CN108020612B - Device and method for analyzing content of trace impurities in hydrogen isotope gas and/or helium gas - Google Patents
Device and method for analyzing content of trace impurities in hydrogen isotope gas and/or helium gas Download PDFInfo
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- CN108020612B CN108020612B CN201711390218.2A CN201711390218A CN108020612B CN 108020612 B CN108020612 B CN 108020612B CN 201711390218 A CN201711390218 A CN 201711390218A CN 108020612 B CN108020612 B CN 108020612B
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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
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Abstract
The invention belongs to the technical field of gas chromatographic analysis, and relates to an analysis device and method for the content of trace impurities in hydrogen isotope gas and/or helium gas. The analysis device comprises a three-way pipeline, a first four-way pipeline, a second four-way pipeline, a six-way valve, a first four-way valve, a second four-way valve, a detector, a mechanical pump, a tritium-containing sample gas recovery tank, a tail gas exhaust outlet, a standard gas steel cylinder, a sample gas injection port, a pressure sensor, a pre-separation column and an analysis column. With the analysis device and method of the present invention, trace impurity components H in the gas for hydrogen isotope and/or helium can be obtained 2 、O 2 、N 2 、CO、CH 4 、CO 2 When the content analysis of the impurity components is finished at one time, the sample consumption is small, the analysis time is short, the exhaust emission is small, and the analysis accuracy is high.
Description
Technical Field
The invention belongs to the technical field of gas chromatographic analysis, and relates to an analysis device and method for the content of trace impurities in hydrogen isotope gas and/or helium gas.
Background
Tritium is a radioisotope of hydrogen, is a very important strategic energy substance, and has very important significance in other fields such as industry, national defense, scientific research and the like.
In liquid hydrogen (D) 2 In the cryogenic system (around 20K) of DT), any gas other than helium solidifies and accumulates in the rectifying column, heat exchanger, connecting piping, etc. Therefore, accurate monitoring of the content of trace impurity components in tritiated process gas by chromatography is required, which ensures proper operation of the process system.
In a plasma ash gas treatment system (TEP) of the international thermonuclear fusion experimental reactor project (ITER), it is required to judge by chromatography whether a mixed gas of helium containing tritium products and other impurity gases can meet emission standards of environmental protection and economic benefits after purification treatment.
At present, a normal (positive) sample injection mode is generally adopted for analyzing the contents of different impurity components in gas by gas chromatography. The gas chromatographic analysis adopting the sample injection mode not only requires that the sample to be analyzed is in a micro-positive pressure system, but also requires that the sample flow in the analysis is in a continuous steady-state process. The system suitable for the normal (positive) sample injection mode is only limited to a micro-positive pressure system (a negative pressure system is not suitable), the sample amount consumed in the gas chromatography analysis process adopting the sample injection mode is large, and the replacement of the pipeline environment before the analysis needs a long time, so that the application of the normal (positive) sample injection mode in the hydrogen isotope gas and/or helium gas analysis is limited.
Currently, gas chromatography is used for analyzing trace impurities (H 2 、O 2 、N 2 、CO、CH 4 、CO 2 ) The content adopts a double-needle sample injection mode, namely, one-needle sample injection aims at trace H in the sample 2 、O 2 、N 2 、CO、CH 4 Analysis of impurity component content (molecular sieve packed column is used as analysis column), and another needle sample is introduced to trace CO in the sample 2 Analysis of impurity component content (HayesepD packed column was used as analytical column). The gas path of the analysis scheme using the sample injection mode is relatively complex, compared with the single-needle sample injection of all impurity components (H 2 、O 2 、N 2 、CO、CH 4 、CO 2 ) The analysis prolongs the analysis period, increases the loss of the sample and the emission of the tail gas.
In addition, molecular sieve packed columns (e.g., 13X column, 5A column) commonly used in current gas chromatography analysis can adsorb trace amounts of oxygen, which affects the accuracy of the trace oxygen component analysis to some extent.
Disclosure of Invention
The primary object of the present invention is to provide an analyzing apparatus for the content of trace impurities in hydrogen isotope gas and/or helium gas so as to be capable of containing trace impurity components H in the hydrogen isotope gas and/or helium gas 2 、O 2 、N 2 、CO、CH 4 、CO 2 When the content analysis of the impurity components is finished at one time, the sample consumption is small, the analysis time is short, the exhaust emission is small, and the analysis accuracy is high.
In order to achieve the aim, in the basic embodiment, the invention provides an analysis device for the trace impurity content in hydrogen isotope gas and/or helium gas, which comprises a three-way pipeline, a first four-way pipeline, a second four-way pipeline, a six-way valve, a first four-way valve, a second four-way valve, a detector, a mechanical pump, a tritium-containing sample gas recovery tank, a tail gas exhaust outlet, a standard gas steel cylinder, a sample gas inlet, a pressure sensor, a pre-separation column and an analysis column,
the mechanical pump for discharging tail gas is connected with one pipeline of the three-way pipeline, and the other two pipelines of the three-way pipeline are respectively connected with the tritium-containing sample gas recovery tank and one pipeline of the first four-way pipeline;
the other three pipelines in the first four-way pipeline are respectively connected with the tail gas exhaust outlet, the standard gas steel cylinder and one pipeline in the second four-way pipeline;
the other three pipelines in the second four-way pipeline are respectively connected with the sample gas inlet, the pressure sensor and the six-way valve;
the sample gas or the standard gas can be controlled to enter the pre-separation column for pre-separation through the six-way valve by controlling the opening and closing of the six-way valve;
the pre-separation column is connected with the first four-way valve, and the opening and closing of the first four-way valve can control the outlet gas of the pre-separation column to enter the analysis column through the first four-way valve for chromatographic analysis;
the analysis column is connected with the second four-way valve, and the opening and closing of the second four-way valve can be controlled to control the outlet gas of the analysis column to enter the detector for detection through the second four-way valve.
In a preferred embodiment, the present invention provides an analysis device for the trace impurity content of hydrogen isotope gas and/or helium gas, wherein the detector is selected from one of a discharge helium ionization detector, a pulse discharge helium ionization detector, and a thermal conductivity detector.
In a preferred embodiment, the invention provides an analysis device for the content of trace impurities in hydrogen isotope gas and/or helium gas, wherein the length of the pre-separation column is 0.1-2.0m, the inner diameter is 2-5mm, and a 80-100-mesh shincarbor filling is filled in the pre-separation column; the length of the analytical column is 1.5-5.0m, the inner diameter is 2-5mm, and 80-100 meshes of shincarbon filler is filled in the analytical column.
In a preferred embodiment, the present invention provides an analysis device for the trace impurity content of hydrogen isotope gas and/or helium gas, wherein said analysis device further comprises a standard gas sampling valve and a pressure reducing valve connected to each other, which are provided on a pipe connecting said first four-way pipe of said standard gas cylinder, thereby connecting said pressure reducing valve to said standard gas cylinder.
In a preferred embodiment, the invention provides an analysis device for the content of trace impurities in hydrogen isotope gas and/or helium gas, wherein the analysis device further comprises a bellows valve, and the connection points of the rest pipelines are connected through the bellows valve except for the connection points on the six-way valve, the first four-way valve and the second four-way valve.
In a preferred embodiment, the invention provides an analysis device for the trace impurity content in hydrogen isotope gas and/or helium gas, wherein the analysis device further comprises a purge gas pipeline connected with the six-way valve, and the high-purity helium gas or high-purity deuterium gas can be controlled to enter the second four-way pipeline through the purge gas pipeline by controlling the opening and closing of the six-way valve.
A second object of the present invention is to provide a method for analyzing the content of trace impurities in hydrogen isotope gas and/or helium gas by using the analyzing apparatus as described above, so as to be able to use trace impurity component H in hydrogen isotope gas and/or helium gas 2 、O 2 、N 2 、CO、CH 4 、CO 2 When the content analysis of the impurity components is finished at one time, the sample consumption is small, the analysis time is short, the exhaust emission is small, and the analysis accuracy is high.
To achieve this object, in a basic embodiment, the present invention provides a method for analyzing the content of trace impurities in hydrogen isotope gas and/or helium gas using an analyzing apparatus as described above, said method comprising the steps of, in order:
(1) Replacement of the sample gas and sample gas sampling pipeline environment: purging pipelines related to sample introduction of the standard gas and the sample gas by introducing gas, and discharging the purged gas by the mechanical pump;
(2) And (3) standard curve preparation: the standard gas led out from the standard gas steel cylinder is respectively analyzed by the analysis column and detected by the detector at different pressures, the pressure measurement result of the pressure sensor is recorded, and a standard curve is drawn according to the detection results of the detector at different sample injection pressures;
(3) Analysis of trace impurity content in hydrogen isotope gas and/or helium: introducing sample gas from the sample gas inlet, analyzing by the analysis column and detecting by the detector, recording the pressure measurement result of the pressure sensor, and calculating the content of trace impurities in hydrogen isotope gas and/or helium according to the detection result, the pressure measurement result and a standard curve of the detector, wherein the trace impurities are H 2 、O 2 、N 2 、CO、CH 4 And CO 2 。
In a preferred embodiment, the present invention provides a method for analyzing the trace impurity content of hydrogen isotope gas and/or helium gas using the analysis apparatus as described above, wherein said method comprises the steps of, in order:
(1) Replacement of the sample gas and sample gas sampling pipeline environment: introducing high-purity helium (purity is more than or equal to 99.999%) or high-purity deuterium (purity is more than or equal to 99.999%) through the purging gas pipeline to purge pipelines related to sample introduction of standard gas and sample gas, and discharging the purged gas through the mechanical pump;
(2) And (3) standard curve preparation: the standard gas led out from the standard gas steel cylinder is respectively analyzed by the analysis column and detected by the detector at different pressures, the pressure measurement result of the pressure sensor is recorded, and a standard curve is drawn according to the detection results of the detector at different sample injection pressures;
(3) Analysis of trace impurity content in hydrogen isotope gas and/or helium: introducing sample gas from the sample gas inlet, analyzing by the analysis column and detecting by the detector, recording the pressure measurement result of the pressure sensor, and calculating the content of trace impurities in hydrogen isotope gas and/or helium according to the detection result, the pressure measurement result and a standard curve of the detector, wherein the trace impurities are H 2 、O 2 、N 2 、CO、CH 4 And CO 2 。
In a more preferred embodiment, the present invention provides a method for analyzing the content of hydrogen isotopes and/or trace impurities in helium using an analysis apparatus as described above, wherein the purge direction of the high purity helium or high purity deuterium is consistent with the pumping direction of the mechanical pump, which facilitates rapid and efficient replacement of clean sample tubing environments.
In a preferred embodiment, the present invention provides a method for analyzing the trace impurity content of hydrogen isotope gas and/or helium gas using the analysis apparatus described above, wherein in step (2) and step (3):
when analyzing the content of trace impurities in hydrogen standard gas or tritium-containing hydrogen, the first four-way valve is in an open state within 0-1.8min, and is in a closed state from 1.8min to the end of single analysis;
when the content of trace impurities in helium standard gas or tritium-containing helium is analyzed, the first four-way valve is always in a closed state.
In a preferred embodiment, the present invention provides a method for analyzing the content of trace impurities in hydrogen isotope gas and/or helium using an analysis apparatus as described above, wherein in step (3), the formula for calculating the content of trace impurities in hydrogen isotope gas and/or helium is:
Cv sample ＝P 1 ×A 2 ×Cv Label (C) /(P 2 ×A 1 )，
Wherein:
Cv label (C) 、Cv Sample The volume concentration of the standard gas and the sample gas are respectively in ppm;
A 1 、A 2 the response areas of the detectors of the components of the standard gas and the sample gas are respectively shown in mv.s;
P 1 、P 2 the sample injection pressures of the standard gas and the sample gas are respectively shown in Pa.
The invention has the beneficial effects that by utilizing the analysis device and the analysis method for the content of the trace impurity in the hydrogen isotope gas and/or helium gas, the trace impurity component H in the hydrogen isotope gas and/or helium gas can be used 2 、O 2 、N 2 、CO、CH 4 、CO 2 When the content analysis of the impurity components is finished at one time, the sample consumption is small, the analysis time is short, the exhaust emission is small, and the analysis accuracy is high.
In order to meet the analysis requirement of the content of trace impurity components in hydrogen isotope gas and/or helium, the invention carries out a reasonable optimization design on the traditional gas chromatograph sample injection system, and is specifically embodied as follows:
(1) Adopting a negative pressure sample injection mode to reduce the sample amount required by analysis;
(2) The environment of the sample pipeline is quickly and effectively replaced by the purging of high-purity helium or high-purity deuterium purging gas and the pumping of a mechanical pump, namely a one-flushing one-pumping mode, so that the loss of the sample gas and the emission of tail gas are reduced;
(3) The double-needle sample injection mode is replaced by the single-needle sample injection mode to finish the trace impurity component H 2 、O 2 、N 2 、CO、CH 4 、CO 2 The content of the sample is analyzed at one time, so that the analysis efficiency is improved, and the loss of the sample and the emission of tail gas are reduced;
(4) Work of replacing one molecular sieve packed column and one HayesepD packed column with two shinccaron packed columnsCan avoid the adsorption of molecular sieve packed column to oxygen and improve trace impurity component O 2 Is determined by the analysis accuracy of (a).
Drawings
Fig. 1 is a composition diagram of an exemplary analysis apparatus for trace impurity content in hydrogen isotope gas and/or helium gas according to the present invention.
FIG. 2 is an exemplary negative pressure sample introduction of different impurity components O 2 、N 2 、CH 4 Is a graph of the sample injection pressure versus the respective response area of each component.
FIG. 3 is an exemplary sample injection pattern of different impurity components H 2 、O 2 、N 2 、CO、CH 4 ，CO 2 Total analytical process chromatogram of the content.
Detailed Description
The composition of the analyzing device for the trace impurity content in the hydrogen isotope gas and/or helium gas of the invention is shown in fig. 1, and the analyzing device comprises a three-way pipeline A, a first four-way pipeline B, a second four-way pipeline C, a six-way valve D, a first four-way valve E, a second four-way valve F, a detector G, a tritium-containing sample gas recovery tank H, a tail gas exhaust outlet I, a standard gas steel bottle J, a sample gas inlet K, a pressure sensor L, a pre-separation column M, an analysis column N, a mechanical pump O, a first carrier gas pipeline P, a second carrier gas pipeline Q, a purge gas pipeline R, a first emptying pipeline S, a third carrier gas pipeline T, a second emptying pipeline U, a pressure display instrument, a sampling valve, a pressure reducing valve, a total exhaust outlet and a corrugated pipe valve.
Three ports of the three-way pipeline A are respectively connected with an air inlet pipeline A of the mechanical pump O 1 Tritium-containing sample gas recovery pipeline A 2 (connected with a tritium-containing sample gas recovery tank H) one end A of a first four-way pipeline B 3 -B 1 Are connected.
The other three ports of the first four-way pipeline B are respectively connected with the standard gas sampling pipeline B 2 (connecting standard gas steel bottle J), one end B of a second four-way pipeline C 3 -C 1 Exhaust gas discharge pipeline B 4 (connected with the tail gas outlet I).
The other three ports of the second four-way pipeline C are respectively connected with a sample gas pressure measuring pipeline for standard gas or tritium-containing sample gasC 2 Sample injection pipeline C of six-way valve D and pressure sensor L 3 -D 1 Tritium-containing sample gas sampling pipeline C 4 (connected with the sample gas inlet K).
When the six-way valve D state is closed, the connection states of the six ports are as follows: d of sample injection pipeline and six-way valve D 1 Point of connection, D 1 Point and D 2 Point is communicated with D 2 The point is connected with the air inlet of the quantitative ring, and the first carrier gas pipeline P and D 3 Point of connection, D 3 Point and D 4 Point is communicated with D 4 The point is connected with the air inlet of the pre-separation column M, and the air outlet of the quantitative ring is connected with the D 5 Connected with D 5 Point and D 6 Point is communicated with D 6 The point purge gas line R is connected.
When the six-way valve D state is open, the connection states of the six ports are as follows: d of sample injection pipeline and six-way valve D 1 Point of connection, D 1 Point and D 6 Point is communicated with D 6 The point is connected with a purging air pipeline R, and the air inlet of the quantitative ring is connected with D 2 Point of connection, D 2 Point and D 3 Point is communicated with D 3 The point is connected with a first carrier gas pipeline P, and the air inlet of the pre-separation column M is connected with a D 4 Point of connection, D 4 Point and D 5 Point is communicated with D 5 The point is connected with the air outlet of the quantitative ring.
When the state of the first four-way valve E is closed, the connection states of the four ports are as follows: e of the air outlet of the pre-separation column M and the first four-way valve E 1 Point of connection, E 1 Point and E 2 Point of communication E 2 The point is connected with the air inlet of the analysis column N, E 3 The point is connected with a second carrier gas pipeline Q, E 3 And E is connected with 4 Communicate with each other E 4 Is connected with the first emptying pipeline S.
When the state of the first four-way valve E is on, the connection states of the four ports are as follows: e of the air outlet of the pre-separation column M and the first four-way valve E 1 Point of connection, E 1 Point and E 4 Point of communication E 4 The point is connected with a first emptying pipeline S, and the air inlet of the analysis column N is connected with E 2 Point of connection, E 2 Point and E 3 Point of communication E 3 The point is connected to a second carrier gas line Q.
When the second four-way valve F state is closed, the connection states of the four ports are as follows: the air outlet of the analysis column N and F of the second four-way valve F 1 Point of connection, F 1 Point and F 2 Point is communicated with F 2 The point being connected to the inlet of the detector G, F 3 The point is connected with a third gas carrying pipeline T, F 3 Point and F 4 Point is communicated with F 4 The point is connected with a second emptying pipeline U.
When the second four-way valve F state is on, the connection states of the four ports are as follows: the air outlet of the analysis column N and F of the second four-way valve F 1 Point of connection, F 1 Point and F 4 Point is communicated with F 4 The point is connected with a second emptying pipeline U, F 2 The point being connected to the inlet of the detector G, F 2 And F is equal to 3 Communicating with each other, F 3 Is connected to a third carrier gas line T.
The detector G is one of a discharge helium ionization detector, a pulse discharge helium ionization detector and a thermal conductivity detector.
The length of the pre-separation column M is 0.1-2.0M, the inner diameter is 2-5mm, and 80-100 meshes of shincarbor filler is filled in the pre-separation column M
The length of the analytical column N is 1.5-5.0m, the inner diameter is 2-5mm, and 80-100 meshes of shincarbon filler is filled in the analytical column N.
The pressure measurement value of the pressure sensor L is displayed by a pressure display instrument.
The purge gas line R may be introduced with high purity helium or high purity deuterium.
Standard gas sample injection pipeline B 2 Is connected with a standard gas steel cylinder J through a standard gas sampling valve and a pressure reducing valve (not shown in the figure) which are arranged on the standard gas steel cylinder J.
The pipeline outlet of the mechanical pump O, the tail gas outlet I, the outlets of the emptying pipelines and the pipeline outlet of the detector G are led to a main air outlet (not shown in the figure).
Except for the connection points on the valve bodies of the six-way valve D, the first four-way valve E and the second four-way valve F, the connection points of the rest pipelines are all connected through a bellows valve.
The exemplary method for analyzing the trace impurity content of hydrogen isotope gas and/or helium using the above-described exemplary analysis apparatus operates as follows. ContainingTritium sample gas recovery pipeline A 2 The valve on this is only opened when sample needs to be recovered.
(1) Replacement of standard gas and sample injection pipeline environment
Opening the gas bottle valve, and sequentially opening the pressure reducing valve, the gas sampling valve and the tail gas discharging pipeline B 4 The valve is characterized in that a standard gas is used for blowing a valve body of the pressure reducing valve, a standard gas sampling valve and a standard gas sampling pipeline B 2 5-8min。
Closing the standard gas sampling pipeline B 2 The valve on the valve closes the tail gas discharge pipeline B 4 Tritium-containing sample gas sampling pipeline C 4 Valve on purging gas pipeline R, open sample gas pressure measuring pipeline C containing standard gas or tritium 2 And the valve pumps the standard gas and the sample injection pipeline environment to be lower than 10Pa through a mechanical pump O.
Closing the air inlet pipeline A of the mechanical pump O 1 Valve on the valve, observe standard gas or sample gas pressure measurement pipeline C containing tritium 2 The upper pressure shows the value of the instrument, the reading has no rising trend (indicating that the system has good tightness), and the R valve of the purge gas pipeline is opened until the high-purity helium enters the pipeline system.
Closing the R valve of the purge gas pipeline and opening the A inlet pipeline of the mechanical pump O 1 And the valve starts to vacuumize until the pressure display value is stable.
Repeating the steps for 2-5 times, and reducing the total content of the impurity components to be analyzed in the pipeline environment to below 50 ppb.
(2) Standard curve making
Regulating the outlet pressure of the pressure reducing valve to a certain pressure range, controlling the sample injection pressure of the standard gas (average sample injection pressures of four sample injection points are 54502Pa, 62451Pa, 70284Pa and 77439Pa respectively) through the standard gas sampling valve, and reading the standard gas or tritium-containing sample gas pressure measuring pipeline C 2 The upper pressure indicates the gauge value.
Closing the valves and opening the sample injection pipeline C of the six-way valve D 3 -D 1 The valve was subjected to chromatography, and the standard curve obtained by specific chromatography is shown in FIG. 2.
(3) Analysis of trace impurity component content in hydrogen isotope gas and/or helium gas
The pipe system is replaced completely as in the step (1), and the tritium-containing sample gas injection pipeline C is opened 4 Valve on the valve, sample gas pressure measuring pipeline C for reading standard gas or tritium 2 The upper pressure indicates the gauge value.
Closing the valves and opening the sample injection pipeline C of the six-way valve D 3 -D 1 The valve was subjected to chromatographic analysis, and the resulting chromatogram is shown in FIG. 3. Finally, the obtained chromatographic result is used for calculating the content of trace impurity components in the hydrogen isotope gas and/or helium to be H through the following formula 2 (C Calculated value ＝1.52ppm，C Theoretical value ＝1.47ppm)，O 2 (C Calculated value ＝2.21ppm，C Theoretical value ＝2.28ppm)，N 2 (C Calculated value ＝2.43ppm，C Theoretical value ＝2.37ppm)，CO(C Calculated value ＝2.35ppm，C Theoretical value ＝2.31ppm)，CH 4 (C Calculated value ＝2.88ppm，C Theoretical value ＝2.92ppm)，CO 2 (C Calculated value ＝3.83ppm，C Theoretical value ＝3.76ppm)。
Cv Sample ＝P 1 ×A 2 ×Cv Label (C) /(P 2 ×A 1 )，
Wherein:
Cv label (C) 、Cv Sample The volume concentration of the standard gas and the sample gas are respectively in ppm;
A 1 、A 2 the response areas of the detectors of the components of the standard gas and the sample gas are respectively shown in mv.s;
P 1 、P 2 the sample injection pressures of the standard gas and the sample gas are respectively shown in Pa.
In addition, the sample gas is recovered through a sample gas recovery pipeline A containing tritium 2 And selectively recycling the sample.
In the method, the purging direction of the purging gas is consistent with the pumping direction of the mechanical pump O.
In the method, the temperature of the pre-separation column M and the analysis column N is 60-70 ℃, the temperature of the detector G is 40-50 ℃, and the carrier gas flow rate at the outlet of the detector G is 40-45mL/min.
In the above method, in the step (2) and the step (3), a trace amount of O in the hydrogen standard gas or the hydrogen isotope gas is analyzed 2 、N 2 、CO、CH 4 、CO 2 When the impurity component content is in the impurity component content, the first four-way valve E is in an open state within 0-1.8min, and is in a closed state after 1.8min until the single analysis is finished; analysis of trace amounts of H in helium marking gas or tritium-containing helium 2 、O 2 、N 2 、CO、CH 4 、CO 2 When the content is in the first four-way valve E, the first four-way valve E is always in the off state.
The sample amount required for completing the primary analysis of the trace impurity content is 0.5-2mL, the time is less than 15min, and the tail gas emission amount is 1-3mL.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof. The foregoing examples or embodiments are merely illustrative of the invention, which may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The described embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. The scope of the invention should be indicated by the appended claims, and any changes that are equivalent to the intent and scope of the claims are intended to be encompassed within the scope of the invention.
Claims (8)
1. An analysis device for the content of trace impurities in hydrogen isotope gas and/or helium gas, which is characterized in that: the analysis device comprises a three-way pipeline, a first four-way pipeline, a second four-way pipeline, a six-way valve, a first four-way valve, a second four-way valve, a detector, a mechanical pump, a tritium-containing sample gas recovery tank, a tail gas exhaust outlet, a standard gas steel cylinder, a sample gas injection port, a pressure sensor, a pre-separation column and an analysis column,
the mechanical pump for discharging tail gas is connected with one pipeline of the three-way pipeline, and the other two pipelines of the three-way pipeline are respectively connected with the tritium-containing sample gas recovery tank and one pipeline of the first four-way pipeline;
the other three pipelines in the first four-way pipeline are respectively connected with the tail gas exhaust outlet, the standard gas steel cylinder and one pipeline in the second four-way pipeline;
the other three pipelines in the second four-way pipeline are respectively connected with the sample gas inlet, the pressure sensor and the six-way valve;
the sample gas or the standard gas can be controlled to enter the pre-separation column for pre-separation through the six-way valve by controlling the opening and closing of the six-way valve;
the pre-separation column is connected with the first four-way valve, and the opening and closing of the first four-way valve can control the outlet gas of the pre-separation column to enter the analysis column through the first four-way valve for chromatographic analysis;
the analysis column is connected with the second four-way valve, and the opening and closing of the second four-way valve can be controlled to control the outlet gas of the analysis column to enter the detector for detection through the second four-way valve;
the length of the pre-separation column is 0.1-2.0m, the inner diameter is 2-5mm, and 80-100 meshes of shincarbon filler is filled in the pre-separation column; the length of the analytical column is 1.5-5.0m, the inner diameter is 2-5mm, and 80-100 meshes of shincarbon filler is filled in the analytical column.
2. The analysis device according to claim 1, wherein: the detector is selected from one of a discharge helium ionization detector, a pulse discharge helium ionization detector and a thermal conductivity detector.
3. The analysis device according to claim 1, wherein: the analysis device also comprises a standard gas sampling valve and a pressure reducing valve which are connected with each other and are arranged on one pipeline connected with the first four-way pipeline of the standard gas steel cylinder, so that the pressure reducing valve is connected with the standard gas steel cylinder.
4. The analysis device according to claim 1, wherein: the analysis device also comprises a bellows valve, and the connection points of the rest pipelines are connected through the bellows valve except the connection points on the six-way valve, the first four-way valve and the second four-way valve body.
5. The analysis device according to claim 1, wherein: the analysis device also comprises a purge gas pipeline connected with the six-way valve, and high-purity helium gas or high-purity deuterium gas can be controlled to enter the second four-way pipeline through the purge gas pipeline by controlling the opening and closing of the six-way valve.
6. A method for analyzing the content of trace impurities in hydrogen isotope gas and/or helium gas by using the analyzing apparatus according to any one of claims 1-5, characterized in that the method comprises the following steps in order:
(1) Replacement of the sample gas and sample gas sampling pipeline environment: purging pipelines related to sample introduction of the standard gas and the sample gas by introducing gas, and discharging the purged gas by the mechanical pump; the introduced gas is high-purity helium or high-purity deuterium;
(2) And (3) standard curve preparation: the standard gas led out from the standard gas steel cylinder is respectively analyzed by the pre-separation column and the analysis column and detected by the detector at different pressures, the pressure measurement result of the pressure sensor is recorded, and a standard curve is drawn according to the detection results of the detector at different sample injection pressures; the temperature of the pre-separation column and the analysis column is 60-70 ℃, the temperature of the detector is 40-50 ℃, and the carrier gas flow rate at the outlet of the detector is 40-45mL/min;
(3) Analysis of trace impurity content in hydrogen isotope gas and/or helium: introducing sample gas from the sample gas inlet, analyzing by the pre-separation column and the analysis column and detecting by the detector, recording the pressure measurement result of the pressure sensor, and detecting according to the detectorThe content of trace impurities in the hydrogen isotope gas and/or helium is calculated by the detection result, the pressure measurement result and the standard curve, wherein the trace impurities are H 2 、O 2 、N 2 、CO、CH 4 And CO 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the pre-separation column and the analysis column is 60-70 ℃, the temperature of the detector is 40-50 ℃, and the carrier gas flow rate at the outlet of the detector is 40-45mL/min.
7. The method according to claim 6, wherein: the purging direction of the high-purity helium or high-purity deuterium is consistent with the pumping direction of the mechanical pump.
8. The method according to claim 6 or 7, wherein in the step (3), the formula for calculating the content of trace impurities in the hydrogen isotope gas and/or helium gas is:
Cv sample =P 1 ×A 2 ×Cv Label (C) /(P 2 ×A 1 )，
Wherein:
Cv label (C) 、Cv Sample The volume concentrations of the standard gas and the sample gas are respectively;
A 1 、A 2 the response areas of the detectors for the components of the target gas and the sample gas, respectively;
P 1 、P 2 the sample injection pressures of the standard gas and the sample gas are respectively.
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