CN114034795B - Method and device for separating and analyzing argon krypton-xenon full-component gas chromatography in atmosphere based on multidimensional chromatography, center cutting and reverse purging - Google Patents
Method and device for separating and analyzing argon krypton-xenon full-component gas chromatography in atmosphere based on multidimensional chromatography, center cutting and reverse purging Download PDFInfo
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- CN114034795B CN114034795B CN202111349363.2A CN202111349363A CN114034795B CN 114034795 B CN114034795 B CN 114034795B CN 202111349363 A CN202111349363 A CN 202111349363A CN 114034795 B CN114034795 B CN 114034795B
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000010926 purge Methods 0.000 title claims abstract description 22
- 238000000148 multi-dimensional chromatography Methods 0.000 title claims abstract description 20
- 238000004817 gas chromatography Methods 0.000 title claims abstract description 15
- VKDJIPBMRCGQMQ-UHFFFAOYSA-N argon krypton xenon Chemical compound [Ar].[Kr].[Xe] VKDJIPBMRCGQMQ-UHFFFAOYSA-N 0.000 title claims description 11
- 238000000926 separation method Methods 0.000 claims abstract description 156
- 239000012159 carrier gas Substances 0.000 claims abstract description 56
- 229910052786 argon Inorganic materials 0.000 claims abstract description 33
- 229910052743 krypton Inorganic materials 0.000 claims abstract description 21
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004458 analytical method Methods 0.000 claims abstract description 16
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002347 injection Methods 0.000 claims abstract description 8
- 239000007924 injection Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 189
- 230000037361 pathway Effects 0.000 claims description 36
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 238000001536 pulsed discharge helium ionisation detection Methods 0.000 claims description 10
- 238000005070 sampling Methods 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 abstract description 8
- 239000011261 inert gas Substances 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 3
- 238000004451 qualitative analysis Methods 0.000 abstract description 2
- 238000004445 quantitative analysis Methods 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000003795 desorption Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000013375 chromatographic separation Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001612 separation test Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- G01N30/60—Construction of the column
- G01N30/6034—Construction of the column joining multiple columns
-
- 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
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
- G01T1/16—Measuring radiation intensity
- G01T1/167—Measuring radioactive content of objects, e.g. contamination
-
- 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
Abstract
The invention belongs to a monitoring system and a monitoring method for monitoring an atmosphere radiation environment and safely operating a nuclear facility, and relates to a method and a device for separating and analyzing argon, krypton and xenon full-component gas chromatography in the atmosphere based on multidimensional chromatography, center cutting and reverse purging. The method comprises the steps of sample injection, component separation and component analysis. The device comprises a ten-way valve V 1 Ten-way valve V 4 Quantitative ring R of sample 1 Quantitative ring R of sample 2 Quantitative ring R of sample 3 Chromatographic column C 1 Chromatographic column C 2 Chromatographic column C 3 Chromatographic column C 4 Six-way valve V 2 Six-way valve V 3 A detector and carrier gas assembly; the invention adopts four pneumatic valves and four chromatographic columns, and can realize the complete separation and qualitative and quantitative analysis of three inert gas components with huge volume ratio concentration differences in the air at the same time by one sample injection.
Description
Technical Field
The invention belongs to a monitoring system and a monitoring method for monitoring an atmosphere radiation environment and safely operating a nuclear facility, in particular to a high-efficiency method and a device for separating and analyzing all components of Ar, kr and Xe in the atmosphere.
Background
The monitoring of the atmosphere radioactive inert gas nuclide has important significance for the monitoring of the atmosphere radiation environment and the safe operation of nuclear facilities. To effectively monitor the activity concentration of radioinert gas species that may be present in the atmosphere, it is necessary to monitor the air background and to enrich the sample for stable Ar, kr, xe concentrations or total amounts.
The concentrations of Ar, kr, xe in the air background vary greatly. Wherein the volume fractions of Xe and Kr are about 0.087pp, respectivelym and 1.4ppm, ar is about 0.9% by volume; air main component N 2 And O 2 The volume fractions of (a) are about 78.1% and 20.9%, respectively. In the field of gas chromatographic separation, the Kr/N in the air is realized under the normal temperature condition 2 Separation, ar/O 2 The separation difficulty is very high; wherein Ar and O 2 Is a well-known problem in the art, and with the state of the art, complete separation of the two is almost impossible.
The Beijing radionuclide laboratory adopts a 5A molecular sieve as an adsorption material, and researches on the gas chromatography separation effect of Ar, kr, xe, rn are developed, so that the separation performance of Ar, kr, xe, rn mixed gas in gas chromatography is primarily examined, a beneficial attempt is provided for gas chromatography to realize the full-component separation analysis of Ar, kr and Xe in air, but a large gap is still reserved between the separation and detection of the full components of Ar, kr and Xe in air background under normal temperature conditions.
Disclosure of Invention
The invention aims to provide a multi-dimensional chromatography, center cutting and reverse purging based method for separating and analyzing argon, krypton and xenon in the atmosphere by using a full-component gas chromatography, and simultaneously provides a system capable of realizing the method, and through the system, the full separation of Xe in the air, and the complete separation of Kr and N can be realized 2 Is completely separated from Ar and O 2 And finally, the complete separation and analysis of Ar, kr and Xe with low content in the atmosphere are effectively realized.
The technical scheme of the invention is to provide a multi-dimensional chromatography, center cutting and reverse purging based method for separating and analyzing argon, krypton and xenon in the atmosphere by using a full-component gas chromatography, which mainly comprises the following three steps:
1) And (3) sample injection:
sample gas enters a sample inlet (positive pressure diffusion or negative pressure sample suction of a sample ring), 3 sample quantitative rings are adopted for quantitative sampling, and the sample gas is divided into 3 parts; ten-way valve V matched with 3 sample quantifying rings through first switching 1 And ten-way valve V 4 3 sample gases are respectively sent into three independent gas paths along with carrier gas in the passage state; three air paths running independently respectively realize Kr/N 2 Separation, xe separation and Ar/O 2 Separating; three air paths which independently run are respectively defined as Kr/N 2 Separation gas circuit, xe separation gas circuit and Ar/O 2 Separating an air path;
2) Component separation:
adopting gas chromatography, combining center cutting and reverse purging to realize Ar, kr and Xe gas components and O 2 And N 2 Is separated from (1):
in Kr/N 2 In the separation gas path, a ten-way valve V 1 Rear end tandem chromatographic column C 1 With chromatographic column C 2 In chromatographic column C 1 With chromatographic column C 2 Six-way valve V connected between 2 In chromatographic column C 2 The rear end is connected with a six-way valve V 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the chromatographic column C 1 And chromatographic column C 2 Is Kr/N 2 A separation column; during the separation process, by controlling the chromatographic column C 1 Column temperature and switching six-way valve V 2 Is to realize the channel states of Kr and N 2 Is separated from the (a);
in the Xe separation gas path, a chromatographic column C is connected in series with the rear end of a ten-way valve V1 3 Chromatographic column C 3 The rear end is connected with the six-way valve V 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the chromatographic column C 3 Is a Xe separation column; during the separation process, by controlling the chromatographic column C 3 Column temperature and switching six-way valve V 3 The separation of Xe from air is realistic;
in Ar/O 2 In the separation gas circuit, the chromatographic column C 4 Is respectively connected with the front end and the rear end of the cross valve V 4 Is a ten-way valve V 4 And the six-way valve V 3 Communicating; wherein the chromatographic column C 4 Is Ar/O 2 A separation column; in the separation process, the ten-way valve V is switched 4 With six-way valve V 3 Is to realize the passage state of Ar and O 2 Is separated from the (a);
3) Component analysis:
and sending the gas components separated by each branch to a detector in sequence for relevant component analysis.
Preferably, since the Kr concentration in air is compared with N 2 The concentration is extremely low, the separation difficulty of the two is high under normal temperature, and the concentration is high for Kr/N 2 The separation gas circuit adopts chromatographic columns C connected in series 1 And chromatographic column C 2 The separation process is specifically as follows: control chromatographic column C 1 The column temperature of (C) is 50-60 ℃, and the sample gas passes through the chromatographic column C 1 Wherein Kr and a small fraction of N 2 Adsorption to chromatographic column C 1 In most of N 2 And O 2 First flow out of column C 1 At the tail end, through switching the six-way valve V for the first time 2 A passage state in which it is discharged into the atmosphere with the carrier gas; after a certain time, N therein 2 And Kr in turn from column C 1 Desorbing and maintaining six-way valve V 2 State of passage, N 2 Through six-way valve V 2 Exhausting the gas into the atmosphere along with the carrier gas;
second switching six-way valve V 2 The state of the passage, the center cut, kr and the remaining small part N 2 Cut into chromatographic column C with carrier gas 2 ；
Third switching six-way valve V 2 A passage state in which the surplus gas is discharged into the air; n (N) 2 And Kr mixture gas enters C 2 After passing through a chromatographic column C 2 After separation, N 2 And Kr passes through six-way valve V 3 Sequentially entering the detector.
Preferably, the control chromatographic column C 1 The column temperature of (2) was 55 ℃.
Preferably in Kr/N 2 In the separation gas path, the sample gas passes through the chromatographic column C 1 In which Kr and a small part of N 2 Adsorption to chromatographic column C 1 In most of N 2 And O 2 First flow out of column C 1 At the tail end, through switching the six-way valve V for the first time 2 The passage state, when it is discharged into the atmosphere along with the carrier gas, the flow route of the sample gas is as follows: "quantitative Ring R 1 Column C 1 Six-way valve V 2 1-2 passage of (2) →six-way valve V 2 2-4 passage to six-way valve V 2 4-3 passages of → needle valve D 1 Air ";
kr and the remaining fraction N 2 Cut into chromatographic column C with carrier gas 2 At the time of Kr and the remaining fraction N 2 The flow route of (2) is: "chromatographic column C 1 Six-way valve V 2 1-6 pathway →Chromatographic column C 2 ”；
N 2 And Kr passes through six-way valve V 3 The flow paths into the detector in turn are: "chromatographic column C 2 Six-way valve V 3 6-1 path of (c 2) detector).
Preferably, in the Xe separation process, a chromatographic column C3 is used, the separation process is specifically as follows:
control chromatographic column C 3 The column temperature of (C) is 50-60 ℃, and the sample gas passes through the chromatographic column C 3 Thereafter, xe, kr, N in the gas 2 、CH 4 、CO 2 Adsorbing on chromatographic column, desorbing adsorbed gas after a certain time, and desorbing Kr and N firstly 2 、CH 4 、CO 2 The gas sequentially passes through the six-way valve V 3 2-3 passages of (D) and needle valve D 2 Discharging into the atmosphere; subsequently switching the six-way valve V for the first time 3 The passage state, the desorbed Xe enters the detector with the carrier gas.
Preferably, the control chromatographic column C 3 The column temperature of (2) was 55 ℃.
Preferably, the six-way valve V is switched for the first time 3 The passage state, the desorbed Xe enters the detector along with the carrier gas, and the gas flow path is: "chromatographic column C 3 Six-way valve V 3 2-1 path of (c 2-1) detector).
Preferably in Ar/O 2 In the separation gas circuit, the chromatographic column adopts Ar/O with excellent performance 2 The separation column comprises the following steps: control chromatographic column C 4 The column temperature of (C) is 40-50deg.C, and the sample gas flows through the chromatographic column C 4 Ar and O 2 First adsorb to chromatographic column C 4 In which the rest of the gas passes through a six-way valve V 3 Discharging into the atmosphere; at the point of Ar coming from chromatographic column C 4 Before outflow, the six-way valve V is switched for the first time 3 A path state, which causes Ar to enter the detector along with carrier gas; after that, the ten-way valve V is switched for the second time 4 The passage state, the chromatographic column C 4 O remaining in (b) 2 Back-blowing is discharged into the atmosphere.
Preferably, the control chromatographic column C 4 The column temperature of (2) was 40 ℃.
Preferably in Ar/O 2 Separation gas circuitIn which the sample gas flows through the chromatographic column C 4 Ar and O 2 First adsorb to chromatographic column C 4 In which the rest of the gas passes through a six-way valve V 3 When the sample gas is discharged into the atmosphere, the flow route of the sample gas is as follows: quantitative ring R 3 Ten-way valve V 4 5-6 passes through column C 4 Ten-way valve V 4 10-9 passage to six-way valve V 3 2-3 passages of → needle valve D 2 Air;
at the point of Ar coming from chromatographic column C 4 Before outflow, the six-way valve V is switched for the first time 3 The path state, make Ar enter the detector along with the carrier gas, the circulation route of the sample gas is: quantitative ring R 3 Ten-way valve V 4 5-6 passes through column C 4 Ten-way valve V 4 10-9 passage to six-way valve V 3 2-1 path of → detector;
after that, the ten-way valve V is switched for the second time 4 In the passage state, the chromatographic column C is carried out by carrier gas 4 O remaining in (b) 2 When back blowing is discharged into the atmosphere, the gas flow route is as follows: carrier gas- & gtTen-way valve V 4 1-10 passes of (C) column 4 Ten-way valve V 4 6-7 passes of → air.
Preferably, the ten-way valve V is switched for the first time 1 The time interval flow start time of the passage state is 0.01min;
first switching six-way valve V 2 The time interval flow start time of the passage state is 0.01min;
second switching six-way valve V 2 The time interval flow start time of the passage state is 3.5min;
third switching six-way valve V 2 The time interval flow start time of the passage state is 3.6min;
the time interval flow starting time for switching the passage state of the six-way valve V3 for the first time is 7min;
the time interval flow starting time for switching the passage state of the ten-way valve V4 for the first time is 0.01min;
the time interval flow of switching the passage state of the ten-way valve V4 for the second time starts for 10.7min.
Preferably, the resetting is achieved by switching the respective valve:
by switching the valve V for the second time 1 Passage state, realizing ten-way valve V 1 Reset, second switching ten-way valve V 1 The time interval flow start time of the passage state is 0.3min;
by fourth switching of six-way valve V 2 Passage state, realizing six-way valve V 2 Reset, fourth switching six-way valve V 2 The time interval flow of the passage state starts 25min;
and resetting the six-way valve V3 is realized by switching the passage state of the six-way valve V3 for the second time, and the time interval flow starting time of switching the passage state of the six-way valve V3 for the second time is 16min.
Preferably, in step 1, the ten-way valve V matched with the 3 sample quantifying rings is switched for the first time 1 And ten-way valve V 4 When 3 sample gases are respectively sent into three independent running gas paths along with carrier gas, the flow paths of the sample gases are as follows:
Kr/N 2 and (3) separating a gas circuit: carrier gas 1- & gt ten-way valve V 1 1-2 pathway of (C2) quantitative ring R 1 Ten-way valve V 1 9-10 passes of (C) column 1 Six-way valve V 2 1-2 passage of (2) →six-way valve V 2 2-4 passage to six-way valve V 2 4-3 passages of → needle valve D 1 Air ";
xe separation gas circuit: carrier gas 2-ten-way valve V 1 6-5 pathway of (C2) quantitative ring R 2 Ten-way valve V 1 8-7 passes through column C 3 Six-way valve V 3 2-3 passages of → needle valve D 2 Air ";
Ar/O 2 and (3) separating a gas circuit: carrier gas 3- & gt ten-way valve V 4 1-2 pathway of (C2) quantitative ring R 3 Ten-way valve V 4 5-6 passes through column C 4 Ten-way valve V 4 10-9 passage to six-way valve V 3 2-3 passages of → needle valve D 2 Air.
The invention also provides a device for realizing the method, which is characterized in that: comprising a ten-way valve V 1 Ten-way valve V 4 Quantitative ring R of sample 1 Quantitative ring R of sample 2 Quantitative ring R of sample 3 Chromatographic column C 1 Chromatographic column C 2 Chromatographic column C 3 Chromatographic column C 4 Six-way valve V 2 Six-way valve V 3 A detector and carrier gas assembly;
ten-way valve V 1 And ten-way valve V 4 Connected, ten-way valve V 1 For sample gas intake;
sample quantifying ring R 1 Is connected with the ten-way valve V at two ends 1 For Kr/N 2 Quantitative sampling of a separation gas circuit;
sample quantifying ring R 2 Is connected with the ten-way valve V at two ends 1 The other two valve positions of the valve are used for quantitative sampling of the Xe separation gas circuit;
sample quantifying ring R 3 Is connected with the ten-way valve V at two ends 4 For Ar/O 2 Quantitative sampling of a separation gas circuit;
chromatographic column C 1 And chromatographic column C 2 Is Kr/N 2 A separation column; chromatographic column C 1 The front end is connected with a ten-way valve V 1 The rear end is sequentially connected with a six-way valve V 2 Chromatographic column C2 and six-way valve V 3 Forming Kr/N 2 Separating an air path; chromatographic column C 1 And chromatographic column C 2 Is Kr/N 2 A separation column;
chromatographic column C 3 Is a Xe separation column; chromatographic column C 3 The front end is connected with a ten-way valve V 1 The rear end is connected with a six-way valve V 3 Forming a Xe separation gas path;
chromatographic column C 4 Is Ar/O 2 A separation column; chromatographic column C 4 The front end and the rear end of the valve are respectively connected with a ten-way valve V 4 Is a ten-way valve V 4 The rear end is connected with a six-way valve V 3 Ar/O formation of 2 Separating an air path;
the detector is connected with the six-way valve V 3 The rear end is used for detecting and analyzing the separated gas components;
outlet of carrier gas assembly and ten-way valve V 1 Ten-way valve V 4 Six-way valve V 2 Six-way valve V 3 And is connected with the detector.
Preferably, the device further comprises a needle valve D 1 And needle valve D 2 ；
Needle valve D 1 Is connected with a six-way valve V 2 For discharging Kr/N 2 Separating N in gas circuit 2 And O 2 Discharging into the atmosphere;
needle valve D 2 Is connected with a six-way valve V 3 An exhaust valve port for desorbing Kr and N in the Xe separation gas path 2 、CH 4 、CO 2 The gas is vented to the atmosphere.
Preferably, kr/N 2 The specification model of the separation column is 5A,1/8 inch and 2m; xe separation column gauge model Propack Q,1/8 inch 4m; ar/O 2 The separation column is a specially treated 5A molecular sieve column, the model FV-4m and the specification is 1/8 inch by 4m.
Preferably Ar/O 2 The separation column is filled with a 5A molecular sieve, and the separation column is obtained through the following treatment: at 800 ℃ continuously to Ar/O 2 Ar gas is introduced into the separation column for 4 hours.
Preferably, the detector comprises a PDHID detector and a TCD detector which are connected in series, and the sample to be tested sequentially enters the PDHID detector and the TCD detector through the gas circuit. In the detection process, two kinds of detectors can be selected for simultaneous analysis, and one kind of detector can be selected for analysis.
Preferably, the device adopts a multi-column box system to control the temperature and Kr/N respectively 2 The separation column and the Xe separation column are arranged in the same column box; ar/O 2 The separation column is arranged in another column box.
The beneficial effects of the invention are as follows:
1. the invention adopts four pneumatic valves and four chromatographic columns, and can realize the complete separation and qualitative and quantitative analysis of three inert gas components with huge volume ratio concentration differences in the air at the same time by one sample injection.
2. N can be realized under the normal temperature condition by the system 2 And complete separation of Kr, O 2 And Ar is completely separated, and finally, simultaneous separation analysis of Ar, kr and Xe in the atmosphere is effectively realized.
3. The PDHID detector and the TCD detector are simultaneously arranged, so that the simultaneous detection of multiple gas components with extremely large concentration difference can be realized.
Drawings
FIG. 1 is a schematic view of the apparatus of the present invention; v in the figure 1 And V 4 Is a ten-way valve V 2 And V 3 Is a six-way valve; c (C) 1 、C 2 All are Kr/N 2 Separation column C 3 Is a xenon separation column, C 4 Is Ar/O 2 A separation column; wherein C is 1 、 C 2 、C 3 Are all positioned in column boxes 1, C 4 Is positioned in the column box 2; r is R 1 ～R 3 All 0.5ml quantitative rings; p (P) 1 、P 2 Is a pressure sensor; d (D) 1 、D 2 Is a needle valve; TCD and PDHID as detectors;
FIG. 2 is a plot of a PDHID channel full-component test;
FIG. 3 is Ar/O 2 Separating the test spectrogram;
FIG. 4 is a chart of Kr/Ar separation test.
Detailed Description
The invention is further described below with reference to the accompanying drawings and specific examples.
In this example, first, a standard gas a was used as a sample gas, and the composition and volume ratio concentration of the standard gas a are shown in table 1.
TABLE 1 Standard gas A component
The sample inlet of the standard gas source communication chromatograph is shown in figure 1, and the chromatograph structure adopted in the embodiment comprises a ten-way valve V 1 Ten-way valve V 4 Quantitative ring R of sample 1 Quantitative ring R of sample 2 Quantitative ring R of sample 3 Chromatographic column C 1 Chromatographic column C 2 Chromatographic column C 3 Chromatographic column C 4 Six-way valve V 2 Six-way valve V 3 A detector and carrier gas assembly; chromatographic column C 1 Chromatographic column C 2 All are Kr/N 2 A separation column, model 5A, specification 1/8 inch x 2m; chromatographic column C 3 Is a xenon separation column, the model is Propack Q,specification is 1/8 inch by 4m; chromatographic column C 4 Is Ar/O 2 The separation column is a specially treated 5A molecular sieve column, and the specification is 1/8 inch by 4m. The method is characterized by comprising the following steps of: ar/O 2 The separation column is filled with 5A molecular sieve, and Ar/O is continuously carried out at 800 DEG C 2 Ar gas is introduced into the separation column for 4 hours. Respectively controlling temperature and Kr/N by adopting a multi-column box system 2 The separation column and the Xe separation column are arranged in the same column box; ar/O 2 The separation column is arranged in another column box.
Ten-way valve V 1 And ten-way valve V 4 Connected, ten-way valve V 1 For sample gas intake; sample quantifying ring R 1 Is connected with the ten-way valve V at two ends 1 Is provided with two valve positions; sample quantifying ring R 2 Is connected with the ten-way valve V at two ends 1 The other two valve positions; sample quantifying ring R 3 Is connected with the ten-way valve V at two ends 4 Is provided with two valve positions; chromatographic column C 1 The front end is connected with a ten-way valve V 1 The rear end is sequentially connected with a six-way valve V 2 Chromatographic column C2 and six-way valve V 3 Forming Kr/N 2 Separating an air path; chromatographic column C 3 The front end is connected with a ten-way valve V 1 The rear end is connected with a six-way valve V 3 Forming a Xe separation gas path; chromatographic column C 4 The front end and the rear end of the valve are respectively connected with a ten-way valve V 4 Is a ten-way valve V 4 The rear end is connected with a six-way valve V 3 Ar/O formation of 2 Separating an air path; the detector is connected with the six-way valve V 3 The rear end is used for detecting and analyzing the separated gas components; outlet of carrier gas assembly and ten-way valve V 1 Ten-way valve V 4 Six-way valve V 2 Six-way valve V 3 And is connected with the detector. Six-way valve V 2 Is also connected with a needle valve D 1 Six-way valve V 3 Is also connected with a needle valve D 2 . The detector comprises a PDHID detector and a TCD detector in series. As can be seen from the figure, the carrier gas in this embodiment adopts He gas, which enters the purifier for purification and then enters the carrier gas path.
First through two ten-way valves (V 1 、V 4 ) With three dosing rings (R) 1 、R 2 、R 3 ) Taking three parts of standard gas asFor the samples, 0.5ml portions. By rapidly switching the ten-way valve V 1 Ten-way valve V 4 Three samples are respectively sent into three gas paths along with carrier gas. The three air paths respectively realize Kr/N 2 Separation, xe separation and Ar/O 2 And (5) separating.
Before the flow is not started, the black dotted lines in fig. 1 are all valve paths, the blue lines in fig. 1 are complete gas paths for sample gas to circulate at the moment, and the paths are as follows: "sample gas source → 3-2 pathway (V 1 ) Quantitative ring R 1 The 9-8 pathway (V 1 ) Quantitative ring R 2 The 5-4 pathway (V 1 ) The 3-2 pathway (V 2 ) Quantitative ring R 3 The 5-4 pathway (V 2 ) In the process, carrier gas independently enters three separation gas paths, and sample gas does not participate in separation.
When the flow starts 0.01min, the ten-way valve V is switched simultaneously 1 Six-way valve V 2 Ten-way valve V 4 And a valve. At this time, the dosing ring R due to the valve passage change 1 、R 2 、R 3 The sample gas in the device enters three separation gas paths along with carrier gas respectively, and the gas paths at the moment are respectively as follows:
Kr/N 2 and (3) separating a gas circuit: carrier gas 1- & gt 1-2 path (V 1 ) Quantitative ring R 1 The 9-10 pathway (V 1 ) Column C 1 The 1-2 pathway (V 2 ) 2-4 pathway (V 2 ) The 4-3 pathway (V 2 ) Needle valve D 1 Air ";
xe separation gas circuit: carrier gas 2- & gt 6-5 passage (V) 1 ) Quantitative ring R 2 The 8-7 pathway (V 1 ) Column C 3 2-3 pathway (V 3 ) Needle valve D 2 Air ";
Ar/O 2 and (3) separating a gas circuit: carrier gas 3- & gt 1-2 passage (V 4 ) Quantitative ring R 3 The 5-6 pathway (V 4 ) Column C 4 The 10-9 pathway (V 4 ) 2-3 pathway (V 3 ) Needle valve D 2 Air.
When the flow starts 0.3min, the ten-way valve V is switched 1 So as to restore the previous path state, and after switching, kr/N 2 SeparationThe gas paths in the gas path and the Xe separation gas path are changed as follows:
Kr/N 2 and (3) separating a gas circuit: carrier gas passage 1-10 (V) 1 ) Column C 1 The 1-2 pathway (V 2 ) 2-4 pathway (V 2 ) The 4-3 pathway (V 2 ) Needle valve D 1 Air ";
xe separation gas circuit: carrier gas 2- & gt 6-7 path (V 1 ) Column C 3 2-3 pathway (V 3 ) Needle valve D 2 Air ";
Ar/O at this time 2 The gas route in the separation gas circuit is unchanged.
As shown in FIG. 1, in Kr/N 2 In the separation gas path, a ten-way valve V 1 Chromatographic column C 1 Six-way valve V 2 Chromatographic column C 2 Six-way valve V 3 Sequentially connected in series, six-way valve V 2 Connecting needle valve D 1 . The flow starts for 0.01min (at this time, the six-way valve V2 is switched for the first time) and before the six-way valve V2 is switched for the next time, the flow route of the sample gas is as follows: carrier gas 1- & gt 1-2 path (V 1 ) Quantitative ring R 1 The 9-10 pathway (V 1 ) Column C 1 The 1-2 pathway (V 2 ) 2-4 pathway (V 2 ) The 4-3 pathway (V 2 ) Needle valve D 1 Air. In this process, the column C is controlled 1 The column temperature of 50-60 ℃, preferably 55 ℃, and the quantitative ring R 1 The sample gas in (a) is firstly passed through a chromatographic column C 1 N in gas 2 And Kr will adsorb to C 1 In which the other components pass through needle valve D 1 Air is discharged.
After a certain time, N 2 And Kr in turn from column C 1 In order to increase the desorption rate, the temperature of the column box can be properly increased, and the desorbed N is firstly carried out 2 The content is large, and at this time, the six-way valve V is maintained 2 And needle valve D 1 The state is unchanged, most N 2 Through six-way valve V 2 When the process starts for 3.5min, the six-way valve V is switched 2 (six-way valve V at this time) 2 Second hand-off), make a small amount of N 2 Feeding the mixed gas with Kr into chromatographic column C 2 Realize central cutting, when the gas flows through the routeThe following are provided: "chromatographic column C 1 The 1-6 pathway (V 2 ) Column C 2 ”；
After 0.1min, the six-way valve V is switched again 2 (six-way valve V at this time) 2 Third switch) to pass the residual gas through the needle valve D 1 Air is discharged. N (N) 2 And Kr mixture gas enters C 2 After that, the re-separation is completed, and the separated N 2 And Kr passes through six-way valve V 3 Sequentially entering a PDD detector for detection. The gas flow path into the detector is: "chromatographic column C 2 The 6-1 pathway (V 3 ) PDD detector→tcd detector.
In the Xe separation gas path, a chromatographic column C 3 The front end is connected with a ten-way valve V 1 The rear end is connected with a six-way valve V 3 In a six-way valve V 3 On which is connected a needle valve D 2 . Quantitative ring R 2 The sample gas in the gas path enters the gas path along with carrier gas, and the route is as follows: carrier gas 2- & gt 6-5 passage (V) 1 ) Quantitative ring R 2 The 8-7 pathway (V 1 ) Column C 3 2-3 pathway (V 3 ) Needle valve D 2 Air control column C 3 The column temperature of (C) is 50-60deg.C, preferably 55deg.C, and the sample gas passes through the chromatographic column C 3 Thereafter, xe, kr, N in the gas 2 、CH 4 、CO 2 Adsorbing on chromatographic column, desorbing adsorbed gas after a certain time, and desorbing Kr and N firstly 2 、CH 4 、CO 2 Equal gas passing through needle valve D 2 The mixture is discharged into the atmosphere, and the six-way valve V is switched before Xe desorption 3 (at the beginning of the flow for 7min, six-way valve V at this time) 3 First switch) to allow Xe to enter the detector for analysis, the route is: "chromatographic column C 3 2-1 pathway (V 3 ) PDD detector→tcd detector.
In Ar/O 2 In the separation gas circuit, a chromatographic column C 4 Both ends are connected with a ten-way valve V 4 The connection is as shown in fig. 1. When the separation process starts 0.01min, the ten-way valve V 4 Switching state (Ten-way valve V at this time) 4 First switch), control column C 4 The column temperature of (C) is 40-50deg.C, preferably 40 deg.C, and the quantitative ring R 3 Along with the sample gas in (1)The carrier gas enters the separation gas path, and the flow path is: carrier gas 3- & gt 1-2 passage (V 4 ) Quantitative ring R 3 The 5-6 pathway (V 4 ) Column C 4 The 10-9 pathway (V 4 ) 2-3 pathway (V 3 ) Needle valve D 2 Air ", in the process, ar and O 2 First adsorb to chromatographic column C 4 In which the rest of the gas passes through a six-way valve V 3 Is discharged into the atmosphere. When the flow starts for 7min, six-way valve V 3 Switching (six-way valve V at this time) 3 First switching) to communicate the separation gas path outlet with the detector; to about 10min, ar is desorbed first and enters the detector; at 10.7min (ten-way valve V at this time) 4 Second switching), switching ten-way valve V 4 Passing through column C 4 Is reversed, and at this time, ar and a small amount of O 2 Desorbing into the detector, leaving most of O 2 Is blown back with other components and discharged into the air, thereby realizing the center cutting. Through needle valve D 2 Regulation of chromatographic column C 3 And C 4 The peak time of the two gas paths can be completely staggered.
In the above process, the valve switching is automatically controlled, and the valve switching time related to each flow is shown in table 2, wherein "0" represents that the valve keeps the existing state unchanged.
TABLE 2 valve State switching time
After the above full component separation analysis is completed, standard gas B is selected for Kr/N 2 The separation effect was verified, and in addition, air was collected for Ar/O 2 And verifying the separation effect.
And air as the sample gas, the composition of the standard gas B is shown in table 3. The test flow is consistent with the whole component separation process, and after the sample enters the chromatograph, the separation analysis flow is automatically carried out, and a test spectrogram is obtained.
TABLE 3 Standard gas B composition Table
Fig. 2 is a full component test spectrum of the PDD channel, and it can be seen that the low content of Ar, kr, xe in the air realizes full separation. Wherein the concentration of Ar is 184.145ppm, the concentration of Kr is 346.225ppm, and the concentration of Xe is 286.962ppm, indicating that the lowest ppb level can be detected for the PDHID detector for Ar, kr, xe. In addition, the peak before the Kr peak in the spectrum is N 2 Peaks, showing that Kr and N are realized by adopting the center cutting technology 2 Is completely separated.
FIG. 3 is Ar/O 2 Separating the test spectrogram, wherein Ar peak and O 2 Complete peak separation, indicating that Ar and O in air are realized 2 The result of the spectrum shows that the Ar concentration obtained by final separation is 0.2086 percent, O 2 A concentration of 99.7914%, an Ar concentration is increased compared to the air level, since the center cut removes a portion of the O 2 ；
FIG. 4 is Kr/N 2 Separation test spectra, it can be seen that Kr, N 2 The signal peaks are completely separated, namely N is realized 2 Complete separation from Kr. The standard gas B also contains a part of Ar, and signal peaks are independent in a spectrogram, so that the Ar is completely separated.
The principle of the invention is as follows:
the invention discloses a multi-dimensional chromatography, center cutting and reverse purging based method for separating and analyzing argon, krypton and xenon in the atmosphere by using a full-component gas chromatography, which mainly comprises the following three steps:
1) And (3) sample injection:
sample gas is diffused into a chromatographic separation system (positive pressure diffusion or sample ring negative pressure suction sampling), 3 sample rings are combined by two ten-way valves for quantitative sampling, and the samples are divided into 3 parts; the three air paths are independently operated and sample injection is realized through a specific air path connection mode of the sample ring and the ten-way valve.
2) Component separation:
adopting gas chromatography, combining center cutting and reverse purging to realize Ar, kr and Xe gas components and O 2 And N 2 Is separated from the other components.
3) Component analysis:
the separated gas components of each branch are sequentially sent to two detectors connected in series, namely PDHID and TCD for relevant component analysis.
The working process of the invention is as follows:
air sample enters the ten-way valve (V) from the sample inlet 1 、V 4 ) After that, the sample was aliquoted into three portions of 0.5ml by three dosing rings. Through a ten-way valve V 1 Ten-way valve V 4 And (3) respectively sending each sample into three gas paths along with the carrier gas. The three air paths respectively realize Kr/N 2 Separation, xe separation and Ar/O 2 And finally, separating Ar, kr and Xe completely.
In Kr/N 2 In the separation gas circuit, a chromatographic column C 1 The front end is connected with a ten-way valve V 1 The rear end is connected with a six-way valve V 2 Chromatographic column C 2 The front end is connected with a six-way valve V 2 The rear end is connected with a six-way valve V 3 . Six-way valve V 2 To which a needle valve D is connected 1 . The temperature of the column box is stabilized at 50-60 ℃, and the ring R is quantified in the sample injection process 1 The gas in (a) is firstly passed through a chromatographic column C 1 N in gas 2 And Kr will adsorb to C 1 Other components pass through needle valve D 1 Into the air. The six-way valve state is kept unchanged, the temperature is increased, N 2 And Kr are sequentially desorbed from the chromatographic column, N due to the background gas being air 2 The content is large, so a six-way valve V is adopted 2 Is switched to perform center cutting to make a large amount of N 2 Through six-way valve V 2 Venting and switching six-way valve V 2 Make a small amount of N 2 Feeding the mixed gas with Kr into chromatographic column C 2 Complete the re-separation and separate N 2 And Kr passes through six-way valve V 3 Sequentially entering a PDD detector for detection, and remaining N 2 And other components through six-way valve V 2 And continuing to empty.
In the Xe separation gas path, a chromatographic column C 3 The front end is connected with a ten-way valve V 1 The rear end is connected with a six-way valve V 3 In a six-way valve V 3 On which is connected a needle valve D 2 . Quantitative ring R 2 The gas in the gas channel enters the gas channel along with the carrier gas and passes through the chromatographic column C 3 After separation, kr, N, desorbed first 2 、CH 4 、CO 2 Equal gas passing through needle valve D 2 Is discharged into the atmosphere, and the six-way valve V is switched before Xe desorption 3 Xe is allowed to enter the detector for analysis.
In Ar/O 2 In the separation gas path, the temperature of the column box is stabilized at 40-50 ℃, and after the separation process is started, the valve V is opened ten times 4 Switching state, wherein the sample gas enters a separation gas path along with the carrier gas, ar and O 2 First adsorb to chromatographic column C 4 In which the rest of the gas passes through needle valve D 2 Into the air, during which Ar and O 2 And not desorbed. After separation by chromatographic column, ar is desorbed first, before Ar desorption, six-way valve V is switched 3 The gas path is communicated with the detector, and after Ar is completely desorbed into the detector, the six-way valve V is switched again 3 To this end Ar and a small amount of O 2 Sequentially entering a detector for detection. After which the ten-way valve V is switched 4 Passing through column C 4 Is reversed, the rest of the carrier gas flow direction is mostly O 2 Is blown back with other components and discharged into the air, thereby realizing the center cutting.
Through needle valve D 2 And (3) adjusting the peak outlet time of the Q column and the oxygen Ar separation column to ensure that peak positions can be completely staggered when two sides are switched. In the process, the valve switching is automatically controlled.
Claims (16)
1. The method for separating and analyzing the argon, krypton and xenon full-component gas chromatography in the atmosphere based on multidimensional chromatography, center cutting and reverse purging is characterized by comprising the following three steps:
step 1, sample injection:
the sample gas enters a sample inlet, 3 sample quantitative rings are adopted for quantitative sampling, and the sample gas is divided into 3 parts; ten-way valve V matched with 3 sample quantifying rings through first switching 1 And ten-way valve V 4 3 sample gases are respectively sent into three independent gas paths along with carrier gas in the passage state; three air paths running independently respectively realize Kr/N 2 Separation, xe separation and Ar/O 2 Separating; three air paths which independently run are respectively defined as Kr/N 2 Separation gas circuit, xe separation gas circuit and Ar/O 2 Separating an air path;
step 2, component separation:
in Kr/N 2 In the separation gas path, a ten-way valve V 1 Rear end tandem chromatographic column C 1 With chromatographic column C 2 In chromatographic column C 1 With chromatographic column C 2 Six-way valve V connected between 2 In chromatographic column C 2 The rear end is connected with a six-way valve V 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the chromatographic column C 1 And chromatographic column C 2 Is Kr/N 2 Separation column, kr/N 2 The model of the separation column is 5A, and the specification is 1/8 inch x 2m; during the separation process, by controlling the chromatographic column C 1 Column temperature and switching six-way valve V 2 Is to realize the channel states of Kr and N 2 Is separated from the (a);
in the Xe separation gas path, a chromatographic column C is connected in series with the rear end of a ten-way valve V1 3 Chromatographic column C 3 The rear end is connected with the six-way valve V 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the chromatographic column C 3 The Xe separation column is a Propack Q with the specification of 1/8 inch x 4m; during the separation process, by controlling the chromatographic column C 3 Column temperature and switching six-way valve V 3 The separation of Xe from air is realistic;
in Ar/O 2 In the separation gas circuit, the chromatographic column C 4 Is respectively connected with the front end and the rear end of the cross valve V 4 Is a ten-way valve V 4 And the six-way valve V 3 Communicating; wherein the chromatographic column C 4 Is Ar/O 2 Separation column, ar/O 2 Separation column model FV-4m, 1/8 inch x 4m, ar/O 2 The separation column is filled with a 5A molecular sieve, and the separation column is obtained through the following treatment: at 800 ℃ continuously to Ar/O 2 Ar gas is introduced into the separation column for 4 hours; in the separation process, the ten-way valve V is switched 4 With six-way valve V 3 Is to realize the passage state of Ar and O 2 Is separated from the (a);
step 3, component analysis:
and sending the gas components separated by each separation gas circuit to a detector in sequence for relevant component analysis, wherein the detector comprises a PDHID detector and a TCD detector which are connected in series.
2. The method for separating and analyzing the argon krypton xenon full-component gas chromatograph in the atmosphere based on multidimensional chromatography, center cutting and reverse purging according to claim 1, wherein in the step 2:
in Kr/N 2 In the separation gas path, the separation process is specifically as follows: control chromatographic column C 1 The column temperature of (C) is 50-60 ℃, and the sample gas passes through the chromatographic column C 1 Wherein Kr and a small fraction of N 2 Adsorption to chromatographic column C 1 In most of N 2 And O 2 First flow out of column C 1 At the tail end, through switching the six-way valve V for the first time 2 A passage state in which it is discharged into the atmosphere with the carrier gas; after a certain time, N therein 2 And Kr in turn from column C 1 Desorbing and maintaining six-way valve V 2 State of passage, N 2 Through six-way valve V 2 Exhausting the gas into the atmosphere along with the carrier gas;
second switching six-way valve V 2 The state of the passage, the center cut, kr and the remaining small part N 2 Cut into chromatographic column C with carrier gas 2 ；
Third switching six-way valve V 2 A passage state in which the surplus gas is discharged into the air; n (N) 2 And Kr mixture gas enters C 2 After passing through a chromatographic column C 2 After separation, N 2 And Kr passes through six-way valve V 3 Sequentially entering the detector.
3. The method for separating and analyzing the argon krypton xenon full-component gas chromatograph in the atmosphere based on multidimensional chromatography, center cutting and reverse purging according to claim 2, wherein the method comprises the following steps: control chromatographic column C 1 The column temperature of (2) was 55 ℃.
4. The method for separating and analyzing the argon krypton xenon full-component gas chromatograph in the atmosphere based on multidimensional chromatography, center cutting and reverse purging according to claim 2, wherein the method comprises the following steps: in Kr/N 2 In the separation gas path, the sample gas passes through the chromatographic column C 1 In which Kr and a small part of N 2 Adsorption to chromatographic column C 1 In most of N 2 And O 2 First flow out of column C 1 At the tail end, through switching the six-way valve V for the first time 2 The passage state, when it is discharged into the atmosphere along with the carrier gas, the flow route of the sample gas is as follows: "quantitative Ring R 1 Column C 1 Six-way valve V 2 1-2 passage of (2) →six-way valve V 2 2-4 passage to six-way valve V 2 4-3 passages of → needle valve D 1 Air ";
kr and the remaining fraction N 2 Cut into chromatographic column C with carrier gas 2 At the time of Kr and the remaining fraction N 2 The flow route of (2) is: "chromatographic column C 1 Six-way valve V 2 1-6 passes of (C) column 2 ”；
N 2 And Kr passes through six-way valve V 3 The flow paths into the detector in turn are: "chromatographic column C 2 Six-way valve V 3 6-1 path of (c 2) detector).
5. The method for analyzing the multi-dimensional chromatography, center-cut and reverse-purge based full-component gas chromatography of argon krypton-xenon in the atmosphere according to any one of claims 1 to 4, wherein in the step 2:
in the Xe separation gas path, the separation process is specifically as follows: control chromatographic column C 3 The column temperature of (C) is 50-60 ℃, and the sample gas passes through the chromatographic column C 3 Thereafter, xe, kr, N in the gas 2 、CH 4 、CO 2 Adsorbing on chromatographic column, desorbing adsorbed gas after a certain time, and desorbing Kr and N firstly 2 、CH 4 、CO 2 The gas sequentially passes through the six-way valve V 3 2-3 passages of (D) and needle valve D 2 Discharging into the atmosphere; subsequently switching the six-way valve V for the first time 3 The passage state, the desorbed Xe enters the detector with the carrier gas.
6. The method for separating and analyzing the argon krypton xenon full-component gas chromatograph in the atmosphere based on multidimensional chromatography, center cutting and reverse purging according to claim 5, wherein the method comprises the following steps: control chromatographic column C 3 The column temperature of (2) was 55 ℃.
7. The method for separating and analyzing argon, krypton and xenon in the atmosphere by using multi-dimensional chromatography, center cutting and reverse purging according to claim 5, wherein the six-way valve V is switched for the first time 3 The passage state, when the desorbed Xe enters the PDD detector and the TCD detector along with the carrier gas, the flow path of the gas is: "chromatographic column C 3 Six-way valve V 3 2-1 path of (c 2-1) detector).
8. The method for separating and analyzing argon, krypton and xenon in the atmosphere by multi-dimensional chromatography, center cutting and reverse purging according to claim 5, wherein in step 2, ar/O is as follows 2 In the separation gas path, the separation process is specifically as follows:
control chromatographic column C 4 The column temperature of (C) is 40-50deg.C, and the sample gas flows through the chromatographic column C 4 Ar and O 2 First adsorb to chromatographic column C 4 In which the rest of the gas passes through a six-way valve V 3 Discharging into the atmosphere; at the point of Ar coming from chromatographic column C 4 Before outflow, the six-way valve V is switched for the first time 3 A path state, which causes Ar to enter the detector along with carrier gas; after that, the ten-way valve V is switched for the second time 4 The passage state, the chromatographic column C 4 O remaining in (b) 2 Back-blowing is discharged into the atmosphere.
9. The method for separating and analyzing the argon krypton xenon full-component gas chromatograph in the atmosphere based on multidimensional chromatography, center cutting and reverse purging according to claim 8, wherein the method comprises the following steps: control chromatographic column C 4 The column temperature of (2) was 40 ℃.
10. The method for separating and analyzing the argon krypton xenon full-component gas chromatograph in the atmosphere based on multidimensional chromatography, center cutting and reverse purging according to claim 9, wherein the method comprises the following steps:
in Ar/O 2 In the separation gas path, the sample gas flows through the chromatographic column C 4 Ar and O 2 First adsorb to chromatographic column C 4 In which the rest of the gas passes through a six-way valve V 3 When discharged into the atmosphere, the sample gasThe flow route of the body is as follows: quantitative ring R 3 Ten-way valve V 4 5-6 passes through column C 4 Ten-way valve V 4 10-9 passage to six-way valve V 3 2-3 passages of → needle valve D 2 Air;
at the point of Ar coming from chromatographic column C 4 Before outflow, the six-way valve V is switched for the first time 3 The path state, make Ar enter the detector along with the carrier gas, the circulation route of the sample gas is: quantitative ring R 3 Ten-way valve V 4 5-6 passes through column C 4 Ten-way valve V 4 10-9 passage to six-way valve V 3 2-1 path of → detector;
after that, the ten-way valve V is switched for the second time 4 In the passage state, the chromatographic column C is carried out by carrier gas 4 O remaining in (b) 2 When back blowing is discharged into the atmosphere, the gas flow route is as follows: carrier gas- & gtTen-way valve V 4 1-10 passes of (C) column 4 Ten-way valve V 4 6-7 passes of → air.
11. The method for separating and analyzing the argon krypton xenon full-component gas chromatograph in the atmosphere based on multidimensional chromatography, center cutting and reverse purging according to claim 10, wherein the method comprises the following steps:
first switching ten-way valve V 1 The time interval flow start time of the passage state is 0.01min;
first switching six-way valve V 2 The time interval flow start time of the passage state is 0.01min;
second switching six-way valve V 2 The time interval flow start time of the passage state is 3.5min;
third switching six-way valve V 2 The time interval flow start time of the passage state is 3.6min;
the time interval flow starting time for switching the passage state of the six-way valve V3 for the first time is 7min;
the time interval flow starting time for switching the passage state of the ten-way valve V4 for the first time is 0.01min;
the time interval flow of switching the passage state of the ten-way valve V4 for the second time starts for 10.7min.
12. The method for separating and analyzing the argon, krypton and xenon full-component gas chromatography in the atmosphere based on multidimensional chromatography, center cutting and reverse purging according to claim 11, wherein the resetting is realized by switching corresponding valves:
by switching the valve V for the second time 1 Passage state, realizing ten-way valve V 1 Reset, second switching ten-way valve V 1 The time interval flow start time of the passage state is 0.3min;
by fourth switching of six-way valve V 2 Passage state, realizing six-way valve V 2 Reset, fourth switching six-way valve V 2 The time interval flow of the passage state starts 25min;
and resetting the six-way valve V3 is realized by switching the passage state of the six-way valve V3 for the second time, and the time interval flow starting time of switching the passage state of the six-way valve V3 for the second time is 16min.
13. The method for separating and analyzing argon, krypton and xenon in the atmosphere by multi-dimensional chromatography, center cutting and reverse purging according to claim 12, wherein in step 1, a ten-way valve V matched with 3 sample quantitative rings is switched for the first time 1 And ten-way valve V 4 When 3 sample gases are respectively sent into three independent running gas paths along with carrier gas, the flow paths of the sample gases are as follows:
Kr/N 2 and (3) separating a gas circuit: carrier gas 1- & gt ten-way valve V 1 1-2 pathway of (C2) quantitative ring R 1 Ten-way valve V 1 9-10 passes of (C) column 1 Six-way valve V 2 1-2 passage of (2) →six-way valve V 2 2-4 passage to six-way valve V 2 4-3 passages of → needle valve D 1 Air ";
xe separation gas circuit: carrier gas 2-ten-way valve V 1 6-5 pathway of (C2) quantitative ring R 2 Ten-way valve V 1 8-7 passes through column C 3 Six-way valve V 3 2-3 passages of → needle valve D 2 Air ";
Ar/O 2 and (3) separating a gas circuit: carrier gas 3- & gt ten-way valve V 4 1-2 general of (2)Road-quantitative ring R 3 Ten-way valve V 4 5-6 passes through column C 4 Ten-way valve V 4 10-9 passage to six-way valve V 3 2-3 passages of → needle valve D 2 Air.
14. An apparatus for realizing the multi-dimensional chromatography, center cutting and reverse purging-based method for separating and analyzing argon krypton-xenon full component gas chromatography in the atmosphere according to any one of claims 1 to 12, which is characterized in that:
comprising a ten-way valve V 1 Ten-way valve V 4 Quantitative ring R of sample 1 Quantitative ring R of sample 2 Quantitative ring R of sample 3 Chromatographic column C 1 Chromatographic column C 2 Chromatographic column C 3 Chromatographic column C 4 Six-way valve V 2 Six-way valve V 3 A detector and carrier gas assembly;
ten-way valve V 1 And ten-way valve V 4 Connected, ten-way valve V 1 For sample gas intake;
sample quantifying ring R 1 Is connected with the ten-way valve V at two ends 1 For Kr/N 2 Quantitative sampling of a separation gas circuit;
sample quantifying ring R 2 Is connected with the ten-way valve V at two ends 1 The other two valve positions of the valve are used for quantitative sampling of the Xe separation gas circuit;
sample quantifying ring R 3 Is connected with the ten-way valve V at two ends 4 For Ar/O 2 Quantitative sampling of a separation gas circuit;
chromatographic column C 1 And chromatographic column C 2 Is Kr/N 2 Separation column, kr/N 2 The model of the separation column is 5A, and the specification is 1/8 inch x 2m; chromatographic column C 1 The front end is connected with a ten-way valve V 1 The rear end is sequentially connected with a six-way valve V 2 Chromatographic column C2 and six-way valve V 3 Forming Kr/N 2 Separating an air path; chromatographic column C 1 And chromatographic column C 2 Is Kr/N 2 A separation column;
chromatographic column C 3 The Xe separation column is a Propack Q with the specification of 1/8 inch x 4m; color ofSpectral column C 3 The front end is connected with a ten-way valve V 1 The rear end is connected with a six-way valve V 3 Forming a Xe separation gas path;
chromatographic column C 4 Is Ar/O 2 Separation column, ar/O 2 Separation column model FV-4m, 1/8 inch x 4m, ar/O 2 The separation column is filled with a 5A molecular sieve, and the separation column is obtained through the following treatment: continuously introducing Ar gas into an Ar/O2 separation column for 4 hours at 800 ℃; chromatographic column C 4 The front end and the rear end of the valve are respectively connected with a ten-way valve V 4 Is a ten-way valve V 4 The rear end is connected with a six-way valve V 3 Ar/O formation of 2 Separating an air path;
the detector is connected with the six-way valve V 3 The rear end is used for detecting and analyzing the separated gas components, and the detector comprises a PDHID detector and a TCD detector which are connected in series;
outlet of carrier gas assembly and ten-way valve V 1 Ten-way valve V 4 Six-way valve V 2 Six-way valve V 3 And is connected with the detector.
15. The apparatus according to claim 14, wherein: also comprises a needle valve D 1 And needle valve D 2 ；
Needle valve D 1 Is connected with a six-way valve V 2 For discharging Kr/N 2 Separating N in gas circuit 2 And O 2 Discharging into the atmosphere;
needle valve D 2 Is connected with a six-way valve V 3 An exhaust valve port for desorbing Kr and N in the Xe separation gas path 2 、CH 4 、CO 2 The gas is vented to the atmosphere.
16. The apparatus according to claim 15, wherein: respectively controlling temperature and Kr/N by adopting a multi-column box system 2 The separation column and the Xe separation column are arranged in the same column box; ar/O 2 The separation column is arranged in another column box.
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| CN202111349363.2A CN114034795B (en) | 2021-11-15 | 2021-11-15 | Method and device for separating and analyzing argon krypton-xenon full-component gas chromatography in atmosphere based on multidimensional chromatography, center cutting and reverse purging |
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| CN102628846A (en) * | 2012-04-19 | 2012-08-08 | 杭州克柔姆色谱科技有限公司 | Gas chromatography detection system and method for analyzing trace impurities in ultrahigh pure gas |
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| CA2643092C (en) * | 2005-02-22 | 2014-04-29 | Systeme Analytique Inc. | Chromatographic methods for measuring impurities in a gas sample |
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