Hydrogen gas analysis system and hydrogen gas analysis method

Abstract

To provide a hydrogen gas analysis system and a hydrogen gas analysis method, each enabling impurities included in hydrogen gas to be analyzed quickly with simple procedures.SOLUTION: A hydrogen gas analysis system for quantitatively analyzing an analyte component included in hydrogen gas which is a sample, is provided comprising a sample supply device, a pretreatment device, and a mass spectroscope. The sample supply device includes a methane conversion unit that converts non-methane hydrocarbon compounds included in the sample to methane. The pretreatment device includes a first separation unit that separates a part of the analyte component from the sample using a separation column including a stationary phase, and a second separation unit that separates a part of the analyte component from the sample by cooling and heating.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a hydrogen gas analysis system and a hydrogen gas analysis method. [Background technology]

[0002] Hydrogen stations are being developed to realize a hydrogen society. As part of the quality control in the operation of hydrogen stations, impurity analysis of hydrogen gas is carried out. For hydrogen gas fuel intended for fuel cell vehicles, the international standard ISO14687 stipulates standard values ​​for impurities. In response to this situation, analytical devices and methods for analyzing impurities in hydrogen gas fuel are being considered. Patent Document 1 discloses an analytical device that combines a jet separator and a multi-turn time-of-flight mass analyzer, and a method for analyzing oxygen, nitrogen, carbon monoxide, carbon dioxide, methane, ammonia, and hydrogen sulfide in hydrogen gas using the analytical device.

[0003] Patent Document 2 discloses a hydrogen gas analysis kit and a hydrogen gas analysis method capable of analyzing and collecting hydrogen gas at a site such as a hydrogen station. The analysis system disclosed in Patent Document 2 is connected to equipment at the hydrogen station. The analysis system includes branch pipes that branch the hydrogen gas collected at the hydrogen station, and an oxygen concentration meter and a dew point meter, a solid collection sampler, a gas chromatograph, a carbon dioxide concentration measuring device, and a carbon monoxide concentration measuring device that are connected to each of the branch pipes. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2017-181345 A [Patent Document 2] JP 2019-132747 A Summary of the Invention [Problem to be solved by the invention]

[0005] When impurity analysis is performed on hydrogen gas collected at hydrogen stations etc., it is desirable that this analysis be performed quickly and with a simple procedure. Therefore, one of the objects of the present disclosure is to provide a hydrogen gas analysis system and a hydrogen gas analysis method that can analyze impurities contained in hydrogen gas quickly and with a simple procedure. [Means for solving the problem]

[0006] The hydrogen gas analysis system according to the present disclosure is a hydrogen gas analysis system for quantitatively analyzing an analyte component contained in hydrogen gas, which is a sample. The hydrogen gas analysis system includes a sample supplying device that supplies the sample from a sample container containing the sample, a pretreatment device that performs pretreatment on the sample supplied by the sample supplying device, and a mass spectrometer that performs quantitative analysis on the sample that has been pretreated by the pretreatment device. The sample supplying device includes a first pipe connected to the sample container and the pretreatment device, and a methane conversion unit installed in the first pipe for converting non-methane hydrocarbon compounds contained in the sample into methane. The pretreatment device includes a first separation unit that separates a portion of the components to be analyzed from the sample supplied by the sample supplying device using a separation column including a stationary phase, a second separation unit that separates a portion of the components to be analyzed from the sample supplied by the sample supplying device by cooling and heating, a third pipe connected to the first separation unit and the mass spectrometer, a fourth pipe connected to the second separation unit and the mass spectrometer, and a carrier gas supply unit that supplies a carrier gas to the inside of the third pipe and the inside of the fourth pipe.

[0007] The hydrogen gas analysis method according to the present disclosure is a hydrogen gas analysis method for quantitatively analyzing an analyte component contained in hydrogen gas, which is a sample. The hydrogen gas analysis method includes: a sample supplying step of supplying the sample from a sample container containing the sample; a pretreatment step for pretreatment of the sample supplied in the sample supply step; and a mass spectrometry step of performing a quantitative analysis of the sample that has been pretreated in the pretreatment step using a mass spectrometer. The pre-treatment step includes: a first separation step of separating a portion of a target component from the sample supplied in the sample supply step using a separation column including a stationary phase; and a second separation step of separating a portion of the analysis target components from the sample supplied in the sample supply step by cooling and heating. Effect of the Invention

[0008] According to the hydrogen gas analysis system of the present disclosure, the analysis of impurities contained in hydrogen gas can be performed quickly and in a simple procedure. Also, according to the hydrogen gas analysis method of the present disclosure, the analysis of impurities contained in hydrogen gas can be performed quickly and in a simple procedure. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is an explanatory diagram showing the configuration of a hydrogen gas analysis system according to an embodiment of the present disclosure. [Diagram 2] FIG. 2 is an explanatory diagram showing the configuration of a pretreatment device in a hydrogen gas analysis system according to an embodiment of the present disclosure. [Diagram 3] FIG. 3 is an explanatory diagram showing the configuration of a pretreatment device in a hydrogen gas analysis system according to an embodiment of the present disclosure. [Figure 4] FIG. 4 is an explanatory diagram showing the configuration of a pretreatment device in a hydrogen gas analysis system according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] [Outline of the embodiment] First, an overview of the hydrogen gas analysis system and hydrogen gas analysis method according to the present disclosure will be listed and described. The hydrogen gas analysis system according to the present disclosure is a hydrogen gas analysis system for quantitatively analyzing an analyte component contained in hydrogen gas, which is a sample. The hydrogen gas analysis system includes a sample supplying device that supplies the sample from a sample container containing the sample, a pretreatment device that pretreatments the sample supplied by the sample supplying device, and a mass spectrometer that performs quantitative analysis of the sample that has been pretreated by the pretreatment device. The sample supplying device includes a first pipe connected to the sample container and the pretreatment device, and a methane conversion unit installed in the first pipe for converting non-methane hydrocarbon compounds contained in the sample into methane. The pretreatment device includes a first separation unit that separates a portion of the components to be analyzed from the sample supplied by the sample supplying device using a separation column including a stationary phase, a second separation unit that separates a portion of the components to be analyzed from the sample supplied by the sample supplying device by cooling and heating, a third pipe connected to the first separation unit and the mass spectrometer, a fourth pipe connected to the second separation unit and the mass spectrometer, and a carrier gas supply unit that supplies a carrier gas to the inside of the third pipe and the inside of the fourth pipe.

[0011] For hydrogen gas fuel supplied to fuel cell vehicles at hydrogen stations, the international standard ISO14687 specifies standard values ​​for impurities. ISO14687 (Grade-D, Table 2) specifies maximum impurity concentrations for 15 types of substances (called "analyzed components"): water, total hydrocarbons, methane, oxygen, helium, nitrogen, argon, carbon dioxide, carbon monoxide, total sulfur compounds, formaldehyde, formic acid, ammonia, halogen compounds, and maximum particulate concentration. When operating a hydrogen station, it is desirable to be able to analyze these impurities in a quick and simple manner.

[0012] Several proposals have already been made regarding analytical systems and analytical methods for hydrogen gas as a sample collected at a hydrogen station (for example, Patent Documents 1 and 2). However, there is a continuing need for an analytical system that can collectively quantify a larger number of components to be analyzed in a shorter time. Under these circumstances, a system for analyzing components to be analyzed contained in hydrogen gas has been considered. Then, it was decided to use a mass spectrometer (MS) as an apparatus for performing quantitative analysis, and further, a pretreatment device for separating the components to be analyzed contained in the sample hydrogen gas as a pre-stage before introducing the measurement sample into the mass spectrometer was repeatedly considered. Then, a separation section in the pretreatment device was found to include two parts: a first separation section that separates a part of the components to be analyzed from the sample hydrogen gas using a separation column including a stationary phase, and a second separation section that separates a part of the components to be analyzed from the sample hydrogen gas by cooling and heating. Furthermore, an analytical system according to the present disclosure was configured as one that includes pipes that connect the first separation section to the mass spectrometer and the second separation section to the mass spectrometer, respectively. The sample supplying device is also equipped with a methane conversion section that converts non-methane hydrocarbon compounds into methane.

[0013] According to this system, by combining a methane conversion section, column separation, and separation by cooling and heating, it is possible to collectively quantify at least 13 components among the components to be analyzed using a single system. According to the system of the present disclosure, the time required for quantifying the 13 components is reduced to 1 / 3 or less compared to the case where a conventional hydrogen analysis system is used. In addition, since the 13 components are measured using a single system, the man-hours required for measurement can be significantly reduced.

[0014] In the hydrogen gas analysis system, the mass spectrometer may be a time-of-flight mass spectrometer (TOFMS). By combining the above-mentioned pretreatment device with the TOFMS, there is an advantage in that it is possible to accurately separate and quantify impurity molecules having approximately the same mass number.

[0015] In the hydrogen gas analysis system, the first separation unit may include a gas chromatography device and separate oxygen, nitrogen, argon, methane, and carbon monoxide from the sample. With this configuration, at least five components among the components to be analyzed can be separated by gas chromatography and then transferred to a mass spectrometer.

[0016] In the hydrogen gas analysis system, the second separation unit may include a collection tube, a cooling unit for cooling the collection tube, and a heating unit for heating the collection tube. The pretreatment device may control the cooling unit so that the collection tube is cooled to a predetermined temperature, and then control the heating unit so that the collection tube is heated in stages. With this configuration, the impurity components contained in the hydrogen gas can be solidified and collected by using the cooled collection tube as a cold trap. Next, the collection tube is heated, and the impurity components are separated by utilizing the difference in vaporization temperature of the collected impurity components, and then the impurity components can be introduced into a mass spectrometer.

[0017] In the hydrogen gas analysis system, the second separation section may separate formic acid, formaldehyde, ammonia, total sulfur compounds, and halogen compounds from the sample. According to this configuration, at least six components of the components to be analyzed, which are different from the five components separated in the first separation section, can be separated in the second separation section. By using the first separation section and the second separation section in combination, many of the components to be analyzed can be separated and transferred to a mass spectrometer.

[0018] In the hydrogen gas analysis system, the pretreatment device may include a first switching unit that is switchable so as to supply the sample supplied by the sample supply device to either the first separation unit or the second separation unit. With this configuration, the first separation unit and the second separation unit can be alternatively selected for use, and impurity analysis can be performed efficiently and reliably.

[0019] In the hydrogen gas analysis system, the sample supplying device may further include a second pipe that is installed separately from the third pipe and the fourth pipe and is connected to the sample container and the mass spectrometer, and the mass spectrometer may further perform a quantitative analysis of helium in the sample supplied by the sample supplying device through the second pipe. With this configuration, even if helium is used as a carrier gas in the analysis of other components, the helium content concentration in the sample, hydrogen gas, can be accurately measured without contamination with the helium carrier gas. In addition, by having a pipe for measuring the helium content in the system, it becomes possible to measure helium in addition to the above-mentioned analysis target components in one system, and impurity analysis can be performed more quickly and in a simple manner.

[0020] The hydrogen gas analysis system may further include a first standard gas supply device that supplies a standard gas from a first standard gas container containing the standard gas, and the mass spectrometer may obtain a calibration curve using the standard gas supplied from the first standard gas supply device. With this configuration, it is possible to accurately quantify each analyte component based on the calibration curve obtained in the same device as the device in which the sample to be analyzed is measured.

[0021] The first standard gas supply device may include a dilution gas inlet for introducing a dilution gas, which is hydrogen gas other than the sample, a fifth pipe connected to the first standard gas container and the mass spectrometer, a dilution container connected to the fifth pipe and filled with the standard gas and the dilution gas, a sixth pipe connected to the dilution gas inlet and the dilution container, a pressure measuring unit for measuring the pressure inside the dilution container, an exhaust pipe connected to the sixth pipe for discharging the gas filled inside the dilution container to the outside of the first standard gas supply device, a standard gas valve installed on the fifth pipe for switching the fifth pipe between a closed state (blocked) and an open state (opened), a dilution gas valve installed on the sixth pipe for switching the sixth pipe between a closed state (blocked) and an open state (opened), and an exhaust valve installed on the exhaust pipe for switching the exhaust pipe between a closed state (blocked) and an open state (opened). According to this configuration, so-called pressure dilution can be performed on the standard gas, and a calibration curve is created using a diluted standard gas obtained by accurately diluting the standard gas. This makes it possible to stably and accurately quantify each analyte component in a sample using an accurate calibration curve.

[0022] The first standard gas supply device can execute a standard gas filling control for controlling the standard gas valve so that the standard gas is filled into the dilution container until the pressure inside the dilution container measured by the pressure measuring unit reaches a predetermined first value, a release control for controlling the exhaust valve so that the gas filled in the dilution container is released until the pressure inside the dilution container measured by the pressure measuring unit reaches a predetermined second value, and a dilution gas filling control for controlling the dilution gas valve so that the dilution gas is filled into the dilution container until the pressure inside the dilution container measured by the pressure measuring unit reaches a predetermined third value. The first standard gas supply device may be configured to dilute the standard gas using the dilution gas by sequentially executing the standard gas filling control and the release control, and then repeatedly executing the dilution gas filling control and the release control. According to this configuration, a calibration curve is created using a diluted standard gas obtained by accurately diluting the standard gas using pressure dilution. Therefore, the quantitative determination of each analysis target component can be performed stably and accurately. These controls may be performed automatically by a control device or manually.

[0023] The hydrogen gas analysis method according to the present disclosure is a hydrogen gas analysis method for quantitatively analyzing an analyte component contained in a sample, which is hydrogen gas. The hydrogen gas analysis method includes a sample supplying step of supplying the sample from a sample container in which the sample is accommodated, a pretreatment step of pretreatment of the sample supplied in the sample supplying step, and a mass analysis step of quantitatively analyzing the sample pretreated in the pretreatment step using a mass spectrometer. The pretreatment step includes a first separation step of separating a part of the analyte component from the sample supplied in the sample supplying step using a separation column including a stationary phase, and a second separation step of separating a part of the analyte component from the sample supplied in the sample supplying step by cooling and heating. According to this method, a plurality of analyte components can be separated by combining separation using a separation column and separation by cooling and heating, and can be introduced into a mass spectrometer for quantitative analysis. According to the method according to the present disclosure, the time required for quantitative analysis of impurities is reduced to 1 / 3 or less compared to conventional hydrogen gas analysis methods.

[0024] In the hydrogen gas analysis method, the sample supply step may include a methane conversion step of introducing the hydrogen gas sample into a methane conversion section to convert non-methane hydrocarbons into methane. According to this method, by combining methane conversion for converting non-methane hydrocarbons into methane, separation using a separation column, and separation by cooling and heating, the quantitative determination of 13 components, excluding moisture and maximum particulate concentration, among the components to be analyzed can be performed collectively through a series of steps.

[0025] In the hydrogen gas analysis method, the first separation step and the second separation step may be alternatively performed. With this configuration, different analysis target components are separated by the first separation step and the second separation step, and the respective components can be quantitatively determined in sequence. This allows the analysis of impurities in hydrogen gas to be performed quickly and simply.

[0026] The hydrogen gas analysis method may further include a dilution step of diluting, with a dilution gas, a standard gas used to obtain a calibration curve in the mass spectrometer. The dilution step may include a standard gas filling step of filling the dilution container with the standard gas until the pressure inside the dilution container reaches a predetermined first value, a discharging step of discharging the gas filled inside the dilution container until the pressure inside the dilution container reaches a predetermined second value, and a dilution gas filling step of filling the dilution container with the dilution gas until the pressure inside the dilution container reaches a predetermined third value. After the standard gas filling step and the discharging step are performed in order, the dilution gas filling step and the discharging step may be repeatedly performed. According to this configuration, a calibration curve is created using a diluted standard gas obtained by accurately diluting a standard gas using pressure dilution. Therefore, the quantitative determination of each analyte component can be performed stably and accurately.

[0027] In the hydrogen gas analysis method, the mass analysis step may include a first mass analysis step of analyzing the analyte components separated in the first separation step, a second mass analysis step of analyzing the analyte components separated in the second separation step, and a third mass analysis step of performing a quantitative analysis of helium on the sample that has not been subjected to the first and second separation steps. According to this configuration, the quantitative analysis of helium is performed without the first and second separation steps. Therefore, even if helium is used as a carrier gas in the first and second separation steps, the helium content in the sample, hydrogen gas, can be accurately measured without contamination with the carrier gas, helium.

[0028] In the mass analysis step, the first mass analysis step quantifies the components to be analyzed, including oxygen, nitrogen, argon, methane, carbon monoxide, and total hydrocarbons (THC); The second mass analysis step can quantify the components to be analyzed, including formic acid, formaldehyde, ammonia, halogen compounds, and total sulfur compounds, and the third mass analysis step can quantify helium. Carbon dioxide can be quantified either in the first mass analysis step or in the second mass analysis step. By grouping the components to be analyzed and quantifying them in this way, impurity analysis in hydrogen gas can be performed efficiently and accurately.

[0029] [Specific example of embodiment] Next, an example of a specific embodiment of the hydrogen gas analysis system and hydrogen gas analysis method according to the present disclosure will be described with reference to the drawings. In the following drawings, the same or corresponding parts are given the same reference characters, and the description thereof will not be repeated.

[0030] (Hydrogen gas analysis system) FIG. 1 is an explanatory diagram showing the configuration of a hydrogen gas analysis system 1 according to an embodiment of the present disclosure. The hydrogen gas analysis system 1 is a hydrogen gas analysis system for performing quantitative analysis of an analysis target component contained in hydrogen gas, which is a sample. Referring to FIG. 1, hydrogen gas, which is a sample, is collected at a hydrogen station, a hydrogen shipping facility, or the like, and is stored in a canister G0, which serves as a sample container. The hydrogen gas analysis system 1 includes a sample supplying device 10, a pretreatment device 60, and a mass spectrometer 100.

[0031] A canister G0 for storing hydrogen gas as a sample, a container G2 for storing hydrogen gas for dilution, a container G3 for storing a standard gas, a container G4 for storing helium gas as a carrier gas for mass spectrometry, a container G5 for storing nitrogen gas as a cooling / instrumentation gas, and a container G6 for storing a gas for quality control are connected to the hydrogen gas analysis system 1. Note that a canister G1, which is a dilution container for diluting the standard gas, may be connected instead of the canister G0.

[0032] (Sample supply device) The sample supplying device 10 will be described. The sample supplying device 10 is a device that supplies hydrogen gas, which is a sample contained in a canister G0, to a pretreatment device 60. The canister G0 and the pretreatment device 60 are connected via a pipe 41 as a first pipe. Hydrogen gas extracted from the canister G0 is transferred to the pretreatment device 60 via the pipe 41. The pipe 41 is provided with a pressure reducing valve 12. The hydrogen gas extracted from the canister G0 is adjusted to a constant pressure (for example, 0.05 MPa) by the pressure reducing valve 12 and sent to the pretreatment device 60. A pressure gauge 32 is provided downstream of the pressure reducing valve 12. The pressure at the outlet side of the pressure reducing valve 12 is confirmed by the pressure gauge 32. A pipe 42 branches off from the pipe 41. The pipe 42 is connected to the mass spectrometer 100 without passing through the pretreatment device 60. The pipe 42 is a pipe used when performing a quantitative analysis of helium in hydrogen gas, which is a sample. A mass flow controller (MFC) 94 is provided in the pipe 42 .

[0033] The sample supplying device 10 includes a methanizer 11 as a methane conversion section. The methanizer 11 is installed in a pipe 41. Specifically, the pipe 41 has branch pipes 47, 48 in which the methanizer 11 is disposed. A valve 26 is provided in the branch pipe 47, and a valve 27 is provided in the branch pipe 48. A valve 25 is provided between the branched portion of the branch pipe 47 and the branched portion of the branch pipe 48 in the pipe 41. This configuration makes it possible to switch between a state in which hydrogen gas extracted from the canister G0 is transferred to the pretreatment device 60 without passing through the methanizer 11, and a state in which hydrogen gas is transferred to the pretreatment device 60 via the methanizer 11.

[0034] The methanizer 11 is used to measure total hydrocarbons (THC) contained in hydrogen gas as a sample. When measuring THC, the hydrogen gas as a sample is passed through the methanizer 11 to convert the hydrocarbons contained in the hydrogen gas into methane. A methanation furnace having a catalyst cylinder filled with Ni catalyst can be used as the methanizer 11. For example, a methanation furnace generally used in gas chromatography analysis can be used. As an example of reaction conditions in the methanizer 11, the catalyst cylinder can be heated to 350°C to 500°C (preferably 400 to 450°C) to react non-methane hydrocarbons contained as impurities in the hydrogen gas with the hydrogen gas to convert it into methane.

[0035] (Standard gas supply device) The hydrogen gas analysis system 1 includes a standard gas supply device 90. In the hydrogen gas analysis system 1, a standard gas serving as a standard for the component to be analyzed is diluted as necessary and then supplied from the sample supply device 10 to the mass spectrometer 100. The diluted standard gas is mainly used to obtain a calibration curve. The standard gas supply device 90 is partially overlapped with the sample supply device 10. The standard gas supply device 90 includes a pipe 45 as a fifth pipe that is connected to a container G3 that contains a standard gas at a standard gas inlet 93. A standard gas can be prepared for each component to be analyzed. For example, 13 types of standard gas are prepared. The pipe 45 includes a pressure reducing valve 29. A canister G1 serving as a dilution container is connected to the pipe 45. The standard gas supplied from the container G3 is controlled to a constant pressure (for example, 0.27 MPa) by the pressure reducing valve 29 and supplied to the canister G1. The piping 45 is provided with a valve 22 as a standard gas valve that switches the piping 45 between a closed state where it is blocked and an open state where it is opened.

[0036] The standard gas supplying device 90 also includes a pipe 46 as a sixth pipe that connects a container G2 that contains a dilution gas (for example, ultra-high purity hydrogen gas that does not contain the component to be analyzed and is 7N or more) for diluting the standard gas and a canister G1. The standard gas supplying device 90 is connected to the container G2 that contains the dilution gas at a dilution gas inlet 92. As the canister G1, for example, two canister containers (for example, with an internal volume of 6 L and a pressure resistance of 0.27 MPa) used for measuring VOCs in the atmosphere can be connected. The canister G1 is preferably one that has an inner surface with low adsorptivity, and it is preferable to use a canister with an inner surface that has been treated with sulfinate. The canister G1 can be filled with the standard gas and the dilution gas. The standard gas can be accurately diluted by pressure dilution using the canister G1. The pipe 46 is provided with a valve 21 as a dilution gas valve that switches the pipe 46 between a closed state in which it is blocked and an open state in which it is opened.

[0037] The standard gas supply device 90 includes a pressure gauge 31. The pressure gauge 31 is a pressure gauge portion that measures the pressure inside the canister G1. It is preferable to use a high-precision pressure gauge that can read to the unit of 0.0001 MPa as the pressure gauge 31 in order to improve the accuracy of dilution.

[0038] The standard gas supply device 90 is provided with an exhaust pipe 49 that is connected to the piping 46 and that exhausts the gas filled inside the canister G1 as a dilution container to the outside of the standard gas supply device 90. The exhaust pipe 49 is provided with a valve 30 that serves as an exhaust valve that switches the exhaust pipe 49 between a closed state in which it is blocked and an open state in which it is opened.

[0039] The standard gas supply device 90 further includes a pipe 50 connected to the canister G1 and equipped with a vacuum pump 13. The canister G1 can be vacuum-cleaned by operating the vacuum pump 13 to exhaust gas from within the canister G1. It is preferable to use a dry vacuum pump as the vacuum pump 13 in order to prevent oil contamination caused by the oil in the vacuum pump diffusing into the pipe. The pipe 50 includes a valve 28 as a switching valve for switching the pipe 50 between a closed state in which the pipe 50 is blocked and an open state in which the pipe 50 is opened.

[0040] The dilution of the standard gas in the standard gas supplying device 90 will be described. The dilution of the standard gas in the standard gas supplying device 90 is carried out in the following procedure. First, in step 0, the inside of the canister G1 is evacuated using the vacuum pump 13. Next, in step 1, the standard gas is filled from the container G3 that stores the standard gas into the canister G1 until the pressure inside the canister G1 reaches a predetermined first value (for example, 0.27 MPaG). At this time, the pressure is measured by the pressure gauge 31, and the pressure is precisely controlled. The filling of the standard gas can be carried out by controlling the pressure reducing valve 29 and the valves 22, 23, and 24.

[0041] Next, as a second step, after a certain time has elapsed, the valve 30 serving as a discharge valve is operated to discharge gas from the canister G1 through the discharge pipe 49 until the pressure inside the canister G1 reaches a predetermined second value (for example, atmospheric pressure).

[0042] Next, in a third step, the dilution gas is filled into the canister G1 from the container G2 that contains hydrogen gas as the dilution gas until the pressure inside the canister G1 reaches a third predetermined value (for example, 0.27 MPaG). The pressure is detected by the pressure gauge 31, and the pressure inside the canister G1 is precisely controlled to a predetermined value. The filling of the dilution gas can be performed by controlling the valves 21, 23, and 24.

[0043] After carrying out the first and second steps, the second and third steps are repeated to dilute the standard gas step by step. The number of dilutions can be selected arbitrarily, but by carrying out 3 to 7 dilution steps, a standard gas with a concentration corresponding to each step can be obtained. A calibration curve can be created using the standard gas thus obtained. The calibration curve will be described later.

[0044] (Pretreatment device) The pretreatment device 60 will now be described. With reference to Fig. 1, the pretreatment device 60 is connected to the sample supplying device 10 via piping 41. The pretreatment device 60 is a device that performs pretreatment on the sample supplied by the sample supplying device 10. Connected to the pretreatment device 60 are a container G4 that contains helium gas, which is a carrier gas for mass spectrometry, a container G5 that contains nitrogen gas, which is a cooling / instrumentation gas, and a container G6 that contains a gas for quality control. The pretreatment device 60 includes a first separation section 61 and a second separation section 62. The first separation section 61 is connected to the mass spectrometer 100 via a pipe 43 serving as a third pipe. The second separation section 62 is connected to the mass spectrometer 100 via a pipe 44 serving as a fourth pipe.

[0045] FIG. 2 is an explanatory diagram showing the configuration of the pretreatment device 60 in more detail. The pretreatment device 60 will be described with reference to FIG. 2. With reference to FIG. 2, the pretreatment device 60 includes a first separation section 61 that separates a part of the analysis target components from the sample supplied by the sample supply device 10 using a separation column 65 including a stationary phase, and a second separation section 62 that separates a part of the analysis target components from the sample supplied by the sample supply device 10 by cooling and heating. The first separation section 61 is mainly composed of a gas chromatography device, and the gas chromatography device is equipped with the above-mentioned separation column 65. The second separation section 62 is mainly composed of a cold trap device, and the collection tube of the cold trap device is cooled by liquefied nitrogen and heated by a heater 84.

[0046] The pretreatment device 60 includes switching valves 71, 72, and 74, which are six-way valves that can be selectively switched between a first connection state and a second connection state, and a switching valve 73, which is a ten-way valve that can be selectively switched between a first connection state and a second connection state. By controlling each of the switching valves 71, 72, and 73 to be in a predetermined connection state, it is possible to selectively switch between a state in which the sample supplied from the sample supplying device 10 is supplied to the first separation section 61 and a state in which the sample supplied from the sample supplying device 10 is supplied to the second separation section 62. The first switching section 70, which includes the first switching section that can be switched to supply the sample supplied from the sample supplying device 10 to either the first separation section 61 or the second separation section 62, is composed of the switching valves 71, 72, and 73.

[0047] 2 shows a state in which the switching valve 71 is in the first connection state, the switching valve 72 is in the first connection state, the switching valve 73 is in the first connection state, and the switching valve 74 is in the first connection state. In this state, the sample supplied from the sample supplying device 10 is introduced into the switching valve 72 via the sample loop 81, and then introduced from the switching valve 72 into the second separation section 62. The second separation section includes a collection tube 82, a cooling section 83 that cools the inside of the collection tube 82, and a heater 84 that is a heating section that heats the inside of the collection tube 82. The cooling section 83 receives liquid nitrogen LN from a container G5 that stores nitrogen gas. 2 Nitrogen gas cooled by the cold nitrogen gas is introduced into the trap tube 82. The cold nitrogen gas cools the trap tube 82 to -180°C. When a sample is introduced into the trap tube 82 while the trap tube 82 is cooled, the high boiling point components in the sample, such as sulfur compounds, formic acid, formaldehyde, ammonia, halogen compounds, and carbon dioxide, are solidified and collected. Since the boiling point of hydrogen gas is -252°C, it is not collected by the trap tube 82 and is discharged to the outside via the discharge pipe 52.

[0048] 3 shows a state where the switching valve 71 is in the first connection state, the switching valve 72 is in the second connection state, the switching valve 73 is in the second connection state, and the switching valve 74 is in the first connection state. In this state, the sample supplied from the sample supplying device 10 is introduced into the switching valve 72 through the sample loop 81, and then discharged to the outside from the switching valve 72 through the discharge pipe 52. Meanwhile, helium gas supplied from a container G4 that contains helium gas, which is a carrier gas for mass spectrometry, is introduced into the switching valve 72 through the switching valve 71 and reaches the collection tube 82. The collection tube 82 is heated at a constant rate by the heater 84. The analysis target components (sulfur compounds, formic acid, formaldehyde, ammonia, halogen compounds, carbon dioxide, etc.) collected in the collection tube 82 are vaporized according to their respective boiling points and transferred to the switching valve 73 through the switching valve 72 together with the helium gas. Helium gas containing the components to be analyzed is introduced into the mass spectrometer 100 via a switching valve 73 and a switching valve 74 .

[0049] FIG. 4 shows a state where the switching valve 71 is in the second connection state, the switching valve 72 is in the first connection state, the switching valve 73 is in the first connection state, and the switching valve 74 is in the first connection state. In this state, the sample supplied from the sample supplying device 10 passes through the switching valves 71 and 72 and is discharged to the outside through the discharge pipe 49. Meanwhile, the sample contained in the sample loop 81 is introduced into the first separation section 61 through the switching valves 72 and 73 together with the helium gas supplied from the container G4. The first separation section 61 includes a gas chromatography device equipped with a PLOT column (separation column 65) on which the molecular sieve 5A is fixed, for example. The column temperature is maintained at a constant temperature (for example, 80° C.), and oxygen, nitrogen, argon, methane, and carbon monoxide can be separated from the components to be analyzed in the first separation section 61. Carbon dioxide can also be separated in addition to the above-mentioned components by selecting the column. The first separation section 61 is connected to the mass spectrometer 100 via a switching valve 73 and a switching valve 74 , and the components to be analyzed separated in the first separation section 61 are introduced into the mass spectrometer 100 .

[0050] (Mass spectrometer) The mass spectrometer 100 includes a mass spectrometer 101. Examples of the mass spectrometer include a time-of-flight mass spectrometer, a quadrupole mass spectrometer, and a magnetic deflection mass spectrometer, but a time-of-flight mass spectrometer is preferable. More specifically, the mass spectrometer 101 is a multi-turn time-of-flight mass spectrometer, and among them, a high-resolution multi-turn time-of-flight mass spectrometer (for example, infiTOF-UHV, manufactured by Kanomax Analytical Co., Ltd.) can be used. Such a mass spectrometer is well known and is a device including an ion source, an entrance electrode, an orbit, four orbit electrodes, an ion gate, an exit electrode, and a detector.

[0051] The mass spectrometer 101 includes a first input port 102 and a second input port 103. A pipe 43 connected to the first separation section 61 and a pipe 44 connected to the second separation section 62 are connected to the first input port 102. That is, the sample supplied from the sample supply device 10 and passed through the first separation section 61 or the second separation section 62 is introduced into the mass spectrometer 101 from the first input port 102. A pipe 42 is connected to the second input port 103. The pipe 42 introduces the sample supplied from the sample supply device 10 into the mass spectrometer 101 without passing through the pretreatment device 60. The sample introduced from the second input port 103 is used to quantify helium in hydrogen gas. An MFC 94 is installed in the pipe 42 leading from the sample supply device 10 to the second input port 103. The amount of the sample introduced into the mass spectrometer 101 is strictly controlled by the MFC 94.

[0052] (Hydrogen gas analysis method) Although the apparatus or system for carrying out the hydrogen gas analysis method according to the present disclosure is not particularly limited, the method is preferably carried out in the above-mentioned hydrogen gas analysis system. A method for carrying out hydrogen gas analysis in the above-mentioned hydrogen gas analysis system will be described below.

[0053] The hydrogen gas analysis method according to the present disclosure includes a sample supply step of supplying a sample from a sample container containing the sample, a pretreatment step of performing pretreatment on the sample supplied in the sample supply step, and a mass analysis step of performing quantitative analysis of the sample pretreated in the pretreatment step using a mass spectrometer.

[0054] The hydrogen gas analysis method according to the present disclosure quantifies 13 components of the analysis target components contained in hydrogen gas: oxygen, nitrogen, argon, methane, carbon monoxide, carbon dioxide, total hydrocarbons, formic acid, formaldehyde, ammonia, halogen compounds, total sulfur compounds, and helium. Water can also be measured.

[0055] In the hydrogen gas analysis method according to the present disclosure, the above-mentioned 13 components or 14 components including water are divided into six groups for analysis. The groups are as follows. Note that water may be measured by the hydrogen gas analysis method according to the present disclosure, or may be analyzed by a method other than the hydrogen gas analysis method according to the present disclosure. Group 1: Oxygen, Nitrogen, Argon, Methane, Carbon Monoxide Group 2: Carbon dioxide, water Group 3: Total Hydrocarbons Group 4: Formaldehyde, formic acid, ammonia, halogen compounds Group 5: Total Sulfur Compounds Group 6: Helium

[0056] According to the above-mentioned hydrogen gas analysis system, it is possible to continuously and collectively carry out the quantitative analysis of the analysis target components belonging to groups 1 to 6. The outline of each of the analysis methods for groups 1 to 6 is as follows. First group: After separation in the first separation section (gas chromatography), mass spectrometry is performed. Second group: After collection and separation in the second separation section (cold trap device), mass spectrometry is performed. Third group: Non-methane hydrocarbon compounds are methanized in a methanizer, then separated in the first separation section (gas chromatography), and then subjected to mass spectrometry. Fourth group: After collection and separation in the second separation section (cold trap device), mass spectrometry is performed. Fifth group: After collection and separation in the second separation section (cold trap device), mass spectrometry is performed. Group 6: No pretreatment is performed and mass spectrometry is performed. Depending on the type of column used in the first separation section, carbon dioxide can also be included in the first group and quantified.

[0057] As described above, the hydrogen gas analysis method according to the present disclosure includes, as a pretreatment for mass spectrometry, a first separation step in which a portion of the components to be analyzed is separated using gas chromatography, and a second separation step in which a portion of the components to be analyzed is separated by cooling and heating using a cold trap device.

[0058] The measurement methods for each group will be described in detail below. (Group 1: oxygen, nitrogen, argon, methane, carbon monoxide) Measurement of target components The sample supplied from the sample supply device is introduced into the first separation section (gas chromatography device), where each component is separated by gas chromatography. The separated components are introduced into a mass spectrometer for quantitative analysis. In the mass spectrometer, oxygen (O 2 ) is m / z = 32, argon (Ar) is m / z = 40, carbon monoxide (CO) and nitrogen (N 2 ) at m / z = 28, methane (CH 4 ) uses m / z = 15. Oxygen and argon have the same retention time RT, so they are separated by mass number. Carbon monoxide and nitrogen have almost the same mass number, so they are separated by the difference in RT. Carbon monoxide and nitrogen can be separated using exact mass, but the measurement sensitivity decreases as the flight distance increases. For this reason, separation at RT is preferred. For methane, CH3 and C.H. 4 However, m / z=16 requires accurate mass separation from O ions, so the CH 3 Quantitative analysis was performed using m / z=15.

[0059] Calibration curve For each component, a calibration curve is created in the range of 0 to 10 ppm. If the impurity concentration in the sample to be measured exceeds 10 ppm, the sample is diluted by the pressure dilution method using a canister, and the impurity concentration in the sample to be measured is adjusted to be within the calibration curve range before quantitative analysis is performed. After quantitative analysis, the impurity content in the sample to be measured is calculated by dividing by the dilution ratio.

[0060] (Group 2: Carbon dioxide, water) Here, a case where carbon dioxide and water are measured as the second group will be described. Pretreatment and quantitative analysis Pretreatment The sample supplied from the sample supply device is introduced into the second separation section (cold trap device), and the components separated by solidification and collection using the cold trap and temperature-programmed desorption are introduced into a mass spectrometer for quantification. More specifically, low-temperature concentration is performed using liquid nitrogen at -180°C for 15 seconds, and then the temperature is raised at a constant rate (3°C / sec) to 200°C for desorption. The desorbed gas is introduced into the mass spectrometer for quantitative analysis. Carbon dioxide has a relatively high lower limit of quantification at 2 ppm, so concentration can be performed in a short time of 15 seconds. Quantitative analysis of carbon dioxide and water For water, m / z=18 or H 2 Quantitative analysis is performed using the mass number of OH ions, which are fragment ions of O, which is 17. Quantitative analysis is performed for carbon dioxide using m / z = 44. 2 In the vicinity of mass number 44, there is propane C 3 H 8 and nitric oxide N 2 Because O and other compounds are present, precise mass separation is performed to prevent interference from other components.

[0061] (Group 3; total hydrocarbons) The ISO standard does not specify specific components for total hydrocarbons (THC), and all hydrocarbons are the target, but it is practically impossible to individually identify and quantify all of the countless target components. Therefore, the sample hydrogen gas is passed through a methanizer (Ni catalytic furnace) to convert all non-methane hydrocarbons into methane, and the methane is separated by gas chromatography and quantified by a mass spectrometer. In the method disclosed herein, the sample hydrogen gas is directly (i.e., without pretreatment) introduced into the Ni catalytic furnace and methanated to quantify all hydrocarbons.

[0062] (Group 4: formaldehyde, formic acid, ammonia, halogen compounds) Pretreatment and quantitative analysis Pretreatment The sample supplied from the sample supply device is introduced into the second separation section (cold trap device), and the components separated by solidification and collection by the cold trap and temperature-elevated desorption are introduced into a mass spectrometer for quantitative analysis. More specifically, low-temperature concentration is performed for 600 seconds at -180°C using liquid nitrogen, and then the temperature is raised to 200°C at a constant rate (3°C / sec) for desorption. The desorbed gas is introduced into a mass spectrometer for quantitative analysis. In the method disclosed herein, a cold trap is used to perform a separation operation in which the temperature is raised relatively slowly at a constant rate (3°C / sec) without column separation, thereby making use of the boiling point difference between the components to make a difference in the outflow time. The concentration of impurities can be increased by extending the collection time (low-temperature concentration time) in the cold trap. By highly concentrating impurities, it is possible to appropriately and easily measure their concentration even when the impurities in the sample are at an extremely low concentration.

[0063] Quantitative analysis of formic acid and formaldehyde Formic acid and formaldehyde have mass numbers of 46 and 30, respectively, but fragmentation occurs due to the energy added during ionization, resulting in a common ion, CHO ion (mass number 29). The peak intensities of 46 and 30 are smaller than that of 29. Furthermore, the boiling points of formic acid are 100.8°C, and those of formaldehyde are -19.3°C. Due to these characteristics, the mass numbers used for quantification are both set to 29, and separation and quantification are performed using the difference in effluent time due to the difference in boiling points. By adjusting the heating rate in the cold trap and clarifying the difference in effluent time, separation and quantification can be performed using a combination of a cold trap and a mass spectrometer.

[0064] Quantitative analysis of ammonia Ammonia has a mass number of 17, but H 2 Since OH ions, which are fragment ions of O, also have the same mass number of 17, interference occurs and quantification is not possible with a normal mass spectrometer. In this regard, the hydrogen gas analysis method according to the present disclosure uses TOFMS for accurate mass separation, making it possible to separate and quantify the ions by utilizing the mass difference between ammonia (17.026) and OH ions (17.003).

[0065] Quantitative analysis of halogen compounds Halogen compounds are defined as inorganic salt compounds such as HCl and organic halogens. There are countless organic halogens and inorganic salt compounds, and although quantification is possible if the components are identified, it is impossible to quantify each one individually. Therefore, quantitative analysis is performed only for HCl. HCl has a mass number of 36, but to prevent interference with other components, quantification is performed using the exact mass of HCl, m / z = 35.9767.

[0066] -Creating a calibration curve The standard values ​​for formic acid, formaldehyde, ammonia, and halogen compounds specified by ISO are very low concentrations of 0.2 ppm, 0.2 ppm, 0.1 ppm, and 0.05 ppm, respectively. In addition, these components are highly adsorbent and reactive, making them difficult to measure. Furthermore, standard gases with such concentrations are not commercially available, and standard gases of about 50 ppm to 200 ppm must be diluted before use. The dilution method includes a flow ratio mixing method, a nozzle type mixing method, a pressure dilution method, etc., but in the method according to the present disclosure, it is preferable to use the pressure dilution method. The pressure dilution method is performed using a canister and a precision pressure gauge provided in the hydrogen gas analysis system. Let's take the dilution of ammonia standard gas as an example. First, N 2 A standard gas containing 100 ppm ammonia and 100 ppm ammonium nitrate is charged into a 6 L canister that has been evacuated to a vacuum at a pressure of 0.27 MPaG. After a certain time has passed, the gas in the canister is released to atmospheric pressure, and then the canister is pressurized to 0.27 MPaG with hydrogen gas. After a certain time has passed, the gas is released again to atmospheric pressure. This operation is repeated five times to obtain the H 2 Using the gas as the balance gas, diluted standard gas containing 2 ppm ammonia can be obtained. Dilution operations are performed 3 to 7 times to obtain diluted standard gas of each concentration. Using these diluted standard gases, a calibration curve for ammonia is created. It has been confirmed that sufficient linearity can be obtained within the required concentration range.

[0067] The components measured in the fourth group (formaldehyde, formic acid, ammonia, and halogen compounds) are highly polar and are easily adsorbed to metal piping, etc. However, all piping, valves, pressure reducing valves, etc. through which the sample gas passes must be free of SiO 2 It has been confirmed that the quantitative determination can be carried out without any problems by using materials that have been inactivated by coating. To further suppress adsorption, all parts through which the gas passes, such as pipes, are heated to 80°C before the measurement.

[0068] (Group 5: All sulfur compounds) Pretreatment method As in the pretreatment for the fourth group, the sample supplied from the sample supply device is introduced into the second separation section (cold trap device), and the components separated by solidification and collection in the cold trap and thermal desorption are introduced into the mass spectrometer for quantification. This concentration operation makes it possible to measure the required lower limit of quantification of 0.004 ppm. Quantitative analysis methods Total sulfur compounds include numerous compounds, but in the method of the present disclosure, H 2 S., C.O.S., C.H. 3 S.H., C.S. 2 These sulfur compounds are highly polar and easily adsorbed to metal piping, but all piping, valves, pressure reducing valves, etc. through which the sample gas passes are free of SiO 2 It has been confirmed that quantification can be performed without problems by using materials that have been inactivated by coating. To measure each component, accurate mass separation of each component is performed, and the measurement is performed under conditions that are not affected by interference from other compounds.

[0069] Although the fourth and fifth groups are measured separately to obtain the required measurement sensitivity, they may be measured simultaneously depending on the sensitivity of the device and the required measurement accuracy. By measuring the fourth and fifth groups simultaneously, the measurement time can be further reduced.

[0070] (Group 6: Helium) Pretreatment method In the quantitative analysis of helium, no pretreatment is performed, and hydrogen gas as a sample is introduced directly into the sample analyzer via a line separate from other measurement systems. By using a line separate from other measurement systems, contamination with helium gas, which is the carrier gas used in the measurement of other components, can be avoided.

[0071] ·Quantitative analysis method When hydrogen gas is introduced into a mass spectrometer, a large amount of hydrogen is ionized in the ionization chamber, which can reduce the sensitivity of other components to about 1 / 100. On the other hand, the standard value for helium in hydrogen gas specified by ISO is relatively high at 300 ppm. Therefore, the hydrogen gas analysis method according to the present disclosure can obtain the required sensitivity even if the hydrogen gas is ionized. Helium has a mass number of 4, but deuterium (D 2 ) interference, which can affect quantification in a typical mass spectrometer. Therefore, by using a high-resolution mass spectrometer (e.g., TOFMS), 2 With this method, the lower limit of helium determination is 30 ppm.

[0072] (Experimental Example) Hydrogen gas samples collected at hydrogen stations were analyzed using the hydrogen gas analysis system whose configuration is shown in Figures 1 to 4. The specific devices used to configure the system are as follows: Sample container (canister): 6L capacity, pressure resistance 0.27MPa, canister with sulfinate-treated inner surface (ENTECH INSTRUMENTS, 6L Can w / TrueSealValve, model number: EN29-10622) Mass flow controller: HORIBA STEC Co., Ltd., SEC series mass flow controller Methanizer: Shimadzu Corporation's Methanizer MTN-1 Gas chromatography apparatus: A gas chromatography apparatus equipped with the following columns and a thermostatic chamber was constructed. Column: Agilent Technologies, CP-Molsieve5A, 25m, 0.32mm, 30μm Mass spectrometer: Kanomax Analytical Co., Ltd., infiTOF-UHV

[0073] The main conditions for each part of the system were as follows: - Canister and sample supply device piping temperature: Maintained at 80℃ Methanizer (Ni catalytic furnace) temperature: 400~450℃ Gas chromatography equipment ··Carrier gas (helium gas) flow rate: 5cc / min Column temperature: 80℃ Cold trap ·Collection temperature: -180℃ ·Collection time: 15 seconds ~ 600 seconds Heating conditions: 3℃ / sec, heating from -180℃ to 200℃

[0074] The components analyzed were oxygen, nitrogen, argon, helium, methane, total hydrocarbons, carbon monoxide, carbon dioxide, ammonia, formaldehyde, formic acid, total sulfur compounds, and halogen compounds. The groups of components analyzed, their standard values ​​in ISO14687, pretreatment methods, and the time required for measurement are summarized in Table 1.

[0075] [Table 1]

[0076] As shown in Table 1, quantitative analysis of the 13 components was completed in a total of 6 to 7 hours. In addition, a demonstration test was conducted using hydrogen gas collected from 16 hydrogen stations actually in commercial operation, and it was confirmed that the analysis could be carried out stably and without any problems. Moisture content was measured using a moisture meter at the hydrogen gas sample collection site.

[0077] The embodiments disclosed herein are illustrative in all respects and should not be construed as limiting. The scope of the present invention is defined by the claims, not the above description, and is intended to include all modifications within the meaning and scope of the claims. [Explanation of symbols]

[0078] 1 Hydrogen gas analysis system, 10 Sample supply device, 11 Methanizer, 12, 37 Pressure reducing valve, 13 Vacuum pump, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 Valve, 31, 32 Pressure gauge, 41, 42, 43, 44, 45, 46, 47, 48, 50, 51, Pipe, 49, 52 Discharge pipe, 60 Pretreatment device, 61 First separation section, 62 Second separation section, 65 Separation column, 70 First switching section, 71, 72, 73, 74 Switching valve, 81 Sample loop, 82 Collection tube, 83 Cooling section, 84 Heater, 90 Standard gas supply device, 92 Dilution gas inlet section, 93 Standard gas inlet section, 100 Mass spectrometer, 101 Mass spectrometer, 102 First input port, 103 Second input port.

Claims

1. A hydrogen gas analysis system for performing a quantitative analysis of an analyte component contained in a sample of hydrogen gas, comprising: a sample supplying device that supplies the sample from a sample container in which the sample is accommodated; a pretreatment device for pretreatment of the sample supplied by the sample supply device; a mass spectrometer for performing a quantitative analysis on the sample that has been pretreated by the pretreatment device, The sample supplying device includes: a first pipe connected to the sample container and the pretreatment device; and a methane conversion unit installed in the first pipe for converting non-methane hydrocarbon compounds contained in the sample into methane, The pretreatment device comprises: a first separation unit that separates a portion of a target component from the sample supplied by the sample supplying device using a separation column including a stationary phase; a second separation unit that separates a part of a target component from the sample supplied by the sample supplying device by cooling and heating; A third pipe connected to the first separation unit and the mass spectrometer; A fourth pipe connected to the second separation unit and the mass spectrometer; A carrier gas supply unit that supplies a carrier gas to the inside of the third pipe and the inside of the fourth pipe, Hydrogen Gas Analysis System.

2. The hydrogen gas analysis system according to claim 1 , wherein the mass spectrometer is a time-of-flight mass spectrometer.

3. 3. The hydrogen gas analysis system according to claim 1, wherein the first separation section includes a gas chromatography device and separates oxygen, nitrogen, argon, methane, and carbon monoxide from the sample.

4. the second separation unit includes a collection tube, a cooling unit that cools the collection tube, and a heating unit that heats the collection tube, 3. The hydrogen gas analysis system according to claim 1, wherein the pretreatment device controls the cooling unit so that the trapping tube is cooled to a predetermined temperature, and then controls the heating unit so that the trapping tube is heated in stages.

5. 5. The hydrogen gas analyzing system according to claim 4, wherein the second separation section separates formic acid, formaldehyde, ammonia, total sulfur compounds, and halogen compounds from the sample.

6. the pretreatment device includes a first switching unit that is switchable so as to supply the sample supplied by the sample supply device to either the first separation unit or the second separation unit; The hydrogen gas analysis system according to claim 1 or 2.

7. the sample supplying device further includes a second pipe that is installed separately from the third pipe and the fourth pipe and is connected to the sample container and the mass spectrometer; The mass spectrometer further performs a quantitative analysis of helium in the sample supplied by the sample supply device through the second pipe. The hydrogen gas analysis system according to claim 1 or 2.

8. The apparatus further includes a first standard gas supply device that supplies the standard gas from a first standard gas container that contains the standard gas; the mass spectrometer obtains a calibration curve using the standard gas supplied from the first standard gas supply device; The hydrogen gas analysis system according to claim 1 or 2.

9. The first standard gas supply device is a dilution gas inlet for introducing a dilution gas, which is hydrogen gas other than the sample; a fifth pipe connected to the first standard gas container and the mass spectrometer; a dilution container connected to the fifth pipe and filled with the standard gas and the dilution gas; a sixth pipe connected to the dilution gas inlet and the dilution container; A pressure measuring unit that measures the pressure inside the dilution container; an exhaust pipe connected to the sixth pipe for exhausting the gas filled in the dilution container to the outside of the first standard gas supply device; a standard gas valve that is installed on the fifth pipe and switches the fifth pipe between a closed state in which the fifth pipe is blocked and an open state in which the fifth pipe is opened; a dilution gas valve that is installed in the sixth pipe and switches the sixth pipe between a closed state in which the sixth pipe is blocked and an open state in which the sixth pipe is opened; The hydrogen gas analysis system according to claim 8 , further comprising: a discharge valve disposed in the discharge pipe and configured to switch the discharge pipe between a closed state in which the discharge pipe is blocked and an open state in which the discharge pipe is opened.

10. The first standard gas supply device is a standard gas filling control for controlling the standard gas valve so that the standard gas is filled into the dilution container until the pressure inside the dilution container measured by the pressure measuring unit reaches a predetermined first value; a release control for controlling the exhaust valve so that the gas filled in the dilution container is released until the pressure inside the dilution container measured by the pressure measuring unit reaches a predetermined second value; a dilution gas filling control for controlling the dilution gas valve so that the dilution gas is filled into the dilution container until the pressure inside the dilution container measured by the pressure measuring unit reaches a predetermined third value, After the standard gas filling control and the release control are executed in sequence, the dilution gas filling control and the release control are repeatedly executed to dilute the standard gas with the dilution gas. The hydrogen gas analysis system of claim 9.

11. A hydrogen gas analysis method for quantitatively analyzing an analyte component contained in a sample of hydrogen gas, comprising: a sample supplying step of supplying the sample from a sample container containing the sample; a pretreatment step for pretreatment of the sample supplied in the sample supply step; A mass spectrometry step of performing a quantitative analysis on the sample that has been pretreated in the pretreatment step using a mass spectrometer, The pre-treatment step includes: a first separation step of separating a portion of a target component from the sample supplied in the sample supply step using a separation column including a stationary phase; A second separation step of separating a part of the analysis target component from the sample supplied in the sample supply step by cooling and heating. Hydrogen gas analysis method.

12. The sample supplying step includes: A methane conversion step of introducing the sample hydrogen gas into a methane conversion section to convert non-methane hydrocarbons into methane; The method for analyzing hydrogen gas according to claim 11.

13. The first separation step and the second separation step are alternatively performed. The method for analyzing hydrogen gas according to claim 11 or 12.

14. The method further includes a dilution step of diluting a standard gas used for obtaining a calibration curve in the mass spectrometer with a dilution gas, The dilution step comprises: a standard gas filling step of filling the dilution container with the standard gas until the pressure inside the dilution container reaches a predetermined first value; a discharging step of discharging the gas filled in the dilution container until the pressure inside the dilution container reaches a predetermined second value; and a dilution gas filling step of filling the dilution container with the dilution gas until a pressure inside the dilution container reaches a third predetermined value; After the standard gas filling step and the release step are carried out in sequence, the dilution gas filling step and the release step are repeatedly carried out. The method for analyzing hydrogen gas according to claim 11 or 12.

15. The mass spectrometry step comprises: a first mass spectrometry step for analyzing the analyte components separated in the first separation step; a second mass spectrometry step for analyzing the analyte components separated in the second separation step; a third mass analysis step of performing a quantitative analysis of helium on the sample that has not been subjected to the first separation step and the second separation step; The method for analyzing hydrogen gas according to claim 11 or 12, comprising:

16. the first mass spectrometry step quantifies analytes including oxygen, nitrogen, argon, methane, carbon monoxide and total hydrocarbons; The second mass spectrometry step quantifies the components to be analyzed, including formic acid, formaldehyde, ammonia, halogen compounds, and total sulfur compounds; The third mass analysis step quantifies helium. The method for analyzing hydrogen gas according to claim 15.

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