CN111257475B - Chromatographic detection method capable of simultaneously detecting contents of various rare gases and chromatograph - Google Patents
Chromatographic detection method capable of simultaneously detecting contents of various rare gases and chromatograph Download PDFInfo
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- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- 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
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- G01N30/10—Preparation using a splitter
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- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
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- G01N30/14—Preparation by elimination of some components
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- 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
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- 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
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- G—PHYSICS
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- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N30/66—Thermal conductivity detectors
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- 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 relates to chromatographic detection, in particular to a chromatographic detection method and a chromatograph capable of simultaneously detecting the contents of multiple rare gases (neon, argon, krypton and xenon). The invention aims to solve the technical problem that the content of neon, argon, krypton and xenon cannot be detected simultaneously in the conventional chromatograph and the detection method thereof, and provides a chromatograph and a chromatographic detection method capable of detecting the content of various rare gases simultaneously. The method comprises the following steps: 1) gas to be detected containing various rare gases enters a preposed pipeline; 2) the gas to be detected is distributed to the first channel and the second channel; 3) carrying out deoxidization, impurity removal, separation and pulse discharge helium ionization detection on the quantified gas to be detected in the first channel by the carrier gas in sequence; and the carrier gas sequentially removes impurities, separates and detects the heat conduction of the quantitative gas to be detected in the second channel. The chromatograph separation detection module comprises a first channel and a second channel, wherein the first channel and the second channel both comprise impurity removal columns.
Description
Technical Field
The invention relates to chromatographic detection, in particular to a chromatographic detection method and a chromatograph capable of simultaneously detecting the contents of multiple rare gases (neon, argon, krypton and xenon).
Background
The chromatography is one of methods for detecting rare gas, which detects rare gas by using a single detector such as a Pulse Discharge Helium Ionization Detector (PDHIDs) or a Thermal Conductivity Detector (TCDs) using a molecular sieve, a carbon molecular sieve, or the like as a stationary phase and helium (He) as a carrier gas, but has two problems in the actual test process:
first, when nitrogen (N) is present in the sample2) Oxygen (O)2) And carbon monoxide (CO) and other interfering components are present in large quantities, quantitative detection of trace amounts of rare gases cannot be achieved. The method for removing impurity components comprises valve switching, pre-column separation, a titanium sponge reaction bed and the like, but the valve switching and the pre-column separation can shift a base line, so that the response of a detector is unstable, and the working temperature of the titanium sponge reaction bed is generally above 650 ℃, the higher the working temperature is, the hydrogen (H) is2) The more the release, the more the baseline noise increases, seriously affecting the stability of the measurement.
Secondly, since the concentration of each sample component is very different when the content of a plurality of rare gases is detected simultaneously, each sample component is required to be within the linear range of the detector when the normalized quantitative measurement is carried out, so that the detector used is required to have a wider linear range, otherwise, a larger error is caused. TCD vs. volume concentration of less than 50ppm (ppm is the volume concentration here, and means 10-6v/v) noble gas (b)Neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe)) are difficult to accurately quantify, and PDHIDs require many times of pressure reduction for rare gases (argon, krypton, and xenon) having a volume concentration of more than 1000ppm to accurately quantify them. Therefore, the single detector has a narrow measurement linear range, and cannot simultaneously detect neon, argon, krypton and xenon with low concentration.
Disclosure of Invention
The invention aims to solve the technical problem that the existing chromatograph and the detection method thereof can not realize the simultaneous consideration of the contents of neon, argon, krypton and xenon with high and low concentrations, and provides a chromatograph and a chromatographic detection method capable of simultaneously detecting the contents of various rare gases.
In order to solve the technical problems, the technical solution provided by the invention is as follows:
a chromatographic detection method capable of simultaneously detecting contents of various rare gases is characterized by comprising the following steps:
1) leading gas to be detected containing various rare gases to enter a preposed pipeline;
2) shunting the gas to be detected to a first channel and a second channel;
3) carrying out deoxidization, impurity removal, 5A molecular sieve capillary chromatographic column separation and pulse discharge helium ionization detection on the quantified gas to be detected in the first channel by using carrier gas in sequence; and (3) carrying out impurity removal, 5A molecular sieve capillary chromatographic column separation and thermal conductivity detection on the quantified gas to be detected in the second channel by using carrier gas in sequence.
Further, the step 1) also comprises the pre-vacuumizing treatment of the preposed pipeline.
Further, in order to buffer the pressure of the calibrated gas, the step 1) is to make the gas to be detected containing various rare gases enter the preposed pipeline after buffer treatment.
A chromatograph capable of simultaneously detecting contents of various rare gases for realizing the detection method is characterized in that:
the device comprises a sample injection module, a four-way valve, a separation detection module, a vacuum pump and carrier gas;
the separation detection module comprises a first channel and a second channel;
the first channel comprises a first six-way valve, a first quantitative ring, a first deoxygenating column, a first depurating column, a first chromatographic column and a pulse discharge helium ionization detector which are sequentially communicated; two ends of the first quantitative ring are respectively connected with a of the first six-way valve1Terminal and d1The inlet end of the first oxygen removing column is communicated with the e of the first six-way valve1The ends are communicated;
the second channel comprises a second six-way valve, a second quantitative ring, a second impurity removal column, a second chromatographic column and a thermal conductivity detector which are sequentially communicated; two ends of the second quantitative ring are respectively connected with a of the second six-way valve2Terminal and d2The ends of the first impurity removing column are communicated with the inlet end of the first six-way valve2The ends are communicated;
the inlet of the four-way valve is connected with the outlet of the sample injection module;
three outlets of the four-way valve are respectively connected with the b of the first six-way valve1B of end and second six-way valve2The end is communicated with the pumping hole of the vacuum pump;
the carrier gas is respectively communicated with f of the first six-way valve1F of end, second six-way valve2The ends are communicated with each other,
the first chromatographic column and the second chromatographic column are both 5A molecular sieve capillary chromatographic columns.
Further, in order to achieve a good impurity removal effect, the first impurity removal column and the second impurity removal column are both stainless steel tubes with the column length of 1m and the inner diameter of 1.75mm, 9.5g of a 30-40-mesh titanium-based zirconium-vanadium-iron alloy getter is filled in each column, and the impurity removal amount is 100 mL/g.
Further, the first quantitative ring is a 0.50mL quantitative ring according to different detectors; the second quantitation loop is a 1.0mL quantitation loop.
Furthermore, the sample introduction module comprises a first calibration gas inlet, a second calibration gas inlet, a first sample gas inlet, a second sample gas inlet, and a first flow path selection switch, a second flow path selection switch, a third flow path selection switch, and a fourth flow path selection switch, which correspond to the first calibration gas inlet, the second calibration gas inlet, the first sample gas inlet, and the second sample gas inlet, respectively.
Further, two solenoid valves V1 and V2 are provided between the first calibration gas inlet and the first flow path selector switch, and two solenoid valves V3 and V4 are provided between the second calibration gas inlet and the first flow path selector switch.
Furthermore, the first flow path selection switch, the second flow path selection switch, the third flow path selection switch and the fourth flow path selection switch are communicated with the inlet of the four-way valve through a solenoid valve V5, among three outlets of the four-way valve, a solenoid valve V7 is arranged between one outlet and one inlet of the first six-way valve, a solenoid valve V8 is arranged between one outlet and one inlet of the second six-way valve, and a solenoid valve V6 is arranged between one outlet and the vacuum pump; and a barometer installed through a three-way valve is also arranged between the electromagnetic valve V5 and the inlet of the four-way valve.
Compared with the prior art, the invention has the following beneficial effects:
1. the chromatographic detection method and the chromatograph capable of simultaneously detecting the contents of various rare gases are provided with double detection channels of a Pulse Discharge Helium Ionization Detector (PDHID) and a Thermal Conductivity Detector (TCD), and an alloy getter impurity removal column is additionally arranged between a quantitative ring and the chromatographic column and can remove nitrogen (N)2) Oxygen (O)2) And carbon monoxide (CO), etc., thereby realizing quantitative detection of neon, argon, krypton, and xenon at different concentrations, and particularly realizing measurement of neon by TCD.
2. The PDHID is used for detecting argon, krypton and xenon with the concentration less than 1000ppm, the TCD is used for detecting neon and argon, krypton and xenon with the concentration more than 50ppm, and the samples with high and low concentrations are taken into consideration. Through one-time sample introduction, the detection of different concentrations and multi-component rare gases by one chromatograph is realized, and the detection efficiency is obviously improved.
3. The method combines the dual-channel detection and impurity removal before chromatographic column separation, and the baseline noise, 30-minute baseline drift and the like of the PDHID and TCD detectors meet technical indexes; the linear correlation coefficients all reach more than 0.999, the calibration deviation is less than 2% in a certain time, and the measurement is stable and reliable.
4. The integrated negative pressure sample injection system can realize pressure reduction and negative pressure gas sample injection through a gas selection flow path and sample injection buffering, and is suitable for the pressure range of sample gas of 5 kPa-133 kPa.
5. The method can be used for measuring the contents of various rare gases in nuclear fuel stack monitoring, environmental monitoring and research and evaluation.
Drawings
FIG. 1 is a schematic diagram of a chromatograph according to the present invention;
FIG. 2-1 is a chromatogram obtained for the first channel, wherein the three peaks are Ar, Kr, Xe, in that order;
FIG. 2-2 is a chromatogram obtained for the second pass, in which the three peaks are Ne, Ar, Kr in that order;
FIG. 3-1 is a standard graph of Ne;
FIG. 3-2 is a standard graph of Ar;
FIGS. 3-3 are standard graphs of Kr;
FIGS. 3-4 are standard graphs of Xe;
FIG. 4-1 is a schematic view of a six-way valve closed state;
FIG. 4-2 is a schematic view of the open state of the six-way valve;
description of reference numerals:
1-a first calibration gas inlet; 2-a second calibration gas inlet; 3-a first sample gas inlet; 4-a second sample gas inlet;
5-a first flow path selection switch; 6-a second flow path selection switch; 7-third flow path selection switch; 8-fourth flow path selection switch;
9-a first six-way valve; 10-a first quantitative ring, 11-a first oxygen removal column; 12-a first impurity removal column; 13-a first chromatography column; 14-pulsed discharge helium ionization detector;
15-a second six-way valve; 16-a second quantification loop; 17-a second impurity removal column; 18-a second chromatography column; 19-a thermal conductivity detector;
20-barometer; 21-a vacuum pump; 22-a carrier gas; 23-a three-way valve; a 24-four-way valve;
v1-first solenoid valve V1; v2-second solenoid valve V2; v3-third solenoid valve V3; v4-fourth solenoid valve V4; v5-fifth solenoid valve V5; v6-sixth solenoid valve V6; v7-seventh solenoid valve V7; v8-eighth solenoid valve V8.
Detailed Description
The invention will be further described with reference to the accompanying drawings.
The invention provides a chromatographic detection method capable of simultaneously detecting contents of various rare gases, which comprises the following steps:
1) pre-vacuumizing the preposed pipeline, so that the gas to be detected containing various rare gases enters the preposed pipeline after being buffered;
2) shunting the gas to be detected to a first channel and a second channel;
3) carrying out deoxidization, impurity removal, 5A molecular sieve capillary chromatographic column separation and pulse discharge helium ionization detection on the quantified gas to be detected in the first channel by using carrier gas 22; meanwhile, the carrier gas 22 is used for removing impurities, separating the 5A molecular sieve capillary chromatographic column and detecting thermal conductivity of the quantified gas to be detected in the second channel in sequence.
The invention also provides a chromatograph capable of simultaneously detecting the contents of various rare gases for realizing the method, which comprises a sample introduction module, a four-way valve 24, a separation detection module, a vacuum pump 21 and a carrier gas 22, wherein the sample introduction module, the four-way valve 24, the separation detection module, the vacuum pump and the carrier gas 22 are arranged in the chromatograph; the separation detection module comprises a first channel and a second channel; the first channel comprises a first six-way valve 9, a first quantitative ring 10, a first deoxygenation column 11, a first impurity removal column 12, a first chromatographic column 13 and a pulse discharge helium ionization detector 14 which are sequentially communicated; both ends of the first quantitative ring 10 are respectively connected with a of the first six-way valve 91Terminal and d1The inlet end of the first oxygen removing column 11 is communicated with the e of the first six-way valve 91The ends are communicated; the second channel comprises a second six-way valve 15, a second quantitative ring 16, a second impurity removal column 17, a second chromatographic column 18 and a thermal conductivity detector 19 which are sequentially communicated; both ends of the second quantitative ring 16 are respectively connected with a of the second six-way valve 152Terminal and d2End-to-end communication, inlet end of the second impurity removing column 17 and e of the second six-way valve 152The ends are communicated; the inlet of the four-way valve 24 is connected with the outlet of the sample injection module; three outlets of the four-way valve 24 are respectively connected with the b of the first six-way valve 91B of end, second six-way valve 152The end is communicated with the air pumping port of the vacuum pump 21; the carrier gas 22 is respectively communicated with f of the first six-way valve 91F of the end, second six-way valve 152End communication. The first chromatographic column 13 and the second chromatographic column 18 are both 5A molecular sieve capillary chromatographic columns. Fig. 4-1 is a schematic view showing a closed state (sample introduction/OFF state) of the six-way valve, and fig. 4-2 is a schematic view showing an open state (sample introduction/ON state) of the six-way valve.
The first impurity removing column 12 and the second impurity removing column 17 are both stainless steel tubes with the column length of 1m and the inner diameter of 1.75mm, 9.5g of a titanium-based zirconium-vanadium-iron alloy getter with the particle size of 30-40 meshes is filled in each column, and the impurity removing amount is 100 mL/g. The first quantitative ring 10 is a 0.50mL quantitative ring; the second quantitation loop 16 is a 1.0mL quantitation loop.
The sample introduction module comprises a first calibration gas inlet 1, a second calibration gas inlet 2, a first sample gas inlet 3, a second sample gas inlet 4, a first flow path selection switch 5, a second flow path selection switch 6, a third flow path selection switch 7 and a fourth flow path selection switch 8, wherein the first flow path selection switch, the second flow path selection switch 6, the third flow path selection switch 7 and the fourth flow path selection switch 8 correspond to the four inlets respectively. The first calibration gas inlet 1 and the first sample gas inlet 3 are used for detecting low-concentration argon, krypton and xenon; the second calibration gas inlet 2 and the second sample gas inlet 4 are used for detecting neon, high-concentration argon, krypton and xenon, and the four are suitable for detecting rare gas diluted by nitrogen. In order to avoid the overlarge calibration gas pressure, buffer processing is needed, two electromagnetic valves V1 and V2 are arranged between the first calibration gas inlet 1 and the first flow path selection switch 5, similarly, two electromagnetic valves V3 and V4 are also arranged between the second calibration gas inlet 2 and the first flow path selection switch 5, and the two electromagnetic valves are used for controlling the sample gas pressure; the pressure of the sample gas injected from the first sample gas inlet 3 and the second sample gas inlet 4 is generally about one atmosphere, and the sample can be directly injected after being vacuumized without buffer treatment. The first flow path selection switch 5, the second flow path selection switch 6, the third flow path selection switch 7 and the fourth flow path selection switch 8 are communicated with the inlet of the four-way valve 24 through a solenoid valve V5, a solenoid valve V7 is arranged between one outlet of the three outlets of the four-way valve 24 and one inlet of the first six-way valve 9, a solenoid valve V8 is arranged between one outlet and one inlet of the second six-way valve 15, and a solenoid valve V6 is arranged between one outlet and the vacuum pump 21; the first flow path selection switch 5, the second flow path selection switch 6, the third flow path selection switch 7 and the fourth flow path selection switch 8 are communicated with the inlet of the four-way valve 24 through a solenoid valve V5, a solenoid valve V7 is arranged between one outlet of the three outlets of the four-way valve 24 and one inlet of the first six-way valve 9, a solenoid valve V8 is arranged between one outlet and one inlet of the second six-way valve 15, and a solenoid valve V6 is arranged between one outlet and the vacuum pump 21; and a barometer 20 installed through a three-way valve 23 is also arranged between the solenoid valve V5 and the inlet of the four-way valve 24.
Examples
1) Parameter setting
A first channel: the temperature of a column box is 40 ℃, the PDHID temperature is 150 ℃, the flow rate of carrier gas 22 (the purity is 99.999%) is 8mL/min, the temperature of a first impurity removal column 12 is 500 ℃, the temperature of a first oxygen removal column 11 is 50 ℃, and the volume of a first quantitative ring 10 is 0.50 mL;
a second channel: the temperature of a column box is 40 ℃, the temperature of TCD is 160 ℃, the flow rate of carrier gas 22 (the purity is 99.999%) is 10mL/min, the temperature of a second impurity removal column 17 is 500 ℃, and the volume of a second quantitative ring 16 is 1.0 mL;
2) procedure for the preparation of the
2.1) opening a vacuum pump 21, opening electromagnetic valves V1, V2, V5, V6, V7 and V8 and a first flow path selection switch 5, vacuumizing a sample introduction pipeline (namely a preposed pipeline) to be less than 0.1hPa, closing the first flow path selection switch 5, and closing the electromagnetic valves V1, V2, V5, V6, V7 and V8;
2.2) opening the electromagnetic valve V1, closing the electromagnetic valve V1 after 10 seconds, opening the electromagnetic valve V2 and the first flow path selection switch 5, closing the electromagnetic valve V2 and the first flow path selection switch 5 after 10 seconds (buffer treatment is performed in the process), opening the electromagnetic valves V5, V7 and V8, allowing gas to enter a quantitative ring, and allowing a pressure gauge to read the sample introduction pressure;
2.3) closing the electromagnetic valves V5, V7 and V8 after the sample injection is finished.
2.4) sampling in a first channel, opening a first six-way valve 9, and enabling a sample to sequentially enter a first oxygen removal column 11, a first impurity removal column 12, a first chromatographic column 13 and a pulse discharge helium ionization detector 14 by carrying a carrier gas 22;
and (3) introducing a sample into the second channel, opening a second six-way valve 15, and enabling the sample to sequentially enter a second quantitative ring 16, a second impurity removal column 17, a second chromatographic column 18 and a thermal conductivity detector 19 by carrying a carrier gas 22.
The method is used for detecting the calibration of low-concentration argon, krypton and xenon by feeding gas from the first calibration gas inlet.
And each sample injection can be carried out by air intake from only one of the first calibration gas inlet 1, the second calibration gas inlet 2, the first sample gas inlet 3 and the second sample gas inlet 4.
When the low-concentration argon, krypton and xenon detection is carried out from the first sample gas inlet gas, the steps 2.1) and 2.2) in the embodiment are replaced as follows:
2.1) opening a vacuum pump 21, opening electromagnetic valves V5, V6, V7, V8 and a third flow path selector switch 7, vacuumizing a sample introduction pipeline (namely a preposed pipeline) to be less than 0.1hPa, closing the third flow path selector switch 7, and closing electromagnetic valves V5, V6, V7 and V8;
2.2) opening electromagnetic valves V5, V7 and V8, allowing gas to enter a quantitative ring, and allowing a pressure gauge to read the sample injection pressure;
when neon and high-concentration argon, krypton and xenon detection is carried out from the inlet gas of the second calibration gas, the step 2.1) and the step 2.2) in the embodiment are replaced as follows:
2.1) opening the vacuum pump 21, opening the electromagnetic valves V3, V4, V5, V6, V7 and V8, and the second flow path selection switch 6, vacuumizing the sample introduction pipeline (i.e. the preposed pipeline) to be less than 0.1hPa, closing the second flow path selection switch 6, and closing the electromagnetic valves V3, V4, V5, V6, V7 and V8;
2.2) opening the electromagnetic valve V3, closing the electromagnetic valve V3 after 10 seconds, opening the electromagnetic valve V4 and the second flow path selection switch 6, closing the electromagnetic valve V4 and the second flow path selection switch 6 after 10 seconds (buffer treatment is performed in the process), opening the electromagnetic valves V5, V7 and V8, allowing gas to enter a quantitative ring, and allowing a pressure gauge to read the sample injection pressure;
when neon and high-concentration argon, krypton and xenon detection is performed from the second sample gas inlet gas, step 2.1) and step 2.2) in the above embodiment are replaced as follows:
2.1) opening the vacuum pump 21, opening the electromagnetic valves V5, V6, V7, V8 and the fourth flow path selection switch 8, vacuumizing the sample introduction pipeline (namely the preposed pipeline) to be less than 0.1hPa, closing the fourth flow path selection switch 8, and closing the electromagnetic valves V5, V6, V7 and V8;
2.2) opening electromagnetic valves V5, V7 and V8, allowing the gas to enter a quantitative ring, and reading the sample injection pressure by a pressure gauge.
In the chromatographic detection, the concentration of each component in the sample is quantified by using an external standard method, a standard curve of response (peak area) and sample injection amount (pressure intensity multiplied by concentration) is obtained by least square fitting, and the content of the component gas in the sample can be obtained according to the response of each component in the sample gas.
Verification of experimental results
(1) Method verification
The results of the test are shown in Table 1.
TABLE 1
The verification result shows that: baseline noise, 30 minute baseline drift, etc. of the PDHID detector and TCD detector meet specifications.
(2) Degree of separation and linearity
The chromatographic test spectrum of Ne, Ar, Kr and Xe is shown in FIG. 2. In FIG. 2-1, the separation degree of Ar and Kr is 3.8, and the separation degree of Kr and Xe is 21.9; in FIG. 2-2, the separation degree of Ne and Ar is 1.8, and the separation degree of Ar and Kr is 5.3.
The standard curve of Ne, Ar, Kr and Xe is shown in figure 3-1, figure 3-2, figure 3-3 and figure 3-4.
Ne linear equation: 0.30157 x-12.58235R2＝0.99961；
Ar linear equation: 0.12894 x-5.53835R2＝0.99997；
Kr linear equation: y 0.00040 x-0.44963R2＝0.99964；
Xe linear equation: y 0.00027 x-0.00933R2＝0.99987；
The four linear correlation coefficients all reach more than 0.999, and the result shows that: the gas chromatograph has stable and reliable measurement.
(3) Test results
The standard gas was denormalized at different times using the standard curve, and the measured concentration values were compared with the nominal values, with the results shown in Table 2.
TABLE 2
The calibration deviation is less than 2% in a certain time, which indicates that the detection method is reliable.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same, and it is obvious for a person skilled in the art to modify the specific technical solutions described in the foregoing embodiments or to substitute part of the technical features, and these modifications or substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions protected by the present invention.
Claims (7)
1. A detection method based on a chromatograph capable of simultaneously detecting contents of various rare gases is characterized by comprising the following steps: the chromatograph comprises a sample introduction module, a four-way valve (24), a separation detection module, a vacuum pump (21) and carrier gas (22);
the separation detection module comprises a first channel and a second channel;
the first channel comprises a first six-way valve (9), a first quantitative ring (10), a first deoxygenation column (11), a first impurity removal column (12), a first chromatographic column (13) and a pulse discharge helium ionization detector (14), which are sequentially communicated; two ends of the first quantitative ring (10) are respectively connected with a of the first six-way valve (9)1Terminal and d1The ends are communicated, the inlet end of the first oxygen removing column (11) is communicated with the e of the first six-way valve (9)1The ends are communicated;
the second channel comprises a second six-way valve (15), a second quantitative ring (16), a second impurity removal column (17), a second chromatographic column (18) and a thermal conductivity detector (19) which are sequentially communicated; two ends of the second quantitative ring (16) are respectively connected with a of the second six-way valve (15)2End and d2The ends are communicated, the inlet end of the second impurity removing column (17) is communicated with the e of the second six-way valve (15)2The ends are communicated;
the inlet of the four-way valve (24) is connected with the outlet of the sample injection module;
three outlets of the four-way valve (24) are respectively connected with b of the first six-way valve (9)1B of end, second six-way valve (15)2The end is communicated with the air pumping port of the vacuum pump (21);
the carrier gas (22) is respectively communicated with f of the first six-way valve (9)1F of end, second six-way valve (15)2The ends are communicated with each other,
the first chromatographic column (13) and the second chromatographic column (18) are both 5A molecular sieve capillary chromatographic columns;
the first impurity removal column (12) and the second impurity removal column (17) are both stainless steel tubes with the column length of 1m and the inner diameter of 1.75mm, 9.5g of a 30-40-mesh titanium-based zirconium-vanadium-iron alloy getter is filled in the columns, and the impurity removal amount is 100 mL/g;
the temperature of a column box of the first channel is 40 ℃, the temperature of PDHID is 150 ℃, the flow rate of carrier gas (22) is 8mL/min, the temperature of a first impurity removal column (12) is 500 ℃, and the temperature of a first oxygen removal column (11) is 50 ℃;
the temperature of a column box of the second channel is 40 ℃, the temperature of TCD is 160 ℃, the flow rate of carrier gas (22) is 10mL/min, and the temperature of a second impurity removal column (17) is 500 ℃;
the chromatographic detection method based on the chromatograph comprises the following steps:
1) enabling the gas to be detected containing various rare gases to enter a sample introduction pipeline;
2) shunting the gas to be detected to a first channel and a second channel;
3) carrying out deoxidization, impurity removal, 5A molecular sieve capillary chromatographic column separation and pulse discharge helium ionization detection on the quantified gas to be detected in the first channel by using carrier gas (22); using carrier gas (22) to sequentially remove impurities, separate a 5A molecular sieve capillary chromatographic column and detect thermal conductivity of the quantified gas to be detected in the second channel;
wherein the multiple rare gases are neon, argon, krypton and xenon.
2. The detection method based on the chromatograph capable of simultaneously detecting the contents of a plurality of rare gases as claimed in claim 1, wherein: the step 1) also comprises the pre-vacuumizing treatment of the sample introduction pipeline.
3. The detection method based on chromatograph capable of simultaneously detecting a plurality of rare gas contents according to claim 1, wherein: the method comprises the step 1) of enabling gas to be detected containing various rare gases to enter a sample introduction pipeline after buffer treatment.
4. The detection method based on chromatograph capable of simultaneously detecting a plurality of rare gas contents according to any one of claims 1 to 3, characterized in that: the first quantitative ring (10) is a 0.50mL quantitative ring; the second quantification loop (16) is a 1.0mL quantification loop.
5. The detection method based on the chromatograph capable of simultaneously detecting the contents of a plurality of rare gases as claimed in claim 4, wherein: the sample introduction module comprises a first calibration gas inlet (1), a second calibration gas inlet (2), a first sample gas inlet (3), a second sample gas inlet (4), and a first flow path selection switch (5), a second flow path selection switch (6), a third flow path selection switch (7) and a fourth flow path selection switch (8) which respectively correspond to the first calibration gas inlet, the second calibration gas inlet, the first sample gas inlet and the second sample gas inlet.
6. The detection method based on the chromatograph capable of simultaneously detecting the contents of a plurality of rare gases as claimed in claim 5, wherein: two first electromagnetic valves (V1) and two second electromagnetic valves (V2) are arranged between the first calibration gas inlet (1) and the first flow path selection switch (5), and two third electromagnetic valves (V3) and two fourth electromagnetic valves (V4) are arranged between the second calibration gas inlet (2) and the first flow path selection switch (5);
the first flow path buffering process is as follows: opening the first electromagnetic valve (V1), closing the first electromagnetic valve (V1) after 10 seconds, opening the second electromagnetic valve (V2) and the first flow path selection switch (5), closing the second electromagnetic valve (V2) and the first flow path selection switch (5) after 10 seconds, and enabling the gas to enter the quantitative ring;
the second flow path buffering process is as follows: the third solenoid valve (V3) is opened, the third solenoid valve (V3) is closed after 10 seconds, the fourth solenoid valve (V4) and the second flow path selection switch (6) are opened, the fourth solenoid valve (V4) and the second flow path selection switch (6) are closed after 10 seconds, and the gas enters the dosing ring.
7. The detection method of claim 6, wherein the detection method is based on a chromatograph capable of simultaneously detecting a plurality of rare gas contents, and is characterized in that: the first flow path selection switch (5), the second flow path selection switch (6), the third flow path selection switch (7) and the fourth flow path selection switch (8) are communicated with the inlet of the four-way valve (24) through a fifth electromagnetic valve (V5), a seventh electromagnetic valve (V7) is arranged between one outlet of the three outlets of the four-way valve (24) and one inlet of the first six-way valve (9), an eighth electromagnetic valve (V8) is arranged between one outlet and one inlet of the second six-way valve (15), and a sixth electromagnetic valve (V6) is arranged between one outlet and the vacuum pump (21); and a barometer (20) installed through a three-way valve (23) is also arranged between the fifth electromagnetic valve (V5) and the inlet of the four-way valve (24).
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| CN112858514B (en) * | 2021-01-18 | 2022-12-13 | 中昊光明化工研究设计院有限公司 | Method for measuring krypton, xenon and methane in air separation oxygen and device for measuring krypton, xenon and methane in air separation oxygen |
| CN113281374B (en) * | 2021-07-13 | 2024-04-12 | 宝武清洁能源鄂州有限公司 | Method for online analysis of helium and neon contents in crude helium-neon |
| CN114034795B (en) * | 2021-11-15 | 2024-03-12 | 北京放射性核素实验室 | 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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