CN108020612A - The analytical equipment and method of trace impurity content in hydrogen isotope gas and/or helium - Google Patents
The analytical equipment and method of trace impurity content in hydrogen isotope gas and/or helium Download PDFInfo
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- CN108020612A CN108020612A CN201711390218.2A CN201711390218A CN108020612A CN 108020612 A CN108020612 A CN 108020612A CN 201711390218 A CN201711390218 A CN 201711390218A CN 108020612 A CN108020612 A CN 108020612A
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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
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
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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
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
- G01N2030/201—Injection using a sampling valve multiport valves, i.e. having more than two ports
Abstract
The invention belongs to gas chromatographic analysis technique field, it is related to the analytical equipment and method of trace impurity content in hydrogen isotope gas and/or helium.The analytical equipment includes three-way pipeline, the first four-way pipeline, the second four-way pipeline, six-way valve, the first four-way valve, the second four-way valve, detector, mechanical pump, the recycling can of sample gas containing tritium, tail gas exhaust mouth, standard gas steel cylinder, sample gas injection port, pressure sensor, pre-separation column, analytical column.Using the present invention analytical equipment and method, can in for hydrogen isotope gas and/or helium trace impurity component H2、O2、N2、CO、CH4、CO2Content analysis when, once complete the analysis of all impurity composition contents, sample consumption is small, and analysis time is short, and exhaust emissions amount is few, with high accuracy.
Description
Technical field
The invention belongs to gas chromatographic analysis technique field, is related to trace impurity content in hydrogen isotope gas and/or helium
Analytical equipment and method.
Background technology
Tritium is the radio isotope of hydrogen, is a kind of highly important strategic energy substance, is ground in industry, national defence and science
Other fields such as study carefully and all have and be of great significance.
In liquid hydrogen (D2- DT) cryogenic system (20K or so) in, any gas in addition to helium can all solidify and in rectifying
Accumulated in the components such as tower, heat exchanger, connecting pipe.Therefore, it is necessary to by micro in process gas of the chromatography accurate measurements containing tritium
The content of impurity composition, this can ensure the normal operation of process system.
It is in the plasma ash discharge gas processing system (TEP) of International Thermal-Nuclear Experimental Reactor plan (ITER), it is necessary to logical
Cross chromatography judge the helium of the product containing tritium and the mixed gas of other foreign gases whether can meet after purified treatment environmental protection and
The discharge standard of economic benefit.
At present, gas-chromatography is normal (just) into sample prescription to the analysis generally use of different impurities constituent content in gas
Formula.Sample to be analysed is not required nothing more than using the gas chromatographic analysis of the input mode and is in micro-positive pressure system, and requires analysis
In sample flow be in continuous steady-state process.Often (just) to be limited only to micro-positive pressure system (negative for system that input mode is applicable in
Laminate system does not apply to), it is larger using the sample size being lost during the gas chromatographic analysis of the input mode, analyze preceding pipeline ring
The displacement in border needs the long period, these all limit normal (just) input mode in hydrogen isotope gas and/or helium analysis
Application.
At present, gas-chromatography is in analysis trace impurity (H2、O2、N2、CO、CH4、CO2) content when using crosspointer sample introduction
Pattern, i.e., a sample needle sample introduction needle is to H micro in sample2、O2、N2、CO、CH4The analysis of impurity composition content (uses molecule
Packed column is sieved as analytical column), in addition a sample needle sample introduction needle is to CO micro in sample2The analysis of impurity composition content (is adopted
Analytical column is used as by the use of HayesepD packed columns).Gas circuit using the analytical plan of the sample introduction pattern is complex, is compared to list
Full impurity composition (the H of pin sample introduction2、O2、N2、CO、CH4、CO2) analysis, extend analytical cycle, add sample waste and
The discharge capacity of tail gas.
In addition, at present the common molecular sieve packed column of gas chromatographic analysis (such as 13X columns, 5A columns) can adsorb it is micro
Oxygen, this have impact on the accuracy of micro amount of oxygen component analysis to a certain extent.
The content of the invention
The primary and foremost purpose of the present invention is to provide the analytical equipment of trace impurity content in hydrogen isotope gas and/or helium, with
Can in for hydrogen isotope gas and/or helium trace impurity component H2、O2、N2、CO、CH4、CO2Content analysis when, one
The secondary analysis for completing all impurity composition contents, sample consumption is small, and analysis time is short, and exhaust emissions amount is few, accuracy of analysis
It is high.
In order to achieve this, in the embodiment on basis, the present invention provides micro miscellaneous in hydrogen isotope gas and/or helium
The analytical equipment of matter content, the analytical equipment include three-way pipeline, the first four-way pipeline, the second four-way pipeline, six-way valve,
First four-way valve, the second four-way valve, detector, mechanical pump, the recycling can of sample gas containing tritium, tail gas exhaust mouth, standard gas steel cylinder, sample
Gas injection port, pressure sensor, pre-separation column, analytical column,
It is connected for discharging the mechanical pump of tail gas with a pipeline in the three-way pipeline, described three
Other two pipelines threaded a pipe respectively with one in the recycling can of sample gas containing tritium, the first four-way pipeline
Pipeline is connected；
Other three pipelines in the first four-way pipeline respectively with the tail gas exhaust mouth, the standard gas steel
A pipeline in bottle, the second four-way pipeline is connected；
Other three pipelines in the second four-way pipeline respectively with the sample gas injection port, the pressure
Sensor, the six-way valve are connected；
By controlling the opening and closing of the six-way valve, can control the sample gas or standard gas through the six-way valve into
Enter the pre-separation column and carry out pre-separation；
The pre-separation column is connected with first four-way valve, by controlling opening for first four-way valve
Close, the exit gas of the pre-separation column can be controlled to enter the analytical column through first four-way valve and carry out chromatography
Analysis；
The analytical column is connected with second four-way valve, by controlling the opening and closing of second four-way valve,
The exit gas of the analytical column can be controlled to be detected through second four-way valve into the detector.
In a preferred embodiment, the present invention provides trace impurity content in hydrogen isotope gas and/or helium
Analytical equipment, wherein the detector is selected from electric discharge helium ionization detector, pulsed discharge helium ionization detector, thermal conductivity inspection
Survey one kind in device.
In a preferred embodiment, the present invention provides trace impurity content in hydrogen isotope gas and/or helium
Analytical equipment, wherein the pre-separation column length is 0.1-2.0m, internal diameter 2-5mm, built-in 80-100 purposes
Shincarbon fillers；The analysis column length is 1.5-5.0m, internal diameter 2-5mm, built-in 80-100 purposes
Shincarbon fillers.
In a preferred embodiment, the present invention provides trace impurity content in hydrogen isotope gas and/or helium
Analytical equipment, wherein the analytical equipment further includes the standard gas sampling valve being connected to each other, pressure reducing valve, they are arranged on connection institute
On one pipeline of the first four-way pipeline for the standard gas steel cylinder stated, so that the pressure reducing valve and the standard gas steel
Bottle is connected.
In a preferred embodiment, the present invention provides trace impurity content in hydrogen isotope gas and/or helium
Analytical equipment, wherein the analytical equipment further includes bellows valve, except the six-way valve, first four-way valve, institute
Outside the tie point on the second four-way valve body stated, the tie point of remaining pipes is connected by the bellows valve.
In a preferred embodiment, the present invention provides trace impurity content in hydrogen isotope gas and/or helium
Analytical equipment, wherein the analytical equipment further includes the purging feed channel being connected with the six-way valve, by controlling
The opening and closing for the six-way valve stated, can control high-purity helium or high pure deuterium gas to enter the second four-way pipe by the purging feed channel
Road.
Second object of the present invention is to provide carries out hydrogen isotope gas and/or helium using analytical equipment as described above
The method of middle trace impurity content analysis, so as to the trace impurity component H in for hydrogen isotope gas and/or helium2、O2、
N2、CO、CH4、CO2Content analysis when, once complete the analysis of all impurity composition contents, sample consumption is small, analysis time
Short, exhaust emissions amount is few, with high accuracy.
In order to achieve this, in the embodiment on basis, the present invention is provided to be carried out using analytical equipment as described above
The method of trace impurity content analysis in hydrogen isotope gas and/or helium, the method in turn include the following steps：
(1) displacement of standard gas and sample gas sample channel environment：By introduce gas to respectively with standard gas and sample gas sample introduction
Relevant pipeline is purged, and discharges purged gas by the mechanical pump；
(2) standard curve making：The standard gas that the standard gas steel cylinder is drawn is taken up in order of priority by described with different pressures
Analytical column carries out analysis with being detected by the detector, and records the pressure measurement knot of the pressure sensor
Fruit, standard curve is drawn according to the detector testing result under different sample introduction pressure；
(3) trace impurity content analysis in hydrogen isotope gas and/or helium：Sample is imported from the sample gas injection port
Gas, successively carries out analysis with being detected by the detector by the analytical column, and records the pressure and pass
The pressure measurements of sensor, it is same to calculate hydrogen according to the testing result, pressure measurements and standard curve of the detector
The content of trace impurity in the plain gas in position and/or helium, the trace impurity is H2、O2、N2、CO、CH4And CO2。
In a preferred embodiment, the present invention is provided carries out hydrogen isotope gas using analytical equipment as described above
And/or in helium trace impurity content analysis method, wherein the method in turn includes the following steps：
(1) displacement of standard gas and sample gas sample channel environment：It is (pure that high-purity helium is introduced by the purging feed channel
Degree >=99.999%) or high pure deuterium gas (purity >=99.999%) to respectively being blown with standard gas and the relevant pipeline of sample gas sample introduction
Sweep, and purged gas is discharged by the mechanical pump；
(2) standard curve making：The standard gas that the standard gas steel cylinder is drawn is taken up in order of priority by described with different pressures
Analytical column carries out analysis with being detected by the detector, and records the pressure measurement knot of the pressure sensor
Fruit, standard curve is drawn according to the detector testing result under different sample introduction pressure；
(3) trace impurity content analysis in hydrogen isotope gas and/or helium：Sample is imported from the sample gas injection port
Gas, successively carries out analysis with being detected by the detector by the analytical column, and records the pressure and pass
The pressure measurements of sensor, it is same to calculate hydrogen according to the testing result, pressure measurements and standard curve of the detector
The content of trace impurity in the plain gas in position and/or helium, the trace impurity is H2、O2、N2、CO、CH4And CO2。
In a kind of more preferred embodiment, the present invention is provided carries out the same position of hydrogen using analytical equipment as described above
The method of trace impurity content analysis in plain gas and/or helium, wherein the high-purity helium or the purging direction of high pure deuterium gas
It is consistent with the draw-off direction of the mechanical pump, be conducive to quick, effective displacement clean sample pipeline environment.
In a preferred embodiment, the present invention is provided carries out hydrogen isotope gas using analytical equipment as described above
And/or in helium trace impurity content analysis method, wherein in step (2) and step (3)：
When analyzing the content of trace impurity in hydrogen standard gas or hydrogen containing tritium, first four-way valve is in 0-1.8min
Open state, off status is at the end of being analyzed to single after 1.8min；
When analyzing the content of trace impurity in helium standard gas or helium containing tritium, first four-way valve is all the time in closing shape
State.
In a preferred embodiment, the present invention is provided carries out hydrogen isotope gas using analytical equipment as described above
And/or in helium trace impurity content analysis method, wherein in step (3), calculate micro in hydrogen isotope gas and/or helium
The formula of the content of impurity is：
CvSample=P1×A2×CvMark/(P2×A1),
Wherein：
CvMark、CvSampleThe respectively volumetric concentration of standard gas and sample gas, unit ppm；
A1、A2The respectively detector response area of standard gas and sample gas component, unit mvs；
P1、P2The respectively sample introduction pressure of standard gas and sample gas, unit Pa.
The beneficial effects of the present invention are utilize trace impurity content in the hydrogen isotope gas and/or helium of the present invention
Analytical equipment and method, can in for hydrogen isotope gas and/or helium trace impurity component H2、O2、N2、CO、CH4、CO2
Content analysis when, once complete the analysis of all impurity composition contents, sample consumption is small, and analysis time is short, exhaust emissions
Amount is few, with high accuracy.
To meet the analysis demand of trace impurity constituent content in hydrogen isotope gas and/or helium, the present invention is to tradition
The sampling system of gas-chromatography carried out again rational optimization design, embody as follows：
(1) sample size needed for analysis is reduced using Ngatively pressurized sampling mode；
(2) extraction of high-purity helium or the purging and mechanical pump of high pure deuterium gas purge gass, i.e. " punching one is taken out " mode are passed through
Clean sample pipeline environment is fast and effectively replaced, reduces the loss of sample gas and the discharge of tail gas；
(3) crosspointer sample introduction pattern is substituted with a pin sample introduction pattern, completes trace impurity component H2、O2、N2、CO、CH4、CO2's
The disposable analysis of content, reduces the waste of sample and the discharge capacity of tail gas while improving analysis efficiency；
(4) work(of a molecular sieve packed column and a HayesepD packed column is replaced with two shincarbon packed columns
Can, absorption of the molecular sieve packed column to oxygen is avoided, improves trace impurity component O2Accuracy of analysis.
Brief description of the drawings
Fig. 1 is the group of the analytical equipment of trace impurity content in exemplary hydrogen isotope gas and/or helium of the invention
Cheng Tu.
Fig. 2 is the exemplary different impurities component O obtained using Ngatively pressurized sampling mode2、N2、CH4Sample introduction pressure with it is each
Component each responds the graph of a relation of area.
Fig. 3 is the different impurities component H that exemplary one pin sample introduction pattern of use obtains2、O2、N2、CO、CH4, CO2Content
Complete analysis process chromatogram.
Embodiment
The composition of the analytical equipment of trace impurity content is as schemed in exemplary hydrogen isotope gas and/or helium of the invention
Shown in 1, including three-way pipeline A, the first four-way pipeline B, the second four-way pipeline C, six-way valve D, the first four-way valve E, the second four-way
Valve F, detector G, the recycling can of sample gas containing tritium H, tail gas exhaust mouth I, standard gas steel cylinder J, sample gas injection port K, pressure sensor
L, pre-separation column M, analytical column N, mechanical pump O, the first gas-carrier pipeline P, the second gas-carrier pipeline Q, purging air pipe R, the first emptying
Pipeline S, the 3rd gas-carrier pipeline T, the second blowdown piping U, pressure display instrument table, sampling valve, pressure reducing valve, total exhaust outlet, bellows
Valve.
Tri- ports of three-way pipeline A respectively with mechanical pump O air inlet pipelines A1, sample gas recovery pipe A containing tritium2(connection contains
Tritium sample gas recycling can H), one end A of the first four-way pipeline B3-B1It is connected.
First four-way pipeline B the other threes port respectively with standard gas sample introduction pipeline B2(connection standard gas steel cylinder J), the second four-way
One end B of pipeline C3-C1, exhaust emissions pipeline B4(connection tail gas exhaust mouth I) is connected.
The second four-way pipeline C the other threes port sample gas pressure measurement pipeline C with standard gas or containing tritium respectively2(connection pressure
Sensor L), the sample introduction pipeline C of six-way valve D3-D1, sample gas sample introduction pipeline C containing tritium4(connection sample gas injection port K) is connected.
When six-way valve D-state is closes, the connection status of six ports is：The D of sample introduction pipeline and six-way valve D1Point is connected, D1
Point and D2Point communicates, D2Point is connected with the air inlet of quantitative loop, the first gas-carrier pipeline P and D3Point is connected, D3Point and D4Point communicates, D4
Point is connected with the air inlet of pre-separation column M, the gas outlet of quantitative loop and D5It is connected, D5Point and D6Point communicates, D6Point purging air pipe
R is connected.
Six-way valve D-state is when opening, the connection status of six ports is：The D of sample introduction pipeline and six-way valve D1Point is connected, D1
Point and D6Point communicates, D6Point is connected with purging air pipe R, the air inlet and D of quantitative loop2Point is connected, D2Point and D3Point communicates, D3Point
It is connected with the first gas-carrier pipeline P, the air inlet and D of pre-separation column M4Point is connected, D4Point and D5Point communicates, D5Point and quantitative loop
Gas outlet is connected.
When first four-way valve E-state is closes, the connection status of four ports is：The gas outlet and the one or four of pre-separation column M
The E of port valve E1Point is connected, E1Point and E2Point communicates, E2Point is connected with the air inlet of analytical column N, E3Point and the second gas-carrier pipeline Q phases
Even, E3With E4Communicate, E4Connect with the first blowdown piping S-phase.
First four-way valve E-state is when opening, the connection status of four ports is：The gas outlet and the one or four of pre-separation column M
The E of port valve E1Point is connected, E1Point and E4Point communicates, E4Point connects with the first blowdown piping S-phase, the air inlet and E of analytical column N2Point phase
Even, E2Point and E3Point communicates, E3Point is connected with the second gas-carrier pipeline Q.
When second four-way valve F states is close, the connection status of four ports is：The gas outlet of analytical column N and the second four-way
The F of valve F1Point is connected, F1Point and F2Point communicates, F2Point is connected with the air inlet of detector G, F3Point connects with the 3rd gas-carrier pipeline T-phase,
F3Point and F4Point communicates, F4Point is connected with the second blowdown piping U.
Second four-way valve F states is when opening, the connection status of four ports are：The gas outlet of analytical column N and the second four-way
The F of valve F1Point is connected, F1Point and F4Point communicates, F4Point is connected with the second blowdown piping U, F2Point is connected with the air inlet of detector G,
F2With F3Communicate, F3Connect with the 3rd gas-carrier pipeline T-phase.
Detector G is one in electric discharge helium ionization detector, pulsed discharge helium ionization detector, thermal conductivity detector (TCD)
Kind.
The length of pre-separation column M is 0.1-2.0m, internal diameter 2-5mm, the shincarbon fillers of built-in 80-100 mesh
Analytical column N length is 1.5-5.0m, internal diameter 2-5mm, the shincarbon fillers of built-in 80-100 mesh.
The pressure measuring value of pressure sensor L is shown by pressure display instrument table.
Purging air pipe R can import high-purity helium or high pure deuterium gas.
Standard gas sample introduction pipeline B2Pass through the standard gas sampling valve, pressure reducing valve (not shown) and standard gas steel cylinder J set thereon
Connection.
The tube outlet of mechanical pump O, tail gas exhaust mouth I, the tube outlet of the outlet of each blowdown piping and detector G draw
To total exhaust outlet (not shown).
In addition to the tie point on six-way valve D, the first four-way valve E, second four-way valve F valve body itself, the connection of remaining pipes
Point is connected by bellows valve.
Utilize trace impurity content in the analytical equipment of above-mentioned example exemplary carry out hydrogen isotope gas and/or helium
The operating procedure of the method for analysis is as follows.Sample gas recovery pipe A containing tritium2On valve only sample need recycling when just beat
Open.
(1) displacement of standard gas and sample feeding pipeline environment
Standard gas bottle valve is opened, and opens pressure reducing valve, standard gas sampling valve and exhaust emissions pipeline B successively4On valve, use
Standard gas purging relief valve body, standard gas sampling valve and standard gas sample introduction pipeline B2 5-8min。
Close standard gas sample introduction pipeline B2On valve, close exhaust emissions pipeline B4, sample gas sample introduction pipeline C containing tritium4、
The valve on air pipe R is purged, opens standard gas or the sample gas pressure measurement pipeline C containing tritium2On valve, will be marked by mechanical pump O
Gas and sample feeding pipeline environment are evacuated to less than 10Pa.
Close mechanical pump O air inlet pipelines A1On valve, observe standard gas or the sample gas pressure measurement pipeline C containing tritium2Upper pressure is shown
Show instrument value, ascendant trend (showing that system sealing is good) does not occur in reading, opens purging air pipe R valves until high-purity
Helium enters pipe-line system.
Purging air pipe R valves are closed, open mechanical pump O air inlet pipelines A1On valve, start to vacuumize until pressure
Show value stabilization.
Repeat the above steps 2-5 times, impurity composition total content to be analyzed in pipeline environment is down to below 50ppb.
(2) standard curve making
Decompression valve outlet pressure is adjusted to certain pressure limit, passes through the sample introduction pressure of standard gas sampling valve control standard gas
(the average sample introduction pressure of four sample delivery points is respectively 54502Pa, 62451Pa, 70284Pa, 77439Pa), reads standard gas or contains
The sample gas pressure measurement pipeline C of tritium2Upper pressure display instrument tabular value.
Above-mentioned each valve is closed, opens the sample introduction pipeline C of six-way valve D3-D1On valve carry out chromatography, specific chromatography
Analysis gained standard curve is as shown in Figure 2.
(3) in hydrogen isotope gas and/or helium trace impurity constituent content analysis
As above-mentioned steps (1) replace pipe-line system clean, the sample gas sample introduction pipeline C containing tritium is opened4On valve,
Read standard gas or the sample gas pressure measurement pipeline C containing tritium2Upper pressure display instrument tabular value.
Above-mentioned each valve is closed, opens the sample introduction pipeline C of six-way valve D3-D1On valve carry out chromatography, gained chromatography
Figure is as shown in Figure 3.Most at last the chromatographic results of gained pass through equation below calculate it is micro miscellaneous in hydrogen isotope gas and/or helium
The content of matter component, is H2(CCalculated value=1.52ppm, CTheoretical value=1.47ppm), O2(CCalculated value=2.21ppm, CTheoretical value=
2.28ppm), N2(CCalculated value=2.43ppm, CTheoretical value=2.37ppm), CO (CCalculated value=2.35ppm, CTheoretical value=2.31ppm), CH4
(CCalculated value=2.88ppm, CTheoretical value=2.92ppm), CO2(CCalculated value=3.83ppm, CTheoretical value=3.76ppm).
CvSample=P1×A2×CvMark/(P2×A1),
Wherein：
CvMark、CvSampleThe respectively volumetric concentration of standard gas and sample gas, unit ppm；
A1、A2The respectively detector response area of standard gas and sample gas component, unit mvs；
P1、P2The respectively sample introduction pressure of standard gas and sample gas, unit Pa.
In addition, pass through the sample gas recovery pipe A containing tritium2Selectivity recycles sample.
In the above method, the purging direction of purge gass is consistent with the draw-off direction of mechanical pump O.
In the above method, pre-separation column M, the temperature of analytical column N are 60-70 DEG C, and the temperature of detector G is 40-50 DEG C, inspection
It is 40-45mL/min to survey device G outlets carrier gas flux.
In the above method, step (2) is with step (3), analyzing O micro in hydrogen standard gas or hydrogen isotope gas2、N2、
CO、CH4、CO2During impurity composition content, the first four-way valve E is in open state in 0-1.8min, analyzes and ties to single after 1.8min
Beam is in off status；Analyze H micro in helium standard gas or helium containing tritium2、O2、N2、CO、CH4、CO2During content, the first four-way valve E
All the time it is in off status.
It is 0.5-2mL to complete the sample size needed for an above-mentioned trace impurity content analysis, and the time is less than 15min, tail gas
Discharge capacity is 1-3mL.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
God and scope.If in this way, belong to the model of the claims in the present invention and its equivalent technology to these modifications and changes of the present invention
Within enclosing, then the present invention is also intended to comprising including these modification and variations.Above-described embodiment or embodiment are simply to the present invention
For example, the present invention can also be implemented with other ad hoc fashions or other particular form, without departing from the present invention's
Main idea or substantive characteristics.Therefore, it is regarded as from the point of view of the embodiment of description is in terms of any illustrative and non-limiting.This
The scope of invention should be illustrated that any change equivalent with the intention of claim and scope should also be included by appended claims
Within the scope of the invention.
Claims (10)
1. the analytical equipment of trace impurity content in hydrogen isotope gas and/or helium, it is characterised in that：The analytical equipment bag
Include three-way pipeline, the first four-way pipeline, the second four-way pipeline, six-way valve, the first four-way valve, the second four-way valve, detector, machinery
Pump, the recycling can of sample gas containing tritium, tail gas exhaust mouth, standard gas steel cylinder, sample gas injection port, pressure sensor, pre-separation column, analysis
Column,
It is connected for discharging the mechanical pump of tail gas with a pipeline in the three-way pipeline, the three-way pipe
Other two pipelines in road respectively with a pipeline in the recycling can of sample gas containing tritium, the first four-way pipeline
It is connected；
Other three pipelines in the first four-way pipeline respectively with the tail gas exhaust mouth, the standard gas steel cylinder,
A pipeline in the second four-way pipeline is connected；
Other three pipelines in the second four-way pipeline respectively with the sample gas injection port, the pressure sensing
Device, the six-way valve are connected；
By controlling the opening and closing of the six-way valve, the sample gas or standard gas can be controlled to enter institute through the six-way valve
The pre-separation column stated carries out pre-separation；
The pre-separation column is connected with first four-way valve, can by controlling the opening and closing of first four-way valve
Chromatography is carried out to control the exit gas of the pre-separation column to enter the analytical column through first four-way valve；
The analytical column is connected with second four-way valve, can be with by controlling the opening and closing of second four-way valve
The exit gas of the control analytical column is detected through second four-way valve into the detector.
2. analytical equipment according to claim 1, it is characterised in that：The detector is selected from helium ionized detection of discharging
One kind in device, pulsed discharge helium ionization detector, thermal conductivity detector (TCD).
3. analytical equipment according to claim 1, it is characterised in that：The pre-separation column length is 0.1-2.0m, interior
Footpath is 2-5mm, the shincarbon fillers of built-in 80-100 mesh；The analysis column length is 1.5-5.0m, internal diameter 2-
5mm, the shincarbon fillers of built-in 80-100 mesh.
4. analytical equipment according to claim 1, it is characterised in that：The analytical equipment further includes the mark being connected to each other
Gas sampling valve, pressure reducing valve, they are arranged on a pipeline of the first four-way pipeline of the connection standard gas steel cylinder,
So that the pressure reducing valve is connected with the standard gas steel cylinder.
5. analytical equipment according to claim 1, it is characterised in that：The analytical equipment further includes bellows valve, removes
The six-way valve, first four-way valve, outside the tie point on second four-way valve body, the connection of remaining pipes
Point is connected by the bellows valve.
6. analytical equipment according to claim 1, it is characterised in that：The analytical equipment is further included to be led to described six
The purging feed channel that valve is connected, by controlling the opening and closing of the six-way valve, can control high-purity helium or high pure deuterium gas to lead to
Cross the purging feed channel and enter the second four-way pipeline.
7. carried out using the analytical equipment described in any one in claim 1-5 micro miscellaneous in hydrogen isotope gas and/or helium
The method of matter content analysis, it is characterised in that the method in turn includes the following steps：
(1) displacement of standard gas and sample gas sample channel environment：By introducing gas to respectively related to standard gas and sample gas sample introduction
Pipeline purged, and pass through the mechanical pump and discharge purged gas；
(2) standard curve making：The standard gas that the standard gas steel cylinder is drawn is taken up in order of priority by the analysis with different pressures
Column carries out analysis with being detected by the detector, and records the pressure measurements of the pressure sensor, root
Standard curve is drawn according to the detector testing result under different sample introduction pressure；
(3) trace impurity content analysis in hydrogen isotope gas and/or helium：Sample gas is imported from the sample gas injection port,
Analysis successively is carried out with being detected by the detector by the analytical column, and records the pressure sensor
Pressure measurements, according to the testing result, pressure measurements and standard curve of the detector calculate hydrogen isotope
The content of trace impurity in gas and/or helium, the trace impurity are H2、O2、N2、CO、CH4And CO2。
8. carry out trace impurity content analysis in hydrogen isotope gas and/or helium using the analytical equipment described in claim 6
Method, it is characterised in that the method in turn includes the following steps：
(1) displacement of standard gas and sample gas sample channel environment：High-purity helium or high-purity is introduced by the purging feed channel
Deuterium discharges purged gas to respectively being purged with standard gas and the relevant pipeline of sample gas sample introduction, and by the mechanical pump
Body；
(2) standard curve making：The standard gas that the standard gas steel cylinder is drawn is taken up in order of priority by the analysis with different pressures
Column carries out analysis with being detected by the detector, and records the pressure measurements of the pressure sensor, root
Standard curve is drawn according to the detector testing result under different sample introduction pressure；
(3) trace impurity content analysis in hydrogen isotope gas and/or helium：Sample gas is imported from the sample gas injection port,
Analysis successively is carried out with being detected by the detector by the analytical column, and records the pressure sensor
Pressure measurements, according to the testing result, pressure measurements and standard curve of the detector calculate hydrogen isotope
The content of trace impurity in gas and/or helium, the trace impurity are H2、O2、N2、CO、CH4And CO2。
9. according to the method described in claim 8, it is characterized in that：The high-purity helium or the purging direction of high pure deuterium gas with
The draw-off direction of the mechanical pump is consistent.
10. the method according to claim 7 or 8, it is characterised in that in step (3), calculate hydrogen isotope gas and/or helium
The formula of the content of trace impurity is in gas：
CvSample=P1×A2×CvMark/(P2×A1),
Wherein：
CvMark、CvSampleThe respectively volumetric concentration of standard gas and sample gas；
A1、A2The respectively detector response area of standard gas and sample gas component；
P1、P2The respectively sample introduction pressure of standard gas and sample gas.
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