CN114544807A - Device and method for analyzing impurities in hydrogen isotope gas - Google Patents
Device and method for analyzing impurities in hydrogen isotope gas Download PDFInfo
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- CN114544807A CN114544807A CN202210135779.2A CN202210135779A CN114544807A CN 114544807 A CN114544807 A CN 114544807A CN 202210135779 A CN202210135779 A CN 202210135779A CN 114544807 A CN114544807 A CN 114544807A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/38—Flow patterns
- G01N30/46—Flow patterns using more than one column
- G01N30/468—Flow patterns using more than one column involving switching between different column configurations
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N30/66—Thermal conductivity detectors
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
- G01N2030/143—Preparation by elimination of some components selective absorption
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/10—Nuclear fusion reactors
Abstract
The invention discloses an impurity analysis device in hydrogen isotope gas, which comprises a carrier gas source, a standard gas source, a sample container, a chromatographic column box, a hydrogen purifier and a thermal conductivity detector, wherein the chromatographic column box comprises a first chromatographic column and a second chromatographic column, and the hydrogen purifier can adsorb the hydrogen isotope gas. According to the invention, the hydrogen purifier is connected in series in front of the first chromatographic column, and the hydrogen purifier can adsorb the hydrogen isotope gas to a position below the detection limit of the thermal conductivity detector so as to eliminate the overlapping between the deuterium-tritium peak and the helium peak, thereby improving the analysis accuracy of helium impurities in the hydrogen isotope gas; the invention also provides a method for analyzing impurities in the hydrogen isotope gas, which utilizes argon as carrier gas to analyze through the second chromatographic column, thereby avoiding the interference of the argon impurities in the hydrogen isotope sample on the analysis of oxygen impurities. The invention realizes the high-precision analysis of the helium and oxygen impurities in the hydrogen isotope gas and simultaneously considers the analysis of the impurities such as nitrogen, methane, carbon monoxide and the like.
Description
Technical Field
The invention relates to the technical field of gas chromatography analysis, in particular to a device and a method for analyzing impurities in hydrogen isotope gas.
Background
International Thermonuclear Fusion Experimental Reactor (ITER), Chinese Fusion Engineering Test Reactor (CFETR) and the like are important items for propelling Fusion power generation, and related technologies such as tritium fuel circulation and tritium balance among them need to quickly and accurately analyze and control impurity levels in hydrogen isotope gas.
Because the hydrogen isotope mixed gas often contains deuterium and tritium isotopes, the chromatographic analysis of impurities in the hydrogen isotope mixed gas is different from the analysis of common hydrogen. The chromatographic analysis of impurities in ordinary hydrogen gas usually adopts high-purity hydrogen as carrier gas, and because the sample gas contains no deuterium and tritium, helium (helium) whose retention time is close to that of deuterium and tritium3He or4He) impurities are not disturbed. When the sample gas contains deuterium or tritium, the deuterium-tritium peak is often far larger than the helium peak under the condition of using hydrogen as carrier gas, and baseline separation between the deuterium-tritium peak and the helium peak is difficult to realize, so that the uncertainty of the helium peak area integral result is increased. To improve the degree of separation between helium and hydrogen isotope gas, a method of greatly increasing the length of the column or lowering the temperature of the column can be employed, but this results in a significant broadening of the chromatographic peak and a significant increase in the analysis time. Therefore, it is difficult to rapidly and accurately analyze helium impurities in hydrogen isotopes using conventional chromatographs.
In addition, process equipment for operating hydrogen isotope gas is often placed in a glove box using argon as a protective atmosphere. In the vacuum state, there is a possibility that argon is mixed in the hydrogen isotope gas by a slight leak of a device such as a pipe. Oxygen and argon are often difficult to effectively separate in a 5A capillary column with hydrogen as a carrier gas at normal temperature, so that the analysis result of the content of oxygen impurities is higher under the condition of argon impurities.
Therefore, how to change the current situation that the analysis accuracy is poor and other gases are easily mixed to affect the analysis result when the impurities in the hydrogen isotope gas are analyzed by using a conventional chromatograph becomes a problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a device and a method for analyzing impurities in hydrogen isotope gas, which are used for solving the problems in the prior art and improving the analysis precision of the impurities in the hydrogen isotope gas, particularly helium and oxygen impurities.
In order to achieve the purpose, the invention provides the following scheme: the invention provides an apparatus for analyzing impurities in hydrogen isotope gas, comprising:
a carrier gas source capable of containing argon gas;
a standard gas source capable of holding a standard gas;
a sample container capable of holding a sample gas;
the chromatographic column box comprises a first chromatographic column and a second chromatographic column, and the first chromatographic column and the second chromatographic column can be switched; the standard gas source and the sample container are capable of communicating with the first chromatography column and the second chromatography column, respectively;
the hydrogen purifier is communicated with the first chromatographic column and is positioned on one side of the first chromatographic column close to the sample container, and the hydrogen purifier can adsorb hydrogen isotope gas;
a thermal conductivity detector capable of detecting effluent gases of the first and second chromatography columns.
Preferably, hydrogen purifier includes top connection, filter tube and lower clutch, the filter tube set up in the top connection, the top connection has gas inlet, gas inlet with the opening of filter tube is linked together just gas inlet with set up the quartz cotton between the filter tube opening, be provided with palladium-loaded alumina in the filter tube, the lateral wall and the diapire of filter tube all have the through-hole, the lower clutch has gas outlet, the filter tube with gap between the top connection with gas outlet is linked together, the lower clutch with the top connection can be dismantled the connection and set up seal gasket between the two.
Preferably, a positioning hole is formed in the upper joint, the opening of the filter pipe extends into the positioning hole, a compression spring is arranged between one end, far away from the opening, of the filter pipe and the lower joint, and the compression spring can enable one end, far away from the opening, of the filter pipe to abut against the positioning hole.
Preferably, the upper joint is in sealing threaded connection with the lower joint; the sealing gasket is made of red copper, a silver coating is arranged on the outer surface of the sealing gasket, and the silver coating is made of silver.
Preferably, the upper joint and the lower joint are provided with joint segments, and the joint segments are in a hexagonal prism structure.
Preferably, the sample container, the standard gas source and the carrier gas source are communicated with the first chromatographic column and the second chromatographic column by using a test pipeline, a first six-way valve and a second six-way valve are arranged on the test pipeline, the first chromatographic column and the second chromatographic column are switched by using the second six-way valve, the first chromatographic column and the second chromatographic column are connected with the thermal conductivity detector by using the second six-way valve, and the carrier gas source is communicated with the first chromatographic column and the second chromatographic column by using the second six-way valve.
Preferably, still be provided with pressure sensor and vacuum gauge on the test pipeline, the test tube coupling has the vacuum pump, the vacuum pump can be right the test pipeline evacuation, vacuum pump connection has the buffer tank, the thermal conductivity detector with the buffer tank links to each other, the buffer tank has the exhaust interface.
Preferably, a stop valve is arranged between the standard gas source and the sample container, and the test pipeline is further connected with an adsorption bed.
The invention also provides a method for analyzing impurities in hydrogen isotope gas, which utilizes the device for analyzing impurities in hydrogen isotope gas and comprises the following steps:
selecting the first chromatographic column or the second chromatographic column according to the type of the analyzed impurities, introducing sample gas and standard gas, and collecting signals of the thermal conductivity detector to obtain a chromatogram;
changing the pressure of the sample gas to obtain chromatograms under different sample introduction pressure conditions;
integrating the peak area of a chromatographic peak of each sample injection of the analytical component in the chromatogram, and obtaining the content of the analytical component according to the integrated area, the sample injection pressure and the temperature;
and step four, averaging the contents under different sample introduction pressure conditions to obtain a chromatographic analysis result of the analysis component.
Preferably, before performing the analysis, the device for analyzing impurities in hydrogen isotope gas is first calibrated, and comprises the following steps:
step one, setting the temperature of the chromatographic column box and the thermal conductivity detector as an activation temperature, and purging the hydrogen purifier, the first chromatographic column and the second chromatographic column by using argon for not less than 4 hours;
step two, cooling the first chromatographic column, the second chromatographic column and the hydrogen purifier to set temperature, and adjusting the temperature of the thermal conductivity detector to working temperature;
step three, standard gas which contains helium and is similar to the gas component of the sample is accessed;
fourthly, vacuumizing and carrying out vacuum leak detection on the device for analyzing the impurities in the hydrogen isotope gas;
observing a base line, acquiring a signal of the thermal conductivity detector after the base line is stable, obtaining a chromatogram under a blank sample condition, and verifying the chromatogram in which the analysis component is not detected under the blank condition according to a blank sample result;
sixthly, after the chromatogram recording time is longer than the retention time of the component to be detected, vacuumizing the impurity analysis device in the hydrogen isotope gas;
step seven, introducing standard gas, collecting the signal of the thermal conductivity detector and obtaining a chromatogram;
step eight, stopping introducing standard gas after the thermal conductivity detector detects a complete chromatographic peak of the component to be detected, and vacuumizing the impurity analysis device in the hydrogen isotope gas;
step nine, changing the sample injection pressure, and repeatedly performing the step seven and the step eight to continuously obtain chromatograms under different sample injection pressure conditions for more than 6 times;
step ten, integrating the peak areas of chromatographic peaks of each component in the chromatogram in each sample injection; drawing the chromatographic peak area and the sample injection pressure of the same component, and obtaining the slope of a fitting straight line and a linear correlation coefficient of the analysis component by least square fitting; and obtaining sensitivity factors of the chromatograph on all components by fitting the slope of the straight line and the content of the helium component in the standard gas.
Compared with the prior art, the invention has the following technical effects: the invention relates to an analysis device for impurities in hydrogen isotope gas, which comprises a carrier gas source, a standard gas source, a sample container, a chromatographic column box, a hydrogen purifier and a thermal conductivity detector, wherein the carrier gas source can contain argon; the standard gas source can contain standard gas; the sample container is capable of holding a sample gas; the chromatographic column box comprises a first chromatographic column and a second chromatographic column, and the first chromatographic column and the second chromatographic column can be switched; the standard gas source and the sample container can be respectively communicated with the first chromatographic column and the second chromatographic column; the hydrogen purifier is communicated with the first chromatographic column and is positioned on one side of the first chromatographic column close to the sample container, and the hydrogen purifier can adsorb hydrogen isotope gas; the thermal conductivity detector can detect the effluent gas of the first chromatographic column and the second chromatographic column.
According to the device for analyzing the impurities in the hydrogen isotope gas, the hydrogen purifier is connected in series before the first chromatographic column, and can adsorb the hydrogen isotope gas to a position below the detection limit of the thermal conductivity detector so as to eliminate the overlapping between a deuterium tritium peak and a helium peak, so that the analysis accuracy of the helium impurities in the hydrogen isotope gas is improved; the invention also provides a method for analyzing impurities in the hydrogen isotope gas, which is characterized in that the device for analyzing the impurities in the hydrogen isotope gas is utilized, the first chromatographic column and the second chromatographic column are arranged in the chromatographic column box, and the gas circuit is switched to the second chromatographic column through the second six-way valve, so that the high-precision analysis of the content of oxygen impurities in the hydrogen isotope gas containing argon impurities is realized, and the analysis of impurities such as nitrogen, methane, carbon monoxide and the like is also considered.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic structural view of a hydrogen purifier of an apparatus for analyzing impurities in hydrogen isotope gas according to the present invention;
fig. 2 is a schematic view of an apparatus for analyzing impurities in a hydrogen isotope gas of the present invention;
wherein, 1 is the carrier gas air supply, 2 is the standard gas air supply, 3 is the stop valve, 4 is the sample container, 5 is pressure sensor, 6 is vacuum sensor, 7 is the vacuum pump, 8 is the buffer tank, 9 is the discharge gas interface, 10 is the ration ring, 11 is the adsorption bed, 12 is first six-way valve, 13 is the second six-way valve, 14 is the thermal conductivity detector, 15 is hydrogen purifier, 1501 is the top connection, 1502 is the filter tube, 1503 is the lower clutch, 1504 is gas inlet, 1505 is the gas outlet, 1506 is pressure spring, 1507 is the gasket, 16 is first chromatographic column, 17 is the second chromatographic column, 18 is the chromatographic column case.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention aims to provide a device and a method for analyzing impurities in hydrogen isotope gas, which are used for solving the problems in the prior art and improving the analysis accuracy of the content of helium impurities and the content of oxygen impurities when oxygen and argon impurities simultaneously exist in the hydrogen isotope gas.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Referring to fig. 1-2, fig. 1 is a schematic diagram of a hydrogen purifier of an apparatus for analyzing impurities in hydrogen isotope gas according to the present invention, and fig. 2 is a schematic diagram of an apparatus for analyzing impurities in hydrogen isotope gas according to the present invention.
The invention provides an analysis device for impurities in hydrogen isotope gas, which comprises a carrier gas source 1, a standard gas source 2, a sample container 4, a chromatographic column box 18, a hydrogen purifier 15 and a thermal conductivity detector 14, wherein the carrier gas source 1 can contain argon gas; the standard gas source 2 can contain standard gas; the sample container 4 is capable of containing a sample gas; the chromatographic column box 18 comprises a first chromatographic column 16 and a second chromatographic column 17, and the first chromatographic column 16 and the second chromatographic column 17 can be switched; the standard gas source 2 and the sample container 4 can be in communication with a first chromatographic column 16 and a second chromatographic column 17, respectively; the hydrogen purifier 15 is communicated with the first chromatographic column 16, the hydrogen purifier 15 is positioned on one side of the first chromatographic column 16 close to the sample container 4, and the hydrogen purifier 15 can adsorb hydrogen isotope gas; the thermal conductivity detector 14 is capable of detecting the gas flowing out of the first chromatography column 16 and the second chromatography column 17.
The device for analyzing the impurities in the hydrogen isotope gas is characterized in that a hydrogen purifier 15 is connected in series before a first chromatographic column 16, and the hydrogen purifier 15 can adsorb the hydrogen isotope gas to a position below the detection limit of a thermal conductivity detector 14 so as to eliminate the overlapping between a deuterium-tritium peak and a helium peak, thereby improving the analysis accuracy of the helium impurities in the hydrogen isotope gas; the first chromatographic column 16 and the second chromatographic column 17 are arranged in the chromatographic column box 18, and the analysis of impurities such as nitrogen, methane, carbon monoxide and the like is considered while the high-precision analysis of helium and oxygen impurities in hydrogen isotope gas is realized by switching the chromatographic columns.
Wherein, hydrogen purifier 15 includes top connection 1501, filter tube 1502 and lower clutch 1503, filter tube 1502 sets up in top connection 1501, top connection 1501 has gas inlet 1504, gas inlet 1504 is linked together with the opening of filter tube 1502 and set up the quartz wool between gas inlet 1504 and the filter tube 1502 opening, be provided with the palladium-loaded alumina in the filter tube 1502, the lateral wall and the diapire of filter tube 1502 all have the through-hole, lower clutch 1503 has gas outlet 1505, the gap between filter tube 1502 and the top connection 1501 is linked together with gas outlet 1505, lower clutch 1503 and top connection 1501 can be dismantled and be connected and set up seal gasket 1507 between the two. The sample gas enters the filter pipe 1502 through the gas inlet 1504, the palladium-loaded alumina in the filter pipe 1502 can adsorb hydrogen isotope gas, and the gas after adsorption by the filter pipe 1502 is guided out through the through hole of the filter pipe 1502 through the gap between the filter pipe 1502 and the inner cavity of the upper joint 1501 and then through the gas outlet 1505 of the lower joint 1503.
Specifically, the locating hole has in the top connection 1501, the opening of filter tube 1502 stretches into in the locating hole, the locating hole provides spacingly for filter tube 1502 installs, filter tube 1502 keeps away from and sets up pressure spring 1506 between open-ended one end and the lower clutch 1503, pressure spring 1506 can make filter tube 1502's opening one end and locating hole butt, pressure spring 1506 and locating hole cooperate, the stability of filter tube 1502 has further been improved, avoid gaseous directly by the gap between filter tube 1502 and the top connection 1501 inner chamber caused the short circuit by gas outlet 1505 outflow after getting into by gas inlet 1504, improve hydrogen purifier 15's operational reliability.
In the embodiment, the upper connector 1501 is in sealed threaded connection with the lower connector 1503, so that the disassembly and the assembly are convenient on the premise of ensuring the sealed connection; the sealing gasket 1507 is made of red copper, and the outer surface of the sealing gasket 1507 is provided with a silver coating which is made of silver.
In order to facilitate connection of the hydrogen purifier 15 with other components, the upper connector 1501 and the lower connector 1503 both have connector segments, and the connector segments are hexagonal prism-shaped structures, so that the hydrogen purifier can be conveniently screwed by using a wrench. In this embodiment, the upper fitting 1501 has a gas inlet 1504 with a length of about 10mm, a diameter of about 3mm, an outer diameter of 1/4 inches, a fitting segment length of about 11mm, a height of about 4.5mm, an intermediate segment outer diameter of about 18.5mm, a wall thickness of 2mm, and a length of 30mm to 40mm, which can be adjusted according to the length of the filter tube 1502. The filter tube 1502 is made of a porous stainless steel material, and has a side wall and a bottom surface of 1.0mm to 1.6mm in thickness and a length of about 20mm to 30mm, and the aperture of the through hole of the filter tube 1502 is 2 μm. The gasket 1507 has an outer diameter of about 19.2mm, an inner diameter of about 16mm, a thickness of about 0.7mm to 1.0mm, a gas outlet 1505 segment length of the lower junction 1503 of about 10mm, a drift diameter of about 3mm, an outer diameter of 1/4 inches, a cross-sectional side length of the junction segment of about 11mm, and a height of about 4.5 mm. In practical application, the sizes of the upper joint 1501, the filter pipe 1502 and the lower joint 1503 can be adjusted correspondingly according to actual needs.
More specifically, the sample container 4, the standard gas source 2 and the carrier gas source 1 are communicated with a first chromatographic column 16 and a second chromatographic column 17 by using a test pipeline, a first six-way valve 12 and a second six-way valve 13 are arranged on the test pipeline, the first chromatographic column 16 and the second chromatographic column 17 are respectively connected into a chromatographic gas circuit by using a switching mode of the second six-way valve 13, the first six-way valve 12 is connected with a quantitative ring 10, the first chromatographic column 16 or the second chromatographic column 17 is connected with a thermal conductivity detector 14 by using the second six-way valve 13, and the carrier gas source 1 is communicated with the first chromatographic column 16 and the second chromatographic column 17 by using the second six-way valve 13. The invention realizes the switching between the first chromatographic column 16 and the second chromatographic column 17 by using the switch second six-way valve 13, so that the device realizes the high-precision analysis of helium and oxygen impurities in hydrogen isotope gas and simultaneously considers the analysis of impurities such as nitrogen, methane, carbon monoxide and the like.
In addition, still be provided with pressure sensor 5 and vacuum sensor 6 on the test pipeline, the test tube coupling has vacuum pump 7, and vacuum pump 7 can be to the test pipeline evacuation, and vacuum pump 7 is connected with buffer tank 8, and thermal conductivity detector 14 links to each other with buffer tank 8, and buffer tank 8 has exhaust interface 9, has improved the operational reliability of device. In addition, set up stop valve 3 between standard gas source 2 and the sample container 4, the test pipeline still is connected with adsorption bed 11, improves the adaptability and the operating safety coefficient of device.
The invention also provides a method for analyzing impurities in hydrogen isotope gas, which utilizes the device for analyzing impurities in hydrogen isotope gas and comprises the following steps:
selecting a first chromatographic column 16 or a second chromatographic column 17 according to the type of the analyzed impurities, introducing sample gas, standard gas and argon, and collecting signals of a thermal conductivity detector 14 to obtain a chromatogram;
changing the pressure of the sample gas to obtain chromatograms under different sample introduction pressure conditions;
integrating the peak area of a chromatographic peak of each sample injection of the analytical component in the chromatogram, and obtaining the content of the analytical component according to the integrated area, the sample injection pressure and the temperature;
and step four, averaging the contents under different sample introduction pressure conditions to obtain a chromatographic analysis result of the analysis component.
According to the method for analyzing the impurities in the hydrogen isotope gas, the argon is used as the carrier gas, so that the interference of the argon in the hydrogen isotope-containing sample on the analysis of the oxygen impurities is avoided, and the analysis precision of the oxygen impurities in the argon-hydrogen isotope-containing gas is improved.
It should be noted that, before performing the analysis, the apparatus for analyzing impurities in hydrogen isotope gas is first calibrated, and includes the following steps:
step one, setting the temperature of a chromatographic column box 18 and a thermal conductivity detector 14 as an activation temperature, and purging a hydrogen purifier 15, a first chromatographic column 16 or a second chromatographic column 17 by using argon for not less than 4 hours;
step two, cooling the first chromatographic column 16, the second chromatographic column 17 and the hydrogen purifier 15 to a set temperature, and adjusting the temperature of the thermal conductivity detector 14 to a working temperature;
step three, standard gas which contains helium and is similar to the gas component of the sample is accessed;
step four, vacuumizing and carrying out vacuum leak detection on the impurity analysis device in the hydrogen isotope gas;
observing the base line, acquiring a signal of the thermal conductivity detector 14 after the base line is stable, obtaining a chromatogram under a blank sample condition, and verifying the chromatogram in which the analysis component is not detected under the blank condition according to a blank sample result;
sixthly, when the chromatogram recording time is longer than the retention time of the component to be detected, vacuumizing an impurity analysis device in the hydrogen isotope gas;
step seven, introducing standard gas with certain pressure, collecting signals of the thermal conductivity detector 14 and obtaining a chromatogram;
step eight, stopping introducing the standard gas after the thermal conductivity detector 14 detects the complete chromatographic peak of the component to be detected, and vacuumizing the impurity analysis device in the hydrogen isotope gas;
step nine, changing the sample injection pressure, and repeatedly performing the step seven and the step eight to continuously obtain chromatograms under different sample injection pressure conditions for more than 6 times;
step ten, integrating the peak areas of chromatographic peaks of each component in the chromatogram in each sample injection; drawing the chromatographic peak area and the sample injection pressure of the same component, and obtaining the slope of a fitting straight line and a linear correlation coefficient of the analysis component by least square fitting; and obtaining sensitivity factors of the chromatograph on all components by fitting the slope of the straight line and the content of the helium component in the standard gas.
The following will explain the analysis of impurities in a hydrogen isotope gas and the method of the present invention by way of specific examples.
Example one
For calibrating the apparatus4He sensitivity
(1) Setting the temperature of the chromatographic column box 18 and the temperature of the thermal conductivity detector 14 to 200 ℃, closing the second six-way valve 13 (at the moment, the first chromatographic column 16 is communicated with the thermal conductivity detector 14), and purging the hydrogen purifier 15 and the chromatographic column by adopting high-purity argon for not less than 4 hours;
(2) cooling the chromatographic column and the hydrogen purifier 15 to 30 ℃, and reducing the temperature of the thermal conductivity detector 14 to 70 ℃;
(3) will be provided with4A standard gas source 2 (the main component is argon) with the He content of 0.1 percent is connected into a vacuum sample introduction system according to the position shown in figure 2;
(4) evacuating the pipeline of the chromatograph and carrying out vacuum leak detection to ensure the air tightness;
(5) observing the base line, opening the first six-way valve 12 after the base line is stable, and simultaneously starting to acquire signals of the thermal conductivity detector 14 so as to obtain a chromatogram under a blank sample introduction condition;
(6) when the time for collecting the signals of the thermal conductivity detector 14 reaches 2min, closing the first six-way valve 12, and evacuating the chromatograph pipeline again; no obvious chromatographic peak exists under the blank sample injection condition, and no false peak exists;
(7) slowly opening a valve of a standard gas source 2, filling 8989Pa standard gas into a vacuum sample injection system pipeline, and then closing the valve of the standard gas source 2;
(8) opening the valve of the first six-way valve 12, and simultaneously starting to acquire a signal of the thermal conductivity detector 14 so as to obtain a chromatogram;
(9) and 2min later, closing the valve 12 of the first six-way valve, and then evacuating the chromatograph pipeline;
(10) repeating the steps (7) to (9), changing the sample injection pressure and continuously obtaining chromatograms under 7 times of different sample injection pressure conditions (8989Pa, 10593Pa, 14421Pa, 19241Pa, 23303Pa, 26461Pa and 34774 Pa);
(11) integrating the peak areas of chromatographic peaks of each component injected for each time according to the obtained chromatogram, wherein the integrated areas are 35317 mu v s, 41150 mu v s, 62131 mu v s, 76627 mu v s, 92574 mu v s, 104552 mu v s and 137755 mu v s respectively, and the retention time is 1.02 min;
(12) plotting the chromatographic peak area of the same component against the injection pressure, obtaining the slope of a fitting straight line with zero intercept of 3.9599 Muv.s/Pa by least square fitting, and obtaining a chromatograph pair4The sensitivity factor for He was 3959.9. mu.v.s/Pa.
Example two
For calibrating the apparatus3He sensitivity.
(1) Setting the temperature of the chromatographic column box 18 and the temperature of the thermal conductivity detector 14 to 200 ℃, closing the second six-way valve 13 (at the moment, the first chromatographic column 16 is communicated with the thermal conductivity detector 14), and purging the hydrogen purifier 15 and the chromatographic column by adopting high-purity argon gas for not less than 4 hours;
(2) cooling the chromatographic column and the hydrogen purifier 15 to 30 ℃, and reducing the temperature of the thermal conductivity detector 14 to 70 ℃;
(3) will be pure3He gas is used as a standard gas source 2 and is connected into a vacuum sample injection system according to the position shown in figure 2;
(4) evacuating the pipeline of the chromatograph and carrying out vacuum leak detection to ensure the air tightness;
(5) observing the base line, opening the first six-way valve 12 after the base line is stable, and simultaneously starting to acquire a signal of the thermal conductivity detector 14 so as to obtain a chromatogram map under a blank sampling condition;
(6) when the time for collecting the signal of the thermal conductivity detector 14 reaches 2min, closing the first six-way valve 12, and evacuating the chromatograph pipeline again; confirming that no false peak exists through no obvious chromatographic peak under the blank sample injection condition;
(7) slowly opening a valve of a standard gas source 2, filling 1246Pa standard gas into a vacuum sample injection system pipeline, and then closing the valve of the standard gas source 2;
(8) opening the valve of the first six-way valve 12, and simultaneously starting to acquire a signal of the thermal conductivity detector 14 so as to obtain a chromatogram;
(9) and after 2min, closing the valve 12 of the first six-way valve, and then evacuating the chromatograph pipeline;
(10) repeating the steps (7) to (9), changing the sample injection pressure and continuously obtaining chromatograms under the conditions of 7 times of different sample injection pressures (1246Pa, 1003Pa, 900Pa, 753Pa, 550Pa, 281Pa and 91 Pa);
(11) integrating the peak areas of chromatographic peaks of each component injected for each time according to the obtained chromatogram, wherein the integrated areas are 5302725 Muv s, 4283820 Muv s, 3786067 Muv s, 3155154 Muv s, 2305113 Muv s, 1168329 Muv s and 387906 Muv s respectively, and the retention time is 1.01 min;
(12) and drawing the chromatographic peak area of the same component to the injection pressure, and obtaining a fitted straight line with the intercept of zero by least square fitting, wherein the slope of the fitted straight line is 4235.2 Muv · s/Pa, and the linear correlation coefficient is 0.9999.
(13) Dividing the slope of the fitted line by the standard gas3He content (100%) to obtain chromatograph pair3The sensitivity factor for He was 4235.2. mu.v.s/Pa.
Example III,
O of calibrating instrument2、N2、CH4CO sensitivity
(1) Setting the temperature of the chromatographic column box 18 and the temperature of the thermal conductivity detector 14 to be 200-250 ℃, starting the second six-way valve 13 (at the moment, the second chromatographic column 17 is communicated with the thermal conductivity detector 14), and purging the second chromatographic column 17 by adopting high-purity argon for not less than 4 hours;
(2) cooling the chromatographic column and the hydrogen purifier 15 to 30 ℃, and reducing the temperature of the thermal conductivity detector 14 to 70 ℃;
(3) the main component is hydrogen, O2、N2、CH4And standard gases with CO contents of 1.00%, 1.00% and 1.00% respectively, and connecting to a vacuum sample injection system according to the position shown in figure 2;
(4) evacuating the pipeline of the chromatograph and carrying out vacuum leak detection to ensure the air tightness;
(5) observing a baseline, opening the first six-way valve 12 after the baseline is stable, and simultaneously starting to collect a signal of the thermal conductivity detector 14 so as to obtain a chromatographic peak under a blank sample condition;
(6) when the time for collecting the signal of the thermal conductivity detector 14 reaches 10min, closing the first six-way valve 12, and evacuating the chromatograph pipeline again; confirming that no false peak exists through no obvious chromatographic peak under the blank sample introduction condition;
(7) slowly opening a standard gas source 2 valve, filling 513Pa standard gas into a vacuum sample injection system pipeline, and then closing the standard gas source 2 valve;
(8) when the first six-way valve 12 is opened, starting to collect signals of the thermal conductivity detector 14 so as to obtain a chromatogram;
(9) after 10min, closing the first six-way valve 12, and then evacuating the chromatograph pipeline;
(10) repeating the steps (7) to (9), changing the sample injection pressure and continuously obtaining chromatograms under different sample injection pressure conditions for 8 times;
(11) obtaining O from the obtained chromatogram2、N2、CH4And the CO retention time is 1.27min, 2.14min, 2.81min and 8.07min respectively, the peak areas of chromatographic peaks of each component in each sample injection are integrated, and the results are summarized in the following table.
TABLE 1 chromatographic peak area obtained under different injection pressure conditions for different components
(12) And drawing the chromatographic peak area of the same component to the sample injection pressure, and obtaining the slope of a fitting straight line with zero intercept and a linear correlation coefficient through least square fitting. To O2、N2、CH4CO, the slope of the fitted straight line is respectively as follows: 7.5749 Muv s/Pa, 6.4163 Muv s/Pa, 17.398 Muv s/Pa and 5.9995 Muv s/Pa, and linear correlation coefficients of the fitted straight line are respectively as follows: 0.9999, 1.0000, 0.9999.
(13) Dividing the slope of each fitted straight line by the content of the corresponding component to obtain the chromatographic instrument pair O2、N2、CH4The sensitivity factors for CO were 757.49. mu. v.s/Pa, 641.63. mu. v.s/Pa, 1739.8. mu. v.s/Pa, and 599.95. mu. v.s/Pa, respectively.
Example four
In the chromatographic analysis of gases containing tritium-hydrogen isotopes3He、O2、N2、CH4CO impurity content
(1) Setting the temperature of the chromatographic column box 18 and the temperature of the thermal conductivity detector 14 to 200 ℃, closing the second six-way valve 13 (the second chromatographic column 17 is communicated with the thermal conductivity detector 14), and purging the hydrogen purifier 15 and the chromatographic column by adopting high-purity argon for not less than 4 hours; then, the second six-way valve 13 is opened (the second chromatographic column 16 is communicated with the thermal conductivity detector 14), and the high-purity argon is continuously used as carrier gas to sweep the chromatographic column, wherein the sweep time is not less than 4 hours;
(2) cooling the chromatographic column and the hydrogen purifier 15 to 30 ℃, and reducing the temperature of the thermal conductivity detector 14 to 70 ℃;
(3) accessing the sample container 4 into the system according to the position shown in the attached figure 2, evacuating the chromatograph pipeline and the joint of the sample container 4, and performing vacuum leak detection to ensure the air tightness;
(4) observing the base line, opening the first six-way valve 12 after the base line is stable, and simultaneously starting to acquire signals of the thermal conductivity detector 14 so as to obtain a chromatogram under a blank sample introduction condition;
(5) when the time for collecting the signal of the thermal conductivity detector 14 reaches 10min, closing the first six-way valve 12, and evacuating the chromatograph pipeline again; confirming no false peak again through no obvious chromatographic peak under the blank sample introduction condition;
(6) slowly opening a valve of the sample container 4, filling 12413Pa sample gas into a vacuum sample injection system pipeline, and then closing the valve of the sample container 4;
(7) opening the first six-way valve 12, and simultaneously starting to acquire signals of the thermal conductivity detector 14 so as to obtain a chromatogram; during the period, the gas in the chromatographic pipeline is adsorbed by the adsorption bed 11, and the valve of the adsorption bed 11 is closed after the pressure is lower than 100 Pa;
(8) after 10min, closing the first six-way valve 12, and then evacuating the chromatograph pipeline;
(9) and integrating peak areas of all components of the chromatogram to obtain peak areas which are respectively as follows: 682 μ v · s/Pa, 678 μ v · s/Pa, 914 μ v · s/Pa, 9254 μ v · s/Pa;
(10) dividing the peak area by the product of the sensitivity factor and the sample injection pressure to obtain O2、N2、CH4And the content of the CO components is respectively as follows: 0.00723%, 0.00851%, 0.00423%, 0.12426%;
(11) changing the sample injection pressure, repeating the steps (6) to (10) to obtain O under the condition of the sample injection pressure of 11143Pa2、N2、CH4And the peak areas of the CO components are respectively as follows: 609 muv.s/Pa, 611 muv.s/Pa, 826 muv.s/Pa and 8304 muv.s/Pa, the contents are respectively as follows: 0.00721%, 0.00855%, 0.00426%, 0.12422%;
(12) changing the sample injection pressure, and repeating the steps (6) to (10) to obtain O under the condition of the sample injection pressure of 19847Pa2、N2、CH4And the peak areas of the CO components are respectively as follows: 1088 μ v · s/Pa, 1090 μ v · s/Pa, 14546 μ v · s/Pa, 14795 μ v · s/Pa, the contents are respectively: 0.00724%, 0.00856%, 0.00421%, 0.12425%;
(13) averaging the three measurement results of each component to obtain O2、N2、CH4And the content of the CO components is respectively as follows: 0.00723%, 0.00854%, 0.0043%, 0.1241%;
(14) closing the second six-way valve 13 (at this time, the first chromatographic column 16 is communicated with the thermal conductivity detector 14), observing the baseline, opening the first six-way valve 12 after the baseline is stable, and simultaneously starting to collect signals of the thermal conductivity detector 14 so as to obtain a chromatogram under a blank sample introduction condition;
(15) when the time for collecting the signal of the thermal conductivity detector 14 reaches 2min, closing the first six-way valve 12, and evacuating the chromatograph pipeline again; confirming that no false peak exists through no obvious chromatographic peak under the blank sample injection condition;
(16) slowly opening a valve of the sample container 4, filling 15239 gas into a vacuum sample injection system pipeline, and then closing the valve of the sample container 4;
(17) opening the first six-way valve 12, and simultaneously starting to acquire signals of the thermal conductivity detector 14 so as to obtain a chromatogram; during the period, the gas in the chromatographic pipeline is adsorbed by the adsorption bed 11, and the valve of the adsorption bed 11 is closed after the pressure is lower than 100 Pa;
(18) after 10min, closing the first six-way valve 12, and then evacuating the chromatograph pipeline;
(19) integrating peak areas of all components of the chromatogram to obtain3The area of the He peak is: 118754 μ v · s/Pa;
(20) dividing the peak area by the product of the sensitivity factor and the sample injection pressure to obtain3The content of the He component is as follows: 0.1840 percent;
(21) changing the sample injection pressure, and repeating the steps (16) to (20) to obtain the sample injection pressure of 15328Pa3The peak area of the He component is 119642 Muv.s/Pa, and the content is 0.1843%;
(22) changing the sample injection pressure, and repeating the steps (16) to (20) to obtain the sample injection pressure 10457Pa3The peak area of the He component is 81533 Muv.s/Pa, and the content is 0.1841%;
(23) averaging the three measurement results of each component to obtain3The content of the He components is respectively as follows: 0.1841 percent.
The device and the method for analyzing the impurities in the hydrogen isotope gas realize the high-precision analysis of helium by additionally arranging the hydrogen purifier at the front end of the chromatographic column, avoid the interference of argon on the high-precision analysis of oxygen impurities by using argon as carrier gas, and realize the high-precision analysis of one chromatograph by arranging two sets of chromatographic columns and adopting a mode of switching the chromatographic columns by adopting a six-way valve4He (or)3He) while considering O2、N2、CH4And high-precision analysis of CO.
The principle and the implementation mode of the invention are explained by applying a specific example, and the description of the embodiment is only used for helping to understand the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (10)
1. An apparatus for analyzing impurities in a hydrogen isotope gas, comprising:
a carrier gas source capable of containing argon gas;
a standard gas source capable of holding a standard gas;
a sample container capable of holding a sample gas;
the chromatographic column box comprises a first chromatographic column and a second chromatographic column, and the first chromatographic column and the second chromatographic column can be switched; the standard gas source and the sample container are capable of communicating with the first chromatography column and the second chromatography column, respectively;
the hydrogen purifier is communicated with the first chromatographic column and is positioned on one side of the first chromatographic column close to the sample container, and the hydrogen purifier can adsorb hydrogen isotope gas;
a thermal conductivity detector capable of detecting effluent gases of the first and second chromatography columns.
2. The apparatus for analyzing impurities in hydrogen isotope gas of claim 1, wherein: the hydrogen purifier includes top connection, filter tube and lower clutch, the filter tube set up in the top connection, the top connection has gas inlet, gas inlet with the opening of filter tube is linked together just gas inlet with set up the quartz cotton between the filter tube opening, be provided with palladium-carrying aluminium oxide in the filter tube, the lateral wall and the diapire of filter tube all have the through-hole, the lower clutch has gas outlet, the filter tube with gap between the top connection with gas outlet is linked together, the lower clutch with the top connection can be dismantled and connect and set up seal gasket between the two.
3. The apparatus for analyzing impurities in hydrogen isotope gas according to claim 2, characterized in that: the upper joint is internally provided with a positioning hole, the opening of the filter pipe extends into the positioning hole, a compression spring is arranged between one end, far away from the opening, of the filter pipe and the lower joint, and the compression spring can enable one end of the opening of the filter pipe to be abutted against the positioning hole.
4. The apparatus for analyzing impurities in hydrogen isotope gas according to claim 2, characterized in that: the upper joint is in sealing threaded connection with the lower joint; the sealing gasket is made of red copper, a silver coating is arranged on the outer surface of the sealing gasket, and the silver coating is made of silver.
5. The apparatus for analyzing impurities in hydrogen isotope gas according to claim 2, characterized in that: the upper joint and the lower joint are both provided with joint sections, and the joint sections are hexagonal prism-shaped structures.
6. The apparatus for analyzing impurities in hydrogen isotope gas according to claim 1, characterized in that: the sample container, the standard gas source and the carrier gas source are communicated with the first chromatographic column and the second chromatographic column by using a test pipeline, a first six-way valve and a second six-way valve are arranged on the test pipeline, the first chromatographic column and the second chromatographic column are switched by using the second six-way valve, the first chromatographic column and the second chromatographic column are connected with the thermal conductivity detector by using the second six-way valve, and the carrier gas source is communicated with the first chromatographic column and the second chromatographic column by using the second six-way valve.
7. The apparatus for analyzing impurities in hydrogen isotope gas according to claim 6, characterized in that: the testing device is characterized in that a pressure sensor and a vacuum gauge are further arranged on the testing pipeline, the testing pipeline is connected with a vacuum pump, the vacuum pump can vacuumize the testing pipeline, the vacuum pump is connected with a buffer tank, the thermal conductivity detector is connected with the buffer tank, and the buffer tank is provided with an exhaust interface.
8. The apparatus for analyzing impurities in hydrogen isotope gas according to claim 6, characterized in that: a stop valve is arranged between the standard gas source and the sample container, and the test pipeline is also connected with an adsorption bed.
9. A method for analyzing impurities in a hydrogen isotope gas, using the apparatus for analyzing impurities in a hydrogen isotope gas according to any one of claims 1 to 8, comprising the steps of:
selecting the first chromatographic column or the second chromatographic column according to the type of the analyzed impurities, introducing sample gas, standard gas and argon, and collecting signals of the thermal conductivity detector to obtain a chromatogram;
changing the pressure of the sample gas to obtain chromatograms under different sample introduction pressure conditions;
integrating the peak area of a chromatographic peak of each sample injection of the analytical component in the chromatogram, and obtaining the content of the analytical component according to the integrated area, the sample injection pressure and the temperature;
and step four, averaging the contents under different sample introduction pressure conditions to obtain a chromatographic analysis result of the analysis component.
10. The method for analyzing impurities in hydrogen isotope gas as recited in claim 9, wherein said apparatus for analyzing impurities in hydrogen isotope gas is first calibrated before the analysis, comprising the steps of:
step one, setting the temperature of the chromatographic column box and the thermal conductivity detector as an activation temperature, and purging the hydrogen purifier, the first chromatographic column and the second chromatographic column by using argon for not less than 4 hours;
step two, cooling the first chromatographic column, the second chromatographic column and the hydrogen purifier to set temperature, and adjusting the temperature of the thermal conductivity detector to working temperature;
step three, standard gas which contains helium and is similar to the gas component of the sample is accessed;
fourthly, vacuumizing and carrying out vacuum leak detection on the device for analyzing the impurities in the hydrogen isotope gas;
observing a base line, acquiring a signal of the thermal conductivity detector after the base line is stable, obtaining a chromatogram under a blank sample condition, and verifying the chromatogram in which the analysis component is not detected under the blank condition according to a blank sample result;
sixthly, after the chromatogram recording time is longer than the retention time of the component to be detected, vacuumizing the impurity analysis device in the hydrogen isotope gas;
step seven, introducing standard gas, collecting the signal of the thermal conductivity detector and obtaining a chromatogram;
step eight, after the thermal conductivity detector detects the complete chromatographic peak of the component to be detected, vacuumizing the impurity analysis device in the hydrogen isotope gas;
step nine, changing the sample injection pressure, and repeatedly performing the step seven and the step eight to continuously obtain chromatograms under different sample injection pressure conditions for more than 6 times;
step ten, integrating the peak areas of chromatographic peaks of each component in the chromatogram in each sample injection; drawing the chromatographic peak area and the sample injection pressure of the same component, and obtaining the slope of a fitting straight line and a linear correlation coefficient of the analysis component by least square fitting; and obtaining sensitivity factors of the chromatograph on all components by fitting the slope of the straight line and the content of the helium component in the standard gas.
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