oxygen gas necessary for the ratio calculated based on the information of the information storage unit 26 (step 102). Based on the calculation result, the control unit 24 operates the gas generation unit 10 so as to generate the required amounts of hydrogen and oxygen (step 103), and controls the operation of the AFC20 and the APC 22 so that the ratio of the respective flow rates of hydrogen and oxygen introduced into the detector 6 is suitable for the detector 6 (step 104).

In a state where the flow rates of the hydrogen gas and the oxygen gas introduced into the detector 6 by the operation are controlled, the sample is injected into the injector 2, and the gas chromatography is started. The sample injected into the injector 2 becomes a sample gas, and is introduced into the separation column 4 by the carrier gas to separate components in the sample (step 105). The components in the sample separated in the separation column 4 are introduced into the detector 6 together with the carrier gas and detected (step 106).

In the above embodiment, the hydrogen gas generated in the gas generator 10 is used as the carrier gas, and a supply source of another carrier gas different from the gas generator 10 may be provided. In this case, a gas other than hydrogen, such as helium or nitrogen, may be used as the carrier gas. In the case of using a gas other than hydrogen as the carrier gas, the control unit 24 controls the operation of the APC 22 so that the ratio of the flow rate of hydrogen to the flow rate of oxygen introduced into the detector 6 as the detector gas is suitable for the detector 6.

The examples described above are merely illustrative of embodiments of the gas chromatography method and system of the present invention. Embodiments of the gas chromatography method and system of the present invention are described below.

One embodiment of the gas chromatography method of the present invention includes: a step of introducing a sample gas into a separation column using a carrier gas to separate components in the sample gas; and a step of introducing the sample gas passed through the separation column to a detector to detect a component in the sample gas; and the detecting step comprises: separately taking out hydrogen and oxygen generated by the electrolysis of water; the flow rates of the extracted hydrogen gas and oxygen gas are controlled, respectively, and the hydrogen gas and oxygen gas are supplied to the detector as detector gases, respectively.

In a specific aspect of the analysis method according to the embodiment, the step of detecting includes adjusting a ratio of hydrogen to oxygen introduced into the detector to a ratio suitable for the detector. According to this aspect, various types of detectors can be used for gas chromatography using hydrogen gas generated by electrolysis of water.

In the specific aspect, the step of separating may include supplying hydrogen gas generated by electrolysis of water as the carrier gas to an upstream side of the separation column, and in the step of detecting, the flow rates of the hydrogen gas and the oxygen gas may be controlled so that a ratio of a total flow rate of the hydrogen gas introduced as the detector gas to the detector and the hydrogen gas introduced as the carrier gas to a flow rate of the oxygen gas introduced to the detector is a ratio suitable for the detector. With this configuration, all the gases used in the gas chromatography are generated by the electrolysis of water without using any other kind of gas than hydrogen or oxygen as the supplementary gas, and therefore, the gas chromatography without using a gas bomb can be realized. By adapting the shape of the detector to the flow rate at the time of use of the capillary column, the spread of the peak in the chromatogram can be suppressed, and a supplementary gas can be eliminated. Further, since the ratio of the total flow rate of hydrogen gas introduced into the detector to the flow rate of oxygen gas introduced into the detector is controlled so as to be suitable for the detector, it is possible to use various types of detectors in gas chromatography without using a gas cylinder.

One embodiment of the gas chromatography system of the present invention includes: a separation column for separating components in the sample gas; a detector fluidly connected downstream of the separation column for detecting components separated by the separation column; a gas generator configured to generate hydrogen gas and oxygen gas by electrolysis of water, and to separately take out the generated hydrogen gas and oxygen gas; a first flow passage for guiding the hydrogen gas generated in the gas generator to the detector as a detector gas; a second flow path that guides the oxygen gas generated in the gas generator to the detector as a detector gas; and a detector gas flow rate adjustment unit configured to adjust a flow rate of the hydrogen gas introduced into the detector through the first flow channel and a flow rate of the oxygen gas introduced into the detector through the second flow channel, respectively.

In the first aspect of the analysis system according to the embodiment, the analysis system further includes a control unit configured to: and controlling the detector gas flow rate adjusting unit to adjust a ratio of a flow rate of the hydrogen gas to a flow rate of the oxygen gas introduced into the detector to a ratio suitable for the detector. According to this aspect, in the gas chromatography system in which hydrogen gas and oxygen gas are generated by electrolysis of water and used as the detector gas, various types of detectors can be used.

In the first aspect, the present invention further includes: a third flow path for guiding the hydrogen gas generated in the gas generator as a carrier gas to the upstream of the separation column; and a carrier gas flow rate adjusting unit that adjusts a flow rate of the hydrogen gas introduced as the carrier gas to the detector, and the control unit may be configured to: and a detector gas flow rate adjusting unit configured to control the detector gas flow rate adjusting unit and the carrier gas flow rate adjusting unit to adjust a ratio of a total flow rate of the hydrogen gas introduced into the detector as the detector gas and the hydrogen gas introduced into the detector as the carrier gas to a flow rate of the oxygen gas introduced into the detector to a ratio suitable for the detector. According to this aspect, when the type of gas other than hydrogen gas and oxygen gas is not used as the supplementary gas, all the gas used for analysis is generated by the gas generation unit, and therefore, a gas chromatography system that does not use a gas cylinder can be realized. By adapting the shape of the detector to the flow rate at the time of use of the capillary column, the spread of the peak in the chromatogram can be suppressed, and a supplementary gas can be made unnecessary. Further, since the ratio of the total flow rate of hydrogen gas introduced into the detector to the flow rate of oxygen gas introduced into the detector is controlled so as to be suitable for the detector, it is possible to use a plurality of types of detectors in a gas chromatography system that does not use a gas cylinder.

In the first aspect, the hydrogen sensor may further include an information storage unit that stores information relating to a correlation between a type of the detector and a ratio of flow rates of hydrogen gas and oxygen gas suitable for the type. In this case, the control unit may be configured to: the type of the detector is identified based on information input by a user or information obtained from the detector, a ratio of hydrogen to oxygen suitable for the type of the detector is calculated from the information storage unit, and the calculated ratio of hydrogen to oxygen is used as a ratio suitable for the detector. In this way, even if the user does not set the flow rates of hydrogen and oxygen, the analysis system automatically calculates the hydrogen flow rate and the oxygen flow rate suitable for the detector.

The separation column in the present invention may also be a capillary column.