CN113419019B - Gas chromatography system and method for detecting content of high-purity germanium tetrafluoride impurities - Google Patents
Gas chromatography system and method for detecting content of high-purity germanium tetrafluoride impurities Download PDFInfo
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Abstract
The invention belongs to the technical field of high-purity germanium tetrafluoride product quality detection, and particularly discloses a gas chromatography system and a method for detecting the content of impurities in high-purity germanium tetrafluoride, which comprise five switching valve systems, a carrier gas system, a sample injection system, a column system, a tail gas treatment system and a detection system which are mutually connected through pipelines, wherein 6 pieces of carrier gas are arranged, two quantitative rings for containing samples in the sample injection system are communicated, the sample injection of the two quantitative rings can be simultaneously completed, two sets of separation systems are arranged, namely different pre-columns and chromatographic columns are used for separating different components of the high-purity germanium tetrafluoride, the impurity gas after the main component is separated enters the corresponding detection system for detection, the main component germanium tetrafluoride is discharged from each tail gas treatment port in a back flushing mode, and the back flushing time is controlled after the sample injection to purge out the main component germanium tetrafluoride by utilizing double back flushing + central cutting, the detection limit of trace impurity analysis and the accuracy of the result are improved.
Description
Technical Field
The invention belongs to the technical field of high-purity germanium tetrafluoride detection, and particularly relates to a gas chromatography system and a gas chromatography method for detecting the impurity content of high-purity germanium tetrafluoride.
Background
Germanium tetrafluoride (GeF) 4 ) Is a fluoride of germanium, and has special chemical properties: the air-purifying agent is colorless gas at normal temperature and normal pressure, and reacts with water vapor in the air to generate smoke violently when contacting the air. Can be hydrolyzed in water to generate GeO 2 And H 2 GeF 6 ；3GeF 4 +2H 2 O→GeO 2 +2H 2 GeF 6 . The completely dry germanium tetrafluoride gas does not corrode glass, but can corrode mercury and lubricating grease, so that the requirement for detecting the germanium tetrafluoride on instruments is very strict, and special corrosion-resistant parts are required. Germanium tetrafluoride gas has a stimulating effect on eyes, skin, upper respiratory mucosa and lungs, and thus cannot leak into the air.
Germanium tetrafluoride is used primarily to produce stable isotopes of germanium 72 and germanium 76, and is used as a dopant and ion implanter in the semiconductor industry. The isotope of electronic grade germanium tetrafluoride is used as a chemical reagent for producing DRAM chips with the size of below 10nm and optimizing the etching and performance, and is used as a high-energy physical isotope tracer atom.
Due to its special chemical properties. In the detection process of the germanium tetrafluoride gas, since the germanium tetrafluoride corrodes the detector, the main component of the germanium tetrafluoride cannot enter the detector. Therefore, the sampling, analysis and the like of germanium tetrafluoride have great difficulty, and the development of the semiconductor industry needs electronic grade germanium tetrafluoride as a raw material, and has specific requirements on the content of gas impurities in the raw material. Electronic grade germanium tetrafluoride has such important application, but due to the special chemical properties and the requirement of ultrahigh purity, no method for detecting the content of gas impurities in the electronic grade germanium tetrafluoride exists at home at present.
Disclosure of Invention
The invention mainly aims to provide a gas chromatography system and a gas chromatography method for detecting the content of high-purity germanium tetrafluoride impurities, which are used for detecting whether the content of gas impurities in high-purity germanium tetrafluoride meets the requirement of required condition content or not, and provide a reliable detection method for production and trade inspection of electronic grade germanium tetrafluoride.
In order to achieve the above purpose, the invention provides the following technical scheme:
a gas chromatography system for detecting the content of high-purity germanium tetrafluoride impurities comprises a switching valve system, a carrier gas system, a sample introduction system, a column system, a tail gas treatment system and a detection system which are mutually connected through pipelines,
the switching valve system comprises a first switching valve, a second switching valve, a third switching valve, a fourth switching valve and a fifth switching valve which are sequentially connected through a pipeline, the first switching valve and the second switching valve are ten-way valves, and the third switching valve, the fourth switching valve and the fifth switching valve are four-way valves;
the carrier gas system comprises a sixth carrier gas communicated with a third port of the first switching valve, a fifth carrier gas communicated with a port on the red side of the first switching valve, a fourth carrier gas communicated with a third port of the second switching valve, a third carrier gas communicated with a port on the red side of the second switching valve, a second carrier gas communicated with the third port of the third switching valve and a first carrier gas communicated with a second port of the fifth switching valve through pipelines, and the pipelines of the carrier gas system are uniformly controlled by a first electronic gas circuit control system;
the sample injection system comprises a sample inlet pipe connected with a first switching valve sixth port, a first quantitative ring arranged on a pipeline for communicating the first switching valve fourth port with the seventh port, and a second quantitative ring arranged on a pipeline for communicating the second switching valve fourth port with the seventh port, wherein the first switching valve fifth port is connected with the second switching valve sixth port through a pipeline, and the second switching valve fifth port is provided with a sample outlet pipe;
the column system comprises a first pre-column arranged on a first switching valve No. opening and a No. opening communicating pipeline, a first chromatographic column arranged on a first switching valve No. opening and a fourth switching valve No. opening communicating pipeline, a second pre-column arranged on a second switching valve No. opening and a No. opening communicating pipeline, and a second chromatographic column arranged on a third switching valve No. opening and a fourth switching valve No. opening communicating pipeline;
the tail gas treatment system comprises a first tail gas treatment pipe arranged on a first switching valve opening, a second tail gas treatment pipe arranged on a second switching valve opening, a third tail gas treatment pipe arranged on a third switching valve opening, and a fourth tail gas treatment pipe arranged on a fourth switching valve opening;
the detection system comprises a DID detector connected with a No. one port of the fifth switching valve through a pipeline and a TCD detector connected with a No. three port of the fifth switching valve, the DID detector is also connected with a discharge gas helium channel, and the TCD detector is respectively connected with a second electronic gas path control system and a third electronic gas path control system through pipelines;
and the port I of the second switching valve is connected with the port I of the third switching valve through a pipeline, and the port I of the fourth switching valve is connected with the port I of the fifth switching valve through a pipeline.
The first switching valve, the second switching valve, the third switching valve, the fourth switching valve, the fifth switching valve, the first quantitative ring, the second quantitative ring and all connecting pipelines are made of hastelloy.
The filler in the first pre-column is diatomite, and the 13X molecular sieve is filled in the first chromatographic column and is connected with the pipeline in a VCR (video cassette recorder) connection mode.
The second pre-column and the second chromatographic column are both meteorological chromatographic columns.
The first switching valve, the second switching valve, the third switching valve, the fourth switching valve and the fifth switching valve are pneumatic purging switching valves, and the switching valves are provided with two different passages of a solid line and a dotted line.
The invention has the following beneficial effects:
the gas chromatography system provides a method for detecting and measuring high-purity germanium tetrafluoride, and the detection system and the method can detect special impurity components and contents and provide reference data for the use of electronic grade germanium tetrafluoride. After the system samples, the back flushing time is controlled to flush out the main components by using double back flushing and center cutting, so that a sample corrosion detector is avoided. The double detectors with different detection limits detect impurities with different contents in the components, so that the accuracy of the trace impurity analysis result is improved.
Drawings
FIG. 1 is a gas circuit flow chart;
FIG. 2 is an enlarged view of the first and second switching valves of FIG. 1;
FIG. 3 is an enlarged view of the third switching valve, the fourth switching valve and the fifth switching valve of FIG. 1;
wherein: 101. a first switching valve; 102. a second switching valve; 103. a third switching valve; 104 a fourth switching valve; 105. a fifth switching valve; 200. a helium gas electronic bleed passage; 201. a first carrier gas; 202. a second carrier gas; 203. a third carrier gas; 204. a fourth carrier gas; 205. a fifth carrier gas; 206. a sixth carrier gas; 301. a first quantity of rings; 302. a second dosing ring; 401. a first pre-column; 402. a second pre-column; 403. a first chromatographic column; 404. a second chromatography column; 501. a first tail gas treatment pipe; 502. a second tail gas treatment pipe; 503. a third tail gas treatment pipe; 504 a fourth off-gas treatment tube; 601. a first electronic gas circuit control system; 602. a second electronic gas circuit control system; 603. and a third electronic gas circuit control system.
Detailed Description
Example 1
As shown in fig. 1 and 2, a gas chromatography system for detecting the content of high-purity germanium tetrafluoride impurities comprises a switching valve system, a carrier gas system, a sample introduction system, a column system, a tail gas treatment system and a detection system which are connected with each other through pipelines:
the switching valve system comprises a first switching valve 101, a second switching valve 102, a third switching valve 103, a fourth switching valve 104 and a fifth switching valve 105 which are sequentially connected through a pipeline, wherein the first switching valve 101 and the second switching valve 102 are ten-way valves, the third switching valve 103, the fourth switching valve 104 and the fifth switching valve 105 are four-way valves, the first switching valve 101, the second switching valve 102, the third switching valve 103, the fourth switching valve 104 and the fifth switching valve 105 are pneumatic purging switching valves, the switching valves are provided with two different passages of a solid line and a dotted line, the switching valves are made of Hastelloy, and the leakage rate is less than 1 x 10-7cc atm/sec;
carrier gas system includes the sixth carrier gas 206 communicated with number one port of first switching valve separately through the pipeline, the fifth carrier gas 205 communicated with number one port of first switching valve, the fourth carrier gas 204 communicated with number one port of second switching valve, the third carrier gas 203 communicated with number one port of second switching valve, the second carrier gas 202 communicated with number one port of third switching valve and the first carrier gas 201 communicated with number one port of fifth switching valve, the carrier gas system pipeline is controlled by the first electronic gas circuit control system 601 uniformly;
the sample injection system comprises a sample inlet pipe connected with a first switching valve sixth port, a first quantitative ring 301 arranged on a first switching valve fourth port and seventh port communication pipeline, a second quantitative ring 302 arranged on a second switching valve fourth port and seventh port communication pipeline, the first switching valve fifth port is connected with a second switching valve sixth port through a pipeline, and the second switching valve fifth port is provided with a sample outlet pipe; the volume of the two quantitative rings is 1ml, and the materials are all Hastelloy.
The column system comprises a first pre-column 401 arranged on a first switching valve (R) port and a (R) port communication pipeline, a first chromatographic column 403 arranged on the first switching valve (R) port and a (R) fourth switching valve (R) port communication pipeline, a second pre-column 402 arranged on the second switching valve (R) port and a (R) port communication pipeline, and a second chromatographic column 404 arranged on the third switching valve (R) port and a (R) fourth switching valve (R) port communication pipeline;
the tail gas treatment system comprises a first tail gas treatment pipe 501 arranged on a first switching valve opening, a second tail gas treatment pipe 502 arranged on a second switching valve opening, a third tail gas treatment pipe 53 arranged on a third switching valve opening, and a fourth tail gas treatment pipe 54 arranged on a fourth switching valve opening;
the detection system comprises a DID Detector (Ionization Detector DID Detector is simply called DID Detector) connected with a number one port of a fifth switching valve through a pipeline, the lowest detection limit is LOD <10ppb, the use temperature is 65 ℃) and a TCD Detector (Thermal Conductivity Detector is simply called TCD Detector) connected with a number three port, the lowest detection limit is LOD <50PPM, the use temperature is 60 ℃, and the bridge current is 160 mA), the DID Detector is also connected with an electricity-discharging helium channel, and the TCD Detector is respectively connected with a second electronic gas circuit control system 602 and a third electronic gas circuit control system 603 through pipelines;
meanwhile, a port I of the second switching valve is connected with a port I of the third switching valve through a pipeline, a port I of the fourth switching valve is connected with a port I of the fifth switching valve through a pipeline, the first switching valve 101, the second switching valve 12, the third switching valve 13, the fourth switching valve 104, the fifth switching valve 105, the first quantitative ring 31, the second quantitative ring 302 and all connecting pipelines are made of Hastelloy, the first pre-column 401 is a packed column with the specification of 6 '. multidot. 1/8 ' ', diatomite is filled in the packed column, the temperature is 55 ℃, the first chromatographic column 403 is a packed column with the specification of 10 '. star 1/', the 13X molecular sieve is filled in the packed column, the temperature is 55 ℃, the VCR is connected with the pipelines through a connection mode, the second pre-column 402 and the second chromatographic column 404 are meteorological columns with the external diameter of 30m multiplied by 0.32mm, and the use temperature is 55 ℃.
The method for detecting the content of the high-purity germanium tetrafluoride impurity by using the gas chromatography system comprises the following steps:
1. and opening a valve of the first electronic gas circuit control system, setting the carrier gas pressure to be 0.1MP, and simultaneously opening a second electronic gas circuit control system and a third electronic gas circuit control system of the supplementary gas channel. The method comprises the steps of switching a first switching valve and a fourth switching valve in a gas phase system to a dotted line passage, opening a sixth carrier gas channel, setting the flow speed of purge gas to be 10ml/min, allowing carrier gas to enter from a port III of the first switching valve, pass through a port IV, purge a first quantity ring, flow to the port IV from the port IV, purge a first pre-column, flow to the port I from the port IV, and purge the first chromatographic column. And the purging time is 5-10 minutes, and the sixth carrier gas channel is closed after purging.
2. The second switching valve, the fourth switching valve and the fifth switching valve are switched to a dotted line passage, the third switching valve is switched to a solid line passage, a fourth carrier gas channel is opened, the flow speed of purge gas is set to 10ml/min, the carrier gas sequentially passes through a number three port and a number four port of the second switching valve, then flows into a number eight port through the number seven port to enter a second pre-column, then sequentially enters the third switching valve through the number two port and the number four port of the third switching valve, sequentially enters a second chromatographic column through the number two port and the number four port of the third switching valve for separation, and then is sequentially purged. And the purging time is 5-10 minutes, and the fourth carrier gas channel is closed after purging.
During purging, the total carrier gas pressure of the EPC electronic gas circuit control system adopts Agilent 6 th generation EPC, and automatic diagnosis test can be carried out and the first carrier gas, the second carrier gas, the third carrier gas and the fifth carrier gas can be adjusted for pressure compensation; the carrier gas partial pressure adopts a high-precision constant-pressure mechanical valve to carry out secondary pressure stabilization, flow change caused by the change of the opening degree of an outdoor pipeline valve or a steel cylinder valve caused by temperature change is avoided, the flow is always constant, and the spectrum peak drift is avoided; key components such as a pipeline joint, a valve and the like are sealed in a box body in a 5N helium environment to operate in a helium environment protection mode, so that air permeation is avoided; all valves and pipelines in contact with the sample gas are made of Hastelloy materials, so that the hydrofluoric acid and the fluorogermanic acid generated by the hydrolysis of the sample gas are prevented from corroding the system.
Setting the initial temperature of the column box at 25 ℃, the heating speed at 5 ℃/min, the final temperature at 75 ℃ and the final temperature heat preservation time at 30 min.
3. And (3) sample introduction, wherein the first switching valve and the second switching valve are switched to a solid line passage, a sample flows into the first quantitative ring from the No. opening of the first switching valve through a sample inlet pipe, flows into the No. opening from the No. opening of the first switching valve, flows into the No. opening of the second switching valve from the No. opening to the No. opening of the second quantitative ring after being filled with the first quantitative ring, and flows into the No. opening from the No. opening of the No. 4 to the No. opening of the second switching valve and then flows into a sample outlet pipe.
4. After sample injection is finished, the first switching valve is switched to a dotted line passage, the fourth switching valve and the fifth switching valve are switched to a solid line passage, the flow rate of carrier gas helium is adjusted to be 20ml/min, a sixth carrier gas passage is opened, the carrier gas flows into a No. b port through a No. c port of the first switching valve, a sample in a first quantitative ring carried with the carrier tape flows into a No. b port through the No. b port to enter a first pre-column for separation, then flows into the No. b port through the No. c port, is separated again through a first chromatographic column, and separation of O2, Ar and HF and a main component GeF4 is realized in the first pre-column and the first chromatographic column. Impurity O separated 2 Ar and HF sequentially flow into a No. four port of a fifth switching valve through a No. two port of a fourth switching valve and a No. one port of a first switching valve and then flow into a TCD detector through a No. three port, after the TCD detector is kept for 8-14 minutes, when O2, Ar and HF enter the TCD detector and a main component GeF4 is not separated from a chromatographic column, the first switching valve is switched to a solid line state, the fourth switching valve is switched to a dotted line state, a sixth carrier gas 206 valve is opened, and carrier gas sequentially flows through the No. three port and the No. two port of the first switching valveAnd then the pre-column 1 is subjected to back flushing, and then flows through a # opening and a # opening of a first switching valve in sequence to enter a first tail gas suction port. Opening the fifth carrier gas 205 valve, the carrier gas flows through the ports on the red and red in turn to blow back the first chromatographic column, then flows through the port on the second and the third in turn to enter the fourth tail gas suction port. Keeping blowback for 10 minutes, enabling the fifth carrier gas 205 and the sixth carrier gas 206 to blowback the main component germanium tetrafluoride in the first pre-column and the first chromatographic column into the tail gas absorption treatment pipe, and then closing the fifth carrier gas 205 and the sixth carrier gas 206. The carrier gas at each position can not only balance the air pressure, but also participate in back flushing, one carrier gas air path back flushes one chromatographic column, the passing pipelines are shorter and less, and the back flushing efficiency and effect can be increased.
5. Switching a second switching valve, a fourth switching valve and a fifth switching valve to a dotted line passage, switching a third switching valve to a solid line passage, adjusting the flow rate of carrier gas to be 20ml/min, opening a channel of fourth carrier gas, allowing the carrier gas to sequentially pass through a third port and a fourth port of the second switching valve, allowing a sample in a second quantitative ring to flow into the third port through the seventh port and enter a second pre-column for separation, allowing the sample to sequentially enter the third switching valve through the fifth port and the fourth port of the third switching valve and enter a second chromatographic column for separation, and allowing the separated N to sequentially enter the second chromatographic column for separation through the fifth port and the fourth port of the third switching valve 2 、CO 2 、SO 2 And after the carrier gas flows through the port I3 and the port I1 of the second switching valve in sequence, the pre-column 2 is subjected to back flushing, and then flows through the port I w and the port I w of the second switching valve in sequence to enter a second tail gas suction port. And opening a carrier gas 203 valve, wherein the carrier gas sequentially flows through an opening (R) and an opening (C) of the second switching valve, then flows into an opening (R) and an opening (C) of the third switching valve, then enters the second chromatographic column, performs back flushing on the second chromatographic column, and then sequentially flows through an opening (C) and an opening (C) of the fourth switching valve, and then enters a fourth tail gas suction port. Keeping back flushing for 10 minutes, and enabling a fourth carrier gas 204 and a third carrier gas 203 to back flush the main component germanium tetrafluoride in the second pre-column and the second chromatographic column into the tailThe gas absorbs the process tube and then the third and fourth carrier gases 203, 204 are turned off.
6. And (4) after the impurity gas enters a detector for detection, obtaining a gas chromatogram of the sample gas.
Three groups of standard impurity gases with different concentrations are sampled and injected by the same sampling device, and the gas chromatogram of the standard impurity gases is obtained by detecting the same parameters and operation steps.
Calculating the content of impurity gas by contrasting the gas chromatogram of the standard impurity
And calculating the content of impurity gas by contrasting the gas chromatogram of the standard impurity. And averaging the impurity contents obtained by the three detections, thereby further evaluating whether the detected high-purity germanium tetrafluoride meets the requirements.
The experiment verifies that the procedure is consistent with that of the example 1, and the retention time of the sample after passing through the chromatographic column is respectively set to be three experimental groups of 8 minutes, 11 minutes and 14 minutes. It was found that N in the same batch of samples was maintained for these three time periods 2 、O 2 、CO 2 The detected content change rate<0.2 percent. At 8 minutes, the test results showed that the content of Ar, HF and SO2 was low, and all impurity components in the experimental groups kept for 11 minutes and 14 minutes were extremely close. The reason for the analysis is as follows: when the reaction is kept for 8 minutes, the retention time is too short, the influence of the components separated first is not large, and the components separated later are not completely separated due to too short retention time, so that the detection result is low. The experimental groups of 11 minutes and 14 minutes are kept, and finally, the data of the detection results are close. A small amount of the major component germanium tetrafluoride may have entered the detector after a hold time of 14 minutes, so 11 minutes is the optimum hold time, which can accurately detect the content of impurities and avoid the major component germanium tetrafluoride entering the detector and corroding the detector.
Table 1 shows that the results measured while maintaining for 11 minutes all met the impurity level requirements for high purity germanium tetrafluoride.
Claims (5)
1. A method for detecting the content of high-purity germanium tetrafluoride impurities is characterized in that a gas chromatography system is used,
the gas chromatography system comprises a switching valve system, a carrier gas system, a sample introduction system, a column system, a tail gas treatment system and a detection system which are mutually connected through pipelines;
the switching valve system comprises a first switching valve, a second switching valve, a third switching valve, a fourth switching valve and a fifth switching valve which are sequentially connected through a pipeline, the first switching valve and the second switching valve are ten-way valves, and the third switching valve, the fourth switching valve and the fifth switching valve are four-way valves;
the carrier gas system includes the sixth carrier gas communicated with port No. C of the first switching valve, the fifth carrier gas communicated with port No. C of the first switching valve, the fourth carrier gas communicated with port No. C of the second switching valve, the third carrier gas communicated with port No. C of the second switching valve, the second carrier gas communicated with port No. C of the third switching valve and the first carrier gas communicated with port No. C of the fifth switching valve through the pipeline, the pipeline of the carrier gas system is controlled by the first electronic gas circuit control system;
the sample injection system comprises a sample inlet pipe connected with a first switching valve sixth port, a first quantitative ring arranged on a pipeline for communicating the first switching valve fourth port with the seventh port, and a second quantitative ring arranged on a pipeline for communicating the second switching valve fourth port with the seventh port, wherein the first switching valve fifth port is connected with the second switching valve sixth port through a pipeline, and the second switching valve fifth port is provided with a sample outlet pipe;
the column system comprises a first pre-column arranged on a first switching valve (R) port and a (R) port communication pipeline, a first chromatographic column arranged on the first switching valve (R) port and a fourth switching valve (R) port communication pipeline, a second pre-column arranged on a second switching valve (R) port and a (R) port communication pipeline, and a second chromatographic column arranged on a third switching valve (R) port and a fourth switching valve (R) port communication pipeline;
the tail gas treatment system comprises a first tail gas treatment pipe arranged on a first switching valve opening, a second tail gas treatment pipe arranged on a second switching valve opening, a third tail gas treatment pipe arranged on a third switching valve opening, and a fourth tail gas treatment pipe arranged on a fourth switching valve opening;
the detection system comprises a DID detector connected with a No. one port of the fifth switching valve through a pipeline and a TCD detector connected with a No. three port of the fifth switching valve, the DID detector is also connected with a discharge gas helium channel, and the TCD detector is respectively connected with a second electronic gas path control system and a third electronic gas path control system through pipelines;
the first port of the second switching valve is connected with the first port of the third switching valve through a pipeline, and the first port of the fourth switching valve is connected with the fourth port of the fifth switching valve through a pipeline;
the first switching valve, the second switching valve, the third switching valve, the fourth switching valve, the fifth switching valve, the first quantitative ring, the second quantitative ring and all connecting pipelines are made of hastelloy;
the filler in the first pre-column is diatomite, and the 13X molecular sieve is filled in the first chromatographic column and is connected with a pipeline in a VCR (video cassette recorder) connection mode;
the second pre-column and the second chromatographic column are both gas chromatographic columns;
the first switching valve, the second switching valve, the third switching valve, the fourth switching valve and the fifth switching valve are pneumatic purging switching valves, and the switching valves are provided with two different passages, namely a solid line passage and a dotted line passage;
the method specifically comprises the following steps:
s1: opening a first electronic gas circuit control system, setting carrier gas pressure, and simultaneously opening a second electronic gas circuit control system and a third electronic gas circuit control system of a supplementary gas channel;
s2: introducing carrier gas into the whole device for purging, and removing impurities in the device;
s3: sample introduction, namely switching a first switching valve and a second switching valve to a solid line passage, allowing a sample to flow from a No. port of the first switching valve to a No. port through a sample inlet pipe, enter a first quantitative ring, flow from a No. port to a No. port after the first quantitative ring is filled, enter a No. port of the second switching valve, enter a second quantitative ring through the No. port, flow from the No. port to the No. port after the second quantitative ring is filled, and enter a sample outlet pipe;
s4: after the sample introduction is finished, the first switching valve is switched to a dotted line passage, the fourth switching valve and the fifth switching valve are switched to a solid line passage, the flow rate of carrier gas is adjusted, a channel of sixth carrier gas is opened, the carrier gas flows into a No. four port through a No. three port of the first switching valve, a sample in a first quantitative ring of the carrier tape flows into a No. eight port through the No. seven port, enters a first pre-column for separation, then flows to the No. four port through the No. seven port, is separated again through a first chromatographic column, and separated impurities O are removed 2 Ar and HF flow into No. four port of fifth switching valve through No. two ports of fourth switching valve and No. one port, then flow into TCD detector through No. three port, after a period of time, wait for O 2 Ar, HF enter TCD detector and main component GeF 4 Just before separating from the first chromatographic column, the fourth switching valve is switched to a dotted line passage, and the main component GeF 4 The waste gas flows out of a fourth tail gas treatment pipe through a No. two port and a No. three port of a fourth switching valve in sequence, and then a sixth carrier gas is closed;
s5: the second switching valve, the fourth switching valve and the fifth switching valve are switched to a dotted line passage, the third switching valve is switched to a solid line passage, the flow rate of carrier gas is adjusted, a fourth carrier gas channel is opened, the carrier gas sequentially passes through a third opening and a fourth opening of the second switching valve, a sample in a second quantitative ring is carried, flows into a eighth opening through the seventh opening, enters a second pre-column for separation, then sequentially enters the third switching valve through the seventh opening and the eighth opening, sequentially enters a second chromatographic column for separation through the eighth opening and the fourth opening of the third switching valve, and sequentially enters the second chromatographic column for separation through the seventh opening and the seventh opening of the third switching valve, and N separated gas is obtained 2 、CO 2 、SO 2 Sequentially passes through a port IV and a port IV of the fourth switching valve and a port IV of the fifth switching valve, enters a DID detector, is kept for a period of time, is switched to a solid line passage, and contains a main component GeF 4 The tail gas flows out of the fourth tail gas treatment pipe through a port IV and a port III of the fourth switching valve in sequence, and then the fourth carrier gas is closed;
s6: and after the impurity gas enters the detector for detection, obtaining a gas chromatogram of the sample gas, setting a plurality of groups of standard impurity gases with different concentrations, detecting by the same parameters and operation steps to obtain the gas chromatogram of the standard impurity gas, and calculating the content of the impurity gas by contrasting the gas chromatogram of the standard impurity.
2. The method as claimed in claim 1, wherein in step S1, the carrier gas pressure of the first electronic gas circuit control system is 0.1MP, the purge gas flow rate is 10ml/min, and the purge time is 5-10 min in step S2.
3. The method as claimed in claim 1, wherein the flow rate of the carrier gas stream in steps S4 and S5 is 20ml/min, and after the impurity gas enters the detector for 8-14 minutes, the fourth switching valve is operated to discharge the tail gas.
4. The method of claim 1, wherein the first and second chromatographic columns are used at a temperature of 55 ℃.
5. The method as claimed in claim 1, wherein the total carrier gas pressure of the first electronic gas circuit control system, the second electronic gas circuit control system and the third electronic gas circuit control system adopts an Agilent generation 6 electronic gas circuit control system, which can perform automatic diagnosis test and adjust the first carrier gas, the second carrier gas, the third carrier gas and the fifth carrier gas for pressure compensation.
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| CN107121520A (en) * | 2017-06-23 | 2017-09-01 | 洛阳黎明大成氟化工有限公司 | Gas-chromatography valve path system and its application method that a kind of high-purity Nitrogen trifluoride analysis is adsorbed with anaerobic |
| CN109613160A (en) * | 2018-12-26 | 2019-04-12 | 同济大学 | It is a kind of to analyze solubilised state gas H in seawater simultaneously2/O2/N2/CH4Headspace gas chromatography system and method |
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