阅读说明：本技术 一种冷阱预浓缩系统及方法 (Cold trap pre-concentration system and method ) 是由 李虹杰 胡超 周洁 陈楠 于 2020-11-02 设计创作，主要内容包括：本发明涉及一种冷阱预浓缩系统及方法,包括一个能够实现连续不间断采样、解析以及加热反吹的双冷阱组件以及与双冷阱组件的输入连接的四通阀二,用于切换空气和内、外标的六位阀一与四通阀二连接双冷阱组件的输出通过十通阀九与若干电磁阀、气体流量控制组件以及泵组件连接；另外气相色谱GC的氢火焰离子检测器FID进样口和气相色谱GC的质谱检测器MS进样口通过六通阀七与双冷阱组件相连,最后通过六通阀八分别与质谱检测器MS检测组件和氢火焰离子检测器FID检测组件连接。因此,本发明具有如下优点：本发明实现了既能保证连续不间断采样(每小时采样时长可达60min),又能保证输出1h时间分辨率的数据。(The invention relates to a cold trap preconcentration system and a method, which comprises a double cold trap component capable of realizing continuous uninterrupted sampling, analysis and heating back flushing, and a four-way valve II connected with the input of the double cold trap component, wherein the output of the double cold trap component for switching air and connecting a six-position valve I of an inner mark and an outer mark and the four-way valve II is connected with a plurality of electromagnetic valves, a gas flow control component and a pump component through a ten-way valve nine; in addition, a hydrogen flame ion detector FID sample inlet of the gas chromatography GC and a mass spectrometer MS sample inlet of the gas chromatography GC are connected with the double cold trap assembly through a six-way valve seven, and finally are respectively connected with a mass spectrometer MS detection assembly and a hydrogen flame ion detector FID detection assembly through a six-way valve eight. Therefore, the invention has the following advantages: the invention can ensure continuous sampling (the sampling time per hour can reach 60min) and output data with 1h time resolution.)

1. A cold trap preconcentration system is characterized by comprising a double cold trap component capable of realizing continuous uninterrupted sampling, analysis and heating blowback, and a four-way valve II connected with the input of the double cold trap component, wherein the output of the double cold trap component for switching air and connecting a first six-position valve I of an inner mark and a second six-position valve II with the four-way valve II is connected with a plurality of electromagnetic valves, a gas flow control component and a pump component through a nine-way valve; in addition, a hydrogen flame ion detector FID sample inlet of the gas chromatography GC and a mass spectrometer MS sample inlet of the gas chromatography GC are connected with the double cold trap assembly through a six-way valve seven, and finally are respectively connected with a mass spectrometer MS detection assembly and a hydrogen flame ion detector FID detection assembly through a six-way valve eight.

2. The twin cold trap preconcentrator according to claim 1, wherein the twin cold trap assembly comprises at least two water removal traps, a first water removal trap and a second water removal trap, two traps, a first trap and a second trap, and two ten-way valves, two twelve-way valves; water trap-CO removal₂The first pipe is sequentially connected with a ten-way valve III and a ten-way valve IV, and then is connected with the first trap I through a twelve-way valve V to remove water trap II through CO removal₂And the second pipe is sequentially connected with a third ten-way valve and a fourth ten-way valve and then connected with a second trap through a sixth twelve-way valve.

3. The dual cold trap preconcentrator according to claim 2, wherein the analysis assembly comprises two six-way valves, a six-way valve seven and a six-way valve eight; the two twelve-way valves are respectively a twelve-way valve five and a twelve-way valve six; carrier gas helium is connected with the No. 4 position of the seventh six-way valve through an FID sample inlet of the GC, and the carrier gas helium is connected with the No. 1 position of the seventh six-way valve through an MS sample inlet of the GC; the number 2 position of the six-way valve seven is connected with the number 4 position of the twelve-way valve five, the number 3 position of the six-way valve seven is connected with the number 9 position of the twelve-way valve five, the number 5 position of the six-way valve seven is connected with the number 9 position of the twelve-way valve six, and the number 6 position of the six-way valve seven is connected with the number 4 position of the twelve-way valve six; the No. 3 position of the twelve-way valve fifth is connected with the No. 6 position of the six-way valve eighth, the No. 10 position of the twelve-way valve fifth is connected with the No. 5 position of the six-way valve eighth, the No. 3 position of the twelve-way valve sixth is connected with the No. 2 position of the six-way valve eighth, and the No. 10 position of the twelve-way valve sixth is connected with the No. 3 position of the six-way valve eighth; MS detection component links to each other with number 1 position of six-way valve eight, and FID detection component links to each other with number 4 position of six-way valve eight.

4. The dual cold trap preconcentrator according to claim 2, wherein the gas flow control assembly comprises three mass flow meters, MFC one, MFC two, and MFC three, respectively; seven electromagnetic valves, respectively electromagnetic valve V1, electromagnetic valve V2, electromagnetic valve V3, electromagnetic valve V4, electromagnetic valve V5, electromagnetic valve V6, and electromagnetic valve V7; nine ten-way valves; and two pumps, pump one and pump two respectively; the output of the double cold trap assembly is respectively connected with a solenoid valve V1, an MFC I, a solenoid valve V2 and an MFC II through a ten-way valve nine and then connected with a pump I through a V6; the back-blowing nitrogen respectively connects with the electromagnetic valve V4 and the electromagnetic valve V5 after passing through the MFC III and the electromagnetic valve V3 in sequence, and then simultaneously connects with the ten-way valve nine; and the electromagnetic valve V7 is respectively connected with a second four-way valve and a second pump.

5. A cold trap preconcentration method, comprising:

(I) instrument calibration

The method comprises the following steps of sampling by using a cold trap I (external standard) and analyzing by using a cold trap II, and specifically comprises the following steps:

step A1.1, sampling is carried out on a first cold trap, pre-analysis is carried out on a second cold trap, a GC-FID/MS analyzer is triggered and operated, and specifically, the first cold trap collects external standard sample gas; the second cold trap switches the gas path to prepare for sample analysis

Step A1.2, sampling by the cold trap I, and analyzing by the cold trap II; particularly, the first cold trap continuously traps external standard gas; the second cold trap carries the trapped substance into the chromatographic column in the GC through the carrier gas by rapid temperature rise for separation, and finally the substances are detected by FID and MS

Step A1.3, sampling is carried out on the first cold trap, and FID trap heating and back flushing are carried out on the second cold trap and the second dewatering trap; particularly, the first cold trap continuously traps external standard gas; the FID trap paths of the second cold trap and the second water trap blow the water and other impurities clean by heating nitrogen and blowing back;

step A1.4, sampling is carried out on the cold trap I, and heating and back flushing of an MS trapping way are carried out on the cold trap II and the dewatering trap II; particularly, the first cold trap continuously traps external standard gas; the MS trapping paths of the cold trap II and the water trap II blow water and other impurities clean by heating nitrogen and blowing back;

step A1.5, sampling is carried out on the cold trap I, and temperature balance is carried out on the cold trap II; specifically, the first cold trap continues to collect external standard gas; the second cold trap keeps refrigeration and reduces the temperature to the set temperature required by trapping;

the method comprises the steps of cold trap one-step analysis and cold trap two-step sampling (external standard), and specifically comprises the following steps:

step A2.1, sampling by a cold trap II, pre-analyzing by the cold trap I, and triggering and operating a GC-FID/MS analyzer; specifically, a first cold trap switches over a gas path to prepare for sample analysis; the cold trap II collects the external standard gas;

step A2.2, sampling by the cold trap II, and analyzing by the cold trap I; specifically, a first cold trap carries trapped substances into a chromatographic column in a GC through a carrier gas by rapid heating for separation, and finally, the separation is carried out by FID and MS, and a second cold trap continues to trap external standard gas;

step A2.3, sampling by a cold trap II, and carrying out FID trap heating and back flushing by the cold trap I and a water trap I; particularly, the first cold trap and the first water removal trap blow water and other impurities clean through heating nitrogen and back blowing; (ii) a The second cold trap continues to trap the external standard gas;

step A2.4, sampling by a cold trap II, and carrying out MS trapping path heating back flushing by the cold trap I and a water trap I; specifically, an MS trapping path of a first cold trap and a first water trap purges water and other impurities through heating nitrogen and back flushing; the second cold trap continues to trap the external standard gas;

step A2.5, sampling by the cold trap II, and balancing the temperature by the cold trap I; particularly, the cold trap keeps refrigeration, and the temperature is reduced to the set temperature required by trapping; the second cold trap continues to trap the external standard gas;

(II) air sample Capture and analysis

The method comprises the steps of sampling by a cold trap and analyzing by a cold trap, and specifically comprises the following steps:

b1.1, sampling by the first cold trap, pre-analyzing by the second cold trap, triggering and operating the GC-FID/MS analyzer, and specifically trapping air by the first cold trap; the second cold trap switches the gas path to prepare for sample analysis;

step B1.2, sampling by the cold trap I, and analyzing by the cold trap II; specifically, the first cold trap continuously traps air, the second cold trap carries trapped substances into a chromatographic column in a GC through carrier gas by rapid temperature rise for separation, and finally, the separation is carried out by FID and MS;

b1.3, sampling the cold trap I, and carrying out FID trap heating and back flushing on the cold trap II and the dewatering trap II; specifically, the first cold trap continuously traps air, and the FID trap path of the second cold trap and the second dewatering trap sweeps water and other impurities clean through heating nitrogen and back flushing;

b1.4, sampling the cold trap I, and carrying out MS trapping path heating back flushing on the cold trap II and the dewatering trap II; specifically, air is continuously trapped by the first cold trap, and moisture and other impurities are blown and cleaned by an MS trapping path of the second cold trap and the second dewatering trap through heating nitrogen and back flushing;

step B1.5, sampling the first cold trap, and balancing the temperature of the second cold trap; specifically, the first cold trap continues to collect air, the second cold trap keeps refrigerating, and the temperature is reduced to a set temperature required by trapping;

the method comprises the steps of cold trap one-step analysis and cold trap two-step sampling, and specifically comprises the following steps:

b2.1, sampling by a cold trap II, pre-analyzing by the cold trap I, and triggering and operating a GC-FID/MS analyzer; specifically, a first cold trap switches over an air path to prepare for sample analysis, and a second cold trap traps air;

step B2.2, sampling by the cold trap II, and analyzing by the cold trap I; specifically, a first cold trap carries trapped substances into a chromatographic column in a GC through carrier gas by rapid heating for separation, and finally, the separation is carried out by FID and MS, and a second cold trap continues to trap air;

b2.3, sampling by the cold trap II, and carrying out FID trap heating and back flushing by the cold trap I and the water trap I; specifically, the first cold trap and the first water removal trap blow water and other impurities clean through heating nitrogen and back blowing, and the second cold trap continues to capture air;

b2.4, sampling by a cold trap II, and carrying out MS trapping path heating back flushing by the cold trap I and the water trap I; specifically, an MS trapping path of a first cold trap and a first water trap purges water and other impurities through heating nitrogen and back flushing; the second cold trap continues to trap air;

step B2.5, sampling by the cold trap II, and balancing the temperature by the cold trap I; particularly, the cold trap keeps refrigeration, and the temperature is reduced to the set temperature required by trapping; and the second cold trap continues to trap air.

6. A cold trap preconcentration method according to claim 1, wherein the gas flow direction in step B1.1 is, in order: the air sample is sequentially as follows: the system comprises a six-position valve I5, a four-way valve II A, a water removing trap I, a ten-way valve III A, a ten-way valve IV, a twelve-way valve V, a number, a ten-way valve nine A, V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and a pump I (on); the nitrogen gas is sequentially as follows: MFC three (off); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a six A position of a twelve-way valve, an eight A position of the six-way valve, an MS detection component and an FID detection component.

7. A cold trap preconcentration method according to claim 1, wherein the gas flow direction in step B1.2 is, in order: the air sample is sequentially as follows: the six-position valve I5, the four-way valve II A, the ten-way valve III A, the ten-way valve IV, the twelve-way valve IV, the ten-way valve IV, the V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and the pump I (on); the nitrogen gas is sequentially as follows: MFC three (off); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a six B position of a twelve-way valve, an eight A position of the six-way valve, an MS detection component and an FID detection component.

8. A cold trap preconcentration method according to claim 1, wherein the gas flow direction in step B1.3 is, in order: the air sample is sequentially as follows: the six-position valve I5, the four-way valve II A, the ten-way valve III A, the ten-way valve IV, the twelve-way valve IV, the ten-way valve IV, the V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and the pump I (on); the nitrogen gas is sequentially as follows: MFC three (on), V3 (on), V4(COM is connected with NC), ten-way valve nine A position, twelve-way valve six A position, ten-way valve four A position, ten-way valve three A position, water removal trap two, four-way valve two A position, V7(COM is connected with NC) and pump two (on); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a six A position of a twelve-way valve, an eight A position of the six-way valve, an MS detection component and an FID detection component.

9. A cold trap preconcentration method according to claim 1, wherein the gas flow direction in step B1.4 is, in order: the air sample is sequentially as follows: the six-position valve I5, the four-way valve II A, the ten-way valve III A, the ten-way valve IV, the twelve-way valve IV, the ten-way valve IV, the V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and the pump I (on); the nitrogen gas is sequentially as follows: MFC three (on), V3 (on), V5(COM is connected with NC), ten-way valve nine A position, twelve-way valve six A position, ten-way valve four A position, ten-way valve three A position, water removal trap two, four-way valve two A position, V7(COM is connected with NC) and pump two (on); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a six A position of a twelve-way valve, an eight A position of the six-way valve, an MS detection component and an FID detection component.

10. A cold trap preconcentration method according to claim 1, wherein the gas flow directions in step B1.5 are, in order: the air sample is sequentially as follows: the six-position valve I5, the four-way valve II A, the ten-way valve III A, the ten-way valve IV, the twelve-way valve IV, the ten-way valve IV, the V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and the pump I (on); the nitrogen gas is sequentially as follows: MFC three (off); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a six A position of a twelve-way valve, an eight A position of the six-way valve, an MS detection component and an FID detection component.

11. A cold trap preconcentration method according to claim 1, wherein the gas flow direction in the step B2.1 is sequentially as follows: the air sample is sequentially as follows: a first 5-position six-position valve, a second B-position four-way valve, a second water removing trap, a third B-position ten-way valve, a fourth B-position ten-way valve, a sixth A-position twelve-way valve, a ninth B-position ten-way valve, V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and a first pump (on); the nitrogen gas is sequentially as follows: MFC three (off); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven A position of a six-way valve, a five A position of a twelve-way valve, an eight B position of a six-way valve, an MS detection component and an FID detection component.

12. A cold trap preconcentration method according to claim 1, wherein the gas flow direction in the step B2.2 is sequentially as follows: the air sample is sequentially as follows: a first 5-position six-position valve, a second B-position four-way valve, a second water removing trap, a third B-position ten-way valve, a fourth B-position ten-way valve, a sixth A-position twelve-way valve, a ninth B-position ten-way valve, V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and a first pump (on); the nitrogen gas is sequentially as follows: MFC three (off); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a five B position of a twelve-way valve, an eight B position of a six-way valve, an MS detection component and an FID detection component.

13. A cold trap preconcentration method according to claim 1, wherein the gas flow direction in step B2.3 is, in order: the air sample is sequentially as follows: a first 5-position six-position valve, a second B-position four-way valve, a second water removing trap, a third B-position ten-way valve, a fourth B-position ten-way valve, a sixth A-position twelve-way valve, a ninth B-position ten-way valve, V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and a first pump (on); the nitrogen gas is sequentially as follows: MFC three (on), V3 (on), V4(COM is connected with NO), ten-way valve nine B position, twelve-way valve five A position, ten-way valve four B position, ten-way valve three B position, water removing trap one, four-way valve two B position, V7(COM is connected with NC) and pump two (on); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a five A position of a twelve-way valve, an eight B position of a six-way valve, an MS detection component and an FID detection component.

14. A cold trap preconcentration method according to claim 1, wherein the gas flow direction in step B2.4 is, in order: the air sample is sequentially as follows: a first 5-position six-position valve, a second B-position four-way valve, a second water removing trap, a third B-position ten-way valve, a fourth B-position ten-way valve, a sixth A-position twelve-way valve, a ninth B-position ten-way valve, V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and a first pump (on); the nitrogen gas is sequentially as follows: MFC three (on), V3 (on), V5(COM is connected with NO), ten-way valve nine B position, twelve-way valve five A position, ten-way valve four B position, ten-way valve three B position, water removing trap one, four-way valve two B position, V7(COM is connected with NC) and pump two (on); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a five A position of a twelve-way valve, an eight B position of a six-way valve, an MS detection component and an FID detection component.

15. A cold trap preconcentration method according to claim 1, wherein the gas flow direction in step B2.5 is, in order: the air sample is sequentially as follows: a first 5-position six-position valve, a second B-position four-way valve, a second water removing trap, a third B-position ten-way valve, a fourth B-position ten-way valve, a sixth A-position twelve-way valve, a ninth B-position ten-way valve, V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and a first pump (on); the nitrogen gas is sequentially as follows: MFC three (off); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a five A position of a twelve-way valve, an eight B position of a six-way valve, an MS detection component and an FID detection component.

16. A cold trap preconcentration method according to claim 1, wherein the gas flow direction of the calibration step coincides with the air sample flow direction except that the first six-position valve switches from position 5 to position 3.

Technical Field

The invention relates to cold trap pre-concentration equipment and a method, which are mainly used in the field of environmental monitoring, in particular to equipment and a method for continuously and uninterruptedly trapping volatile organic compounds.

Background

Volatile organic compounds in the air are various in types, have large difference of physical and chemical properties (boiling point and polarity), are low in concentration and large in difference (the concentration range is between ppt-ppb), and are difficult to directly measure by using an analytical instrument; therefore, it is necessary to collect and concentrate organic compounds in the air and then measure the organic compounds.

The method for trapping and concentrating the volatile organic compounds in the air mainly comprises the steps of adsorbent adsorption concentration and cold trap freezing concentration; compared with an adsorbent, the cold trap concentration has the advantages of simple structure, high trapping efficiency, rapid thermal desorption, no residue and the like; the principle of cold trap trapping analysis is that after being trapped and concentrated, the sample is heated and analyzed, carried into a chromatographic column by a carrier gas of a GC sample inlet for separation, and then detected by a FID detector and an MS detector.

The technical requirements and detection method of an environmental air volatile organic compound gas chromatography continuous monitoring system of HJ-2010 published in 7 months in 2019 make requirements on the sampling time of volatile organic compounds, namely that the accumulated sampling time per hour is not less than 30min, and the data of 1h time resolution can be output.

The monitoring process of the gas chromatography continuous monitoring system for the volatile organic compounds in the ambient air comprises the processes of collecting an air sample, collecting an internal standard sample, analyzing, balancing an instrument and the like; in the process, the chromatographic-mass spectrometric separation and analysis time is at least more than 35 minutes, so that the single cold trap trapping mode cannot meet the requirements of the existing standard before the market.

Therefore, there is a need to develop an apparatus and method that can ensure continuous sampling (the cumulative sampling time per hour should be no less than 30min) and output data with 1h time resolution.

Disclosure of Invention

The invention mainly meets the technical problems of 'the accumulated sampling time per hour is not less than 30min and the data of 1h time resolution can be ensured to be output' which are required by the existing standard and the method problem of adopting double cold traps to realize the requirement; an apparatus and method for continuous uninterrupted sampling and trapping of volatile organic compounds is provided.

The technical problem of the invention is mainly solved by the following technical scheme:

a cold trap preconcentration system is characterized by comprising a double cold trap component capable of realizing continuous uninterrupted sampling, analysis and heating blowback, and a four-way valve II connected with the input of the double cold trap component, wherein the output of the double cold trap component for switching air and connecting a first six-position valve I of an inner mark and a second six-position valve II with the four-way valve II is connected with a plurality of electromagnetic valves, a gas flow control component and a pump component through a nine-way valve; in addition, a hydrogen flame ion detector FID sample inlet of the gas chromatography GC and a mass spectrometer MS sample inlet of the gas chromatography GC are connected with the double cold trap assembly through a six-way valve seven, and finally are respectively connected with a mass spectrometer MS detection assembly and a hydrogen flame ion detector FID detection assembly through a six-way valve eight.

In the above-mentioned double-cold-trap preconcentrator, the double-cold-trap assembly includes at least two dewatering traps, which are a dewatering trap one and a dewatering trap two, respectively, two trapping traps, which are a trapping trap one and a trapping trap two, respectively, and two ten-way valves and two twelve-way valves; water trap-CO removal₂The first pipe is sequentially connected with a ten-way valve III and a ten-way valve IV, and then is connected with the first trap I through a twelve-way valve V to remove water trap II through CO removal₂And the second pipe is sequentially connected with a third ten-way valve and a fourth ten-way valve and then connected with a second trap through a sixth twelve-way valve.

In the above double cold trap preconcentration device, the analysis assembly includes two six-way valves, namely a six-way valve seven and a six-way valve eight; the two twelve-way valves are respectively a twelve-way valve five and a twelve-way valve six; carrier gas helium is connected with the No. 4 position of the seventh six-way valve through an FID sample inlet of the GC, and the carrier gas helium is connected with the No. 1 position of the seventh six-way valve through an MS sample inlet of the GC; the number 2 position of the six-way valve seven is connected with the number 4 position of the twelve-way valve five, the number 3 position of the six-way valve seven is connected with the number 9 position of the twelve-way valve five, the number 5 position of the six-way valve seven is connected with the number 9 position of the twelve-way valve six, and the number 6 position of the six-way valve seven is connected with the number 4 position of the twelve-way valve six; the No. 3 position of the twelve-way valve fifth is connected with the No. 6 position of the six-way valve eighth, the No. 10 position of the twelve-way valve fifth is connected with the No. 5 position of the six-way valve eighth, the No. 3 position of the twelve-way valve sixth is connected with the No. 2 position of the six-way valve eighth, and the No. 10 position of the twelve-way valve sixth is connected with the No. 3 position of the six-way valve eighth; MS detection component links to each other with number 1 position of six-way valve eight, and FID detection component links to each other with number 4 position of six-way valve eight.

In the above dual cold trap preconcentrator, the gas flow control assembly includes three mass flow meters, which are MFC one, MFC two, and MFC three, respectively; seven electromagnetic valves, respectively electromagnetic valve V1, electromagnetic valve V2, electromagnetic valve V3, electromagnetic valve V4, electromagnetic valve V5, electromagnetic valve V6, and electromagnetic valve V7; nine ten-way valves; and two pumps, pump one and pump two respectively; the output of the double cold trap assembly is respectively connected with a solenoid valve V1, an MFC I, a solenoid valve V2 and an MFC II through a ten-way valve nine and then connected with a pump I through a V6; the back-blowing nitrogen respectively connects with the electromagnetic valve V4 and the electromagnetic valve V5 after passing through the MFC III and the electromagnetic valve V3 in sequence, and then simultaneously connects with the ten-way valve nine; the electromagnetic valve V7 is respectively connected with a four-way valve II and a pump II,

a cold trap preconcentration method, comprising:

(I) instrument calibration

The method comprises the following steps of sampling by using a cold trap I (external standard) and analyzing by using a cold trap II, and specifically comprises the following steps:

step A1.1, sampling is carried out on a first cold trap, pre-analysis is carried out on a second cold trap, a GC-FID/MS analyzer is triggered and operated, and specifically, the first cold trap collects external standard sample gas; the second cold trap switches the gas path to prepare for sample analysis

Step A1.2, sampling by the cold trap I, and analyzing by the cold trap II; particularly, the first cold trap continuously traps external standard gas; the second cold trap carries the trapped substance into the chromatographic column in the GC through the carrier gas by rapid temperature rise for separation, and finally the substances are detected by FID and MS

Step A1.3, sampling is carried out on the first cold trap, and FID trap heating and back flushing are carried out on the second cold trap and the second dewatering trap; particularly, the first cold trap continuously traps external standard gas; the FID trap paths of the second cold trap and the second water trap blow the water and other impurities clean by heating nitrogen and blowing back;

step A1.4, sampling is carried out on the cold trap I, and heating and back flushing of an MS trapping way are carried out on the cold trap II and the dewatering trap II; particularly, the first cold trap continuously traps external standard gas; the MS trapping paths of the cold trap II and the water trap II blow water and other impurities clean by heating nitrogen and blowing back;

step A1.5, sampling is carried out on the cold trap I, and temperature balance is carried out on the cold trap II; specifically, the first cold trap continues to collect external standard gas; the second cold trap keeps refrigeration and reduces the temperature to the set temperature required by trapping;

the method comprises the steps of cold trap one-step analysis and cold trap two-step sampling (external standard), and specifically comprises the following steps:

step A2.1, sampling by a cold trap II, pre-analyzing by the cold trap I, and triggering and operating a GC-FID/MS analyzer; specifically, a first cold trap switches over a gas path to prepare for sample analysis; the cold trap II collects the external standard gas;

step A2.2, sampling by the cold trap II, and analyzing by the cold trap I; specifically, a first cold trap carries trapped substances into a chromatographic column in a GC through a carrier gas by rapid heating for separation, and finally, the separation is carried out by FID and MS, and a second cold trap continues to trap external standard gas;

step A2.3, sampling by a cold trap II, and carrying out FID trap heating and back flushing by the cold trap I and a water trap I; particularly, the first cold trap and the first water removal trap blow water and other impurities clean through heating nitrogen and back blowing; (ii) a The second cold trap continues to trap the external standard gas;

step A2.4, sampling by a cold trap II, and carrying out MS trapping path heating back flushing by the cold trap I and a water trap I; specifically, an MS trapping path of a first cold trap and a first water trap purges water and other impurities through heating nitrogen and back flushing; the second cold trap continues to trap the external standard gas;

step A2.5, sampling by the cold trap II, and balancing the temperature by the cold trap I; particularly, the cold trap keeps refrigeration, and the temperature is reduced to the set temperature required by trapping; the second cold trap continues to trap the external standard gas;

(II) air sample Capture and analysis

The method comprises the steps of sampling by a cold trap and analyzing by a cold trap, and specifically comprises the following steps:

b1.1, sampling by the first cold trap, pre-analyzing by the second cold trap, triggering and operating the GC-FID/MS analyzer, and specifically trapping air by the first cold trap; the second cold trap switches the gas path to prepare for sample analysis;

step B1.2, sampling by the cold trap I, and analyzing by the cold trap II; specifically, the first cold trap continuously traps air, the second cold trap carries trapped substances into a chromatographic column in a GC through carrier gas by rapid temperature rise for separation, and finally, the separation is carried out by FID and MS;

b1.3, sampling the cold trap I, and carrying out FID trap heating and back flushing on the cold trap II and the dewatering trap II; specifically, the first cold trap continuously traps air, and the FID trap path of the second cold trap and the second dewatering trap sweeps water and other impurities clean through heating nitrogen and back flushing;

b1.4, sampling the cold trap I, and carrying out MS trapping path heating back flushing on the cold trap II and the dewatering trap II; specifically, air is continuously trapped by the first cold trap, and moisture and other impurities are blown and cleaned by an MS trapping path of the second cold trap and the second dewatering trap through heating nitrogen and back flushing;

step B1.5, sampling the first cold trap, and balancing the temperature of the second cold trap; specifically, the first cold trap continues to collect air, the second cold trap keeps refrigerating, and the temperature is reduced to a set temperature required by trapping;

the method comprises the steps of cold trap one-step analysis and cold trap two-step sampling, and specifically comprises the following steps:

b2.1, sampling by a cold trap II, pre-analyzing by the cold trap I, and triggering and operating a GC-FID/MS analyzer; specifically, a first cold trap switches over an air path to prepare for sample analysis, and a second cold trap traps air;

step B2.2, sampling by the cold trap II, and analyzing by the cold trap I; specifically, a first cold trap carries trapped substances into a chromatographic column in a GC through carrier gas by rapid heating for separation, and finally, the separation is carried out by FID and MS, and a second cold trap continues to trap air;

b2.3, sampling by the cold trap II, and carrying out FID trap heating and back flushing by the cold trap I and the water trap I; specifically, the first cold trap and the first water removal trap blow water and other impurities clean through heating nitrogen and back blowing, and the second cold trap continues to capture air;

b2.4, sampling by a cold trap II, and carrying out MS trapping path heating back flushing by the cold trap I and the water trap I; specifically, an MS trapping path of a first cold trap and a first water trap purges water and other impurities through heating nitrogen and back flushing; the second cold trap continues to trap air;

step B2.5, sampling by the cold trap II, and balancing the temperature by the cold trap I; particularly, the cold trap keeps refrigeration, and the temperature is reduced to the set temperature required by trapping; and the second cold trap continues to trap air.

In the cold trap preconcentration method, the gas flow direction in the step B1.1 sequentially includes: the air sample is sequentially as follows: the system comprises a six-position valve I5, a four-way valve II A, a water removing trap I, a ten-way valve III A, a ten-way valve IV, a twelve-way valve V, a number, a ten-way valve nine A, V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and a pump I (on); the nitrogen gas is sequentially as follows: MFC three (off); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a six A position of a twelve-way valve, an eight A position of the six-way valve, an MS detection component and an FID detection component

In the cold trap preconcentration method, the gas flow direction in the step B1.2 sequentially includes: the air sample is sequentially as follows: the six-position valve I5, the four-way valve II A, the ten-way valve III A, the ten-way valve IV, the twelve-way valve IV, the ten-way valve IV, the V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and the pump I (on); the nitrogen gas is sequentially as follows: MFC three (off); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a six B position of a twelve-way valve, an eight A position of the six-way valve, an MS detection component and an FID detection component.

In the cold trap preconcentration method, the gas flow direction in step B1.3 sequentially includes: the air sample is sequentially as follows: the six-position valve I5, the four-way valve II A, the ten-way valve III A, the ten-way valve IV, the twelve-way valve IV, the ten-way valve IV, the V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and the pump I (on); the nitrogen gas is sequentially as follows: MFC three (on), V3 (on), V4(COM is connected with NC), ten-way valve nine A position, twelve-way valve six A position, ten-way valve four A position, ten-way valve three A position, water removal trap two, four-way valve two A position, V7(COM is connected with NC) and pump two (on); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a six A position of a twelve-way valve, an eight A position of the six-way valve, an MS detection component and an FID detection component

In the cold trap preconcentration method, the gas flow direction in step B1.4 sequentially includes: the air sample is sequentially as follows: the six-position valve I5, the four-way valve II A, the ten-way valve III A, the ten-way valve IV, the twelve-way valve IV, the ten-way valve IV, the V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and the pump I (on); the nitrogen gas is sequentially as follows: MFC three (on), V3 (on), V5(COM is connected with NC), ten-way valve nine A position, twelve-way valve six A position, ten-way valve four A position, ten-way valve three A position, water removal trap two, four-way valve two A position, V7(COM is connected with NC) and pump two (on); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a six A position of a twelve-way valve, an eight A position of the six-way valve, an MS detection component and an FID detection component

In the cold trap preconcentration method, the gas flow direction in step B1.5 sequentially includes: the air sample is sequentially as follows: the six-position valve I5, the four-way valve II A, the ten-way valve III A, the ten-way valve IV, the twelve-way valve IV, the ten-way valve IV, the V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and the pump I (on); the nitrogen gas is sequentially as follows: MFC three (off); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a six A position of a twelve-way valve, an eight A position of the six-way valve, an MS detection component and an FID detection component

In the cold trap preconcentration method, the gas flow direction in the step B2.1 sequentially includes: the air sample is sequentially as follows: a first 5-position six-position valve, a second B-position four-way valve, a second water removing trap, a third B-position ten-way valve, a fourth B-position ten-way valve, a sixth A-position twelve-way valve, a ninth B-position ten-way valve, V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and a first pump (on); the nitrogen gas is sequentially as follows: MFC three (off); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven A position of a six-way valve, a five A position of a twelve-way valve, an eight B position of a six-way valve, an MS detection component and an FID detection component

In the cold trap preconcentration method, the gas flow direction in the step B2.2 sequentially includes: the air sample is sequentially as follows: a first 5-position six-position valve, a second B-position four-way valve, a second water removing trap, a third B-position ten-way valve, a fourth B-position ten-way valve, a sixth A-position twelve-way valve, a ninth B-position ten-way valve, V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and a first pump (on); the nitrogen gas is sequentially as follows: MFC three (off); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a five B position of a twelve-way valve, an eight B position of a six-way valve, an MS detection component and an FID detection component

In the cold trap preconcentration method, the gas flow direction in the step B2.3 sequentially includes: the air sample is sequentially as follows: a first 5-position six-position valve, a second B-position four-way valve, a second water removing trap, a third B-position ten-way valve, a fourth B-position ten-way valve, a sixth A-position twelve-way valve, a ninth B-position ten-way valve, V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and a first pump (on); the nitrogen gas is sequentially as follows: MFC three (on), V3 (on), V4(COM is connected with NO), ten-way valve nine B position, twelve-way valve five A position, ten-way valve four B position, ten-way valve three B position, water removing trap one, four-way valve two B position, V7(COM is connected with NC) and pump two (on); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a five A position of a twelve-way valve, an eight B position of a six-way valve, an MS detection component and an FID detection component

In the cold trap preconcentration method, the gas flow direction in step B2.4 sequentially includes: the air sample is sequentially as follows: a first 5-position six-position valve, a second B-position four-way valve, a second water removing trap, a third B-position ten-way valve, a fourth B-position ten-way valve, a sixth A-position twelve-way valve, a ninth B-position ten-way valve, V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and a first pump (on); the nitrogen gas is sequentially as follows: MFC three (on), V3 (on), V5(COM is connected with NO), ten-way valve nine B position, twelve-way valve five A position, ten-way valve four B position, ten-way valve three B position, water removing trap one, four-way valve two B position, V7(COM is connected with NC) and pump two (on); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a five A position of a twelve-way valve, an eight B position of a six-way valve, an MS detection component and an FID detection component

In the cold trap preconcentration method, the gas flow direction in the step B2.5 sequentially includes: the air sample is sequentially as follows: a first 5-position six-position valve, a second B-position four-way valve, a second water removing trap, a third B-position ten-way valve, a fourth B-position ten-way valve, a sixth A-position twelve-way valve, a ninth B-position ten-way valve, V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and a first pump (on); the nitrogen gas is sequentially as follows: MFC three (off); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a five A position of a twelve-way valve, an eight B position of a six-way valve, an MS detection component and an FID detection component

In the cold trap preconcentration method, the gas flow direction of the calibration step is consistent with the air sample flow direction, and only the first six-position valve is switched from the No. 5 position to the No. 3 position.

Therefore, the invention has the following advantages: 1. the invention can ensure continuous sampling (the sampling time per hour can reach 60min) and output data with 1h time resolution; 2. the invention provides sufficient time for the analysis of the chromatography-mass spectrometry, thereby expanding the separation and detection of more substance types; 3. by skillfully matching a plurality of valves, the invention can really realize the orderly continuous sampling, analysis and back flushing by only one set of flow control and one set of analysis equipment, and has high efficiency and cost saving; 4. according to the invention, the cold trap is used for directly trapping the sample, and the sample directly enters the analysis equipment after being analyzed, so that the problems of uncertain pollution, adsorption and the like possibly caused by other indirect sampling processes are avoided.

Drawings

FIG. 1 is a schematic diagram of the present invention;

Detailed Description

The technical scheme of the invention is further specifically described by the following embodiments and the accompanying drawings.

Example (b):

a,

The invention relates to a cold trap preconcentration system, which comprises a double cold trap component capable of realizing continuous uninterrupted sampling, analysis and heating back flushing, and a four-way valve II connected with the input of the double cold trap component, wherein the output of the double cold trap component for switching air and connecting a six-position valve I of an inner mark and an outer mark and the four-way valve II is connected with a plurality of electromagnetic valves, gas flow control components and pump components through a ten-way valve nine; in addition, a hydrogen flame ion detector FID sample inlet of the gas chromatography GC and a mass spectrometer MS sample inlet of the gas chromatography GC are connected with the double cold trap assembly through a six-way valve seven, and finally are respectively connected with a mass spectrometer MS detection assembly and a hydrogen flame ion detector FID detection assembly through a six-way valve eight.

The double-cold-trap assembly comprises at least two water removing traps, namely a first water removing trap and a second water removing trap, two trapping traps, namely a first trapping trap and a second trapping trap, two ten-way valves and two twelve-way valves; water trap-CO removal₂The first pipe is sequentially connected with a ten-way valve III and a ten-way valve IV, and then is connected with the first trap I through a twelve-way valve V to remove water trap II through CO removal₂And the second pipe is sequentially connected with a third ten-way valve and a fourth ten-way valve and then connected with a second trap through a sixth twelve-way valve.

The analysis component comprises two six-way valves, namely a six-way valve seven and a six-way valve eight; the two twelve-way valves are respectively a twelve-way valve five and a twelve-way valve six; carrier gas helium is connected with the No. 4 position of the seventh six-way valve through an FID sample inlet of the GC, and the carrier gas helium is connected with the No. 1 position of the seventh six-way valve through an MS sample inlet of the GC; the number 2 position of the six-way valve seven is connected with the number 4 position of the twelve-way valve five, the number 3 position of the six-way valve seven is connected with the number 9 position of the twelve-way valve five, the number 5 position of the six-way valve seven is connected with the number 9 position of the twelve-way valve six, and the number 6 position of the six-way valve seven is connected with the number 4 position of the twelve-way valve six; the No. 3 position of the twelve-way valve fifth is connected with the No. 6 position of the six-way valve eighth, the No. 10 position of the twelve-way valve fifth is connected with the No. 5 position of the six-way valve eighth, the No. 3 position of the twelve-way valve sixth is connected with the No. 2 position of the six-way valve eighth, and the No. 10 position of the twelve-way valve sixth is connected with the No. 3 position of the six-way valve eighth; MS detection component links to each other with number 1 position of six-way valve eight, and FID detection component links to each other with number 4 position of six-way valve eight.

The gas flow control assembly comprises three mass flowmeters, namely an MFC I, an MFC II and an MFC III; seven electromagnetic valves, respectively electromagnetic valve V1, electromagnetic valve V2, electromagnetic valve V3, electromagnetic valve V4, electromagnetic valve V5, electromagnetic valve V6, and electromagnetic valve V7; nine ten-way valves; and two pumps, pump one and pump two respectively; the output of the double cold trap assembly is respectively connected with a solenoid valve V1, an MFC I, a solenoid valve V2 and an MFC II through a ten-way valve nine and then connected with a pump I through a V6; the back-blowing nitrogen respectively connects with the electromagnetic valve V4 and the electromagnetic valve V5 after passing through the MFC III and the electromagnetic valve V3 in sequence, and then simultaneously connects with the ten-way valve nine; the electromagnetic valve V7 is respectively connected with a four-way valve II and a pump II,

secondly, the cold trap preconcentration method adopting the system comprises the following steps:

(I) instrument calibration

The method comprises the following steps of sampling by using a cold trap I (external standard) and analyzing by using a cold trap II, and specifically comprises the following steps:

step A1.1, sampling is carried out on a first cold trap, pre-analysis is carried out on a second cold trap, a GC-FID/MS analyzer is triggered and operated, and specifically, the first cold trap collects external standard sample gas; the second cold trap switches the gas path to prepare for sample analysis

Step A1.2, sampling by the cold trap I, and analyzing by the cold trap II; particularly, the first cold trap continuously traps external standard gas; the second cold trap carries the trapped substance into the chromatographic column in the GC through the carrier gas by rapid temperature rise for separation, and finally the substances are detected by FID and MS

Step A1.3, sampling is carried out on the first cold trap, and FID trap heating and back flushing are carried out on the second cold trap and the second dewatering trap; particularly, the first cold trap continuously traps external standard gas; the FID trap paths of the second cold trap and the second water trap blow the water and other impurities clean by heating nitrogen and blowing back;

step A1.4, sampling is carried out on the cold trap I, and heating and back flushing of an MS trapping way are carried out on the cold trap II and the dewatering trap II; particularly, the first cold trap continuously traps external standard gas; the MS trapping paths of the cold trap II and the water trap II blow water and other impurities clean by heating nitrogen and blowing back;

step A1.5, sampling is carried out on the cold trap I, and temperature balance is carried out on the cold trap II; specifically, the first cold trap continues to collect external standard gas; the second cold trap keeps refrigeration and reduces the temperature to the set temperature required by trapping;

the method comprises the steps of cold trap one-step analysis and cold trap two-step sampling (external standard), and specifically comprises the following steps:

step A2.1, sampling by a cold trap II, pre-analyzing by the cold trap I, and triggering and operating a GC-FID/MS analyzer; specifically, a first cold trap switches over a gas path to prepare for sample analysis; the cold trap II collects the external standard gas;

step A2.2, sampling by the cold trap II, and analyzing by the cold trap I; specifically, a first cold trap carries trapped substances into a chromatographic column in a GC through a carrier gas by rapid heating for separation, and finally, the separation is carried out by FID and MS, and a second cold trap continues to trap external standard gas;

step A2.3, sampling by a cold trap II, and carrying out FID trap heating and back flushing by the cold trap I and a water trap I; specifically, the first cold trap and the first water trap blow water and other impurities clean through heating nitrogen and back blowing, and the second cold trap continues to capture external standard gas;

step A2.4, sampling by a cold trap II, and carrying out MS trapping path heating back flushing by the cold trap I and a water trap I; specifically, an MS trapping path of a first cold trap and a first water trap purges water and other impurities through heating nitrogen and back flushing; the second cold trap continues to trap the external standard gas;

step A2.5, sampling by the cold trap II, and balancing the temperature by the cold trap I; particularly, the cold trap keeps refrigeration, and the temperature is reduced to the set temperature required by trapping; the second cold trap continues to trap the external standard gas;

(II) air sample Capture and analysis

The method comprises the steps of sampling by a cold trap and analyzing by a cold trap, and specifically comprises the following steps:

b1.1, sampling by the first cold trap, pre-analyzing by the second cold trap, triggering and operating the GC-FID/MS analyzer, and specifically trapping air by the first cold trap; the second cold trap switches the gas path to prepare for sample analysis;

step B1.2, sampling by the cold trap I, and analyzing by the cold trap II; specifically, the first cold trap continuously traps air, the second cold trap carries trapped substances into a chromatographic column in a GC through carrier gas by rapid temperature rise for separation, and finally, the separation is carried out by FID and MS;

b1.3, sampling the cold trap I, and carrying out FID trap heating and back flushing on the cold trap II and the dewatering trap II; specifically, the first cold trap continuously traps air, and the FID trap path of the second cold trap and the second dewatering trap sweeps water and other impurities clean through heating nitrogen and back flushing;

b1.4, sampling the cold trap I, and carrying out MS trapping path heating back flushing on the cold trap II and the dewatering trap II; specifically, air is continuously trapped by the first cold trap, and moisture and other impurities are blown and cleaned by an MS trapping path of the second cold trap and the second dewatering trap through heating nitrogen and back flushing;

step B1.5, sampling the first cold trap, and balancing the temperature of the second cold trap; specifically, the first cold trap continues to collect air, the second cold trap keeps refrigerating, and the temperature is reduced to a set temperature required by trapping;

the method comprises the steps of cold trap one-step analysis and cold trap two-step sampling, and specifically comprises the following steps:

b2.1, sampling by a cold trap II, pre-analyzing by the cold trap I, and triggering and operating a GC-FID/MS analyzer; specifically, a first cold trap switches over an air path to prepare for sample analysis, and a second cold trap traps air;

step B2.2, sampling by the cold trap II, and analyzing by the cold trap I; specifically, a first cold trap carries trapped substances into a chromatographic column in a GC through carrier gas by rapid heating for separation, and finally, the separation is carried out by FID and MS, and a second cold trap continues to trap air;

b2.3, sampling by the cold trap II, and carrying out FID trap heating and back flushing by the cold trap I and the water trap I; specifically, the first cold trap and the first water removal trap blow water and other impurities clean through heating nitrogen and back blowing, and the second cold trap continues to capture air;

b2.4, sampling by a cold trap II, and carrying out MS trapping path heating back flushing by the cold trap I and the water trap I; specifically, an MS trapping path of a first cold trap and a first water trap purges water and other impurities through heating nitrogen and back flushing; the second cold trap continues to trap air;

step B2.5, sampling by the cold trap II, and balancing the temperature by the cold trap I; particularly, the cold trap keeps refrigeration, and the temperature is reduced to the set temperature required by trapping; and the second cold trap continues to trap air.

Third, the air flow direction is explained as follows.

The flow direction of the gas in the step B1.1 is as follows in sequence: the air sample is sequentially as follows: the system comprises a six-position valve I5, a four-way valve II A, a water removing trap I, a ten-way valve III A, a ten-way valve IV, a twelve-way valve V, a number, a ten-way valve nine A, V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and a pump I (on); the nitrogen gas is sequentially as follows: MFC three (off); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a six A position of a twelve-way valve, an eight A position of the six-way valve, an MS detection component and an FID detection component

The flow direction of the gas in the step B1.2 is as follows in sequence: the air sample is sequentially as follows: the six-position valve I5, the four-way valve II A, the ten-way valve III A, the ten-way valve IV, the twelve-way valve IV, the ten-way valve IV, the V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and the pump I (on); the nitrogen gas is sequentially as follows: MFC three (off); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a six B position of a twelve-way valve, an eight A position of the six-way valve, an MS detection component and an FID detection component.

The flow direction of the gas in the step B1.3 is as follows in sequence: the air sample is sequentially as follows: the six-position valve I5, the four-way valve II A, the ten-way valve III A, the ten-way valve IV, the twelve-way valve IV, the ten-way valve IV, the V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and the pump I (on); the nitrogen gas is sequentially as follows: MFC three (on), V3 (on), V4(COM is connected with NC), ten-way valve nine A position, twelve-way valve six A position, ten-way valve four A position, ten-way valve three A position, water removal trap two, four-way valve two A position, V7(COM is connected with NC) and pump two (on); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a six A position of a twelve-way valve, an eight A position of the six-way valve, an MS detection component and an FID detection component

The flow direction of the gas in the step B1.4 is as follows in sequence: the air sample is sequentially as follows: the six-position valve I5, the four-way valve II A, the ten-way valve III A, the ten-way valve IV, the twelve-way valve IV, the ten-way valve IV, the V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and the pump I (on); the nitrogen gas is sequentially as follows: MFC three (on), V3 (on), V5(COM is connected with NC), ten-way valve nine A position, twelve-way valve six A position, ten-way valve four A position, ten-way valve three A position, water removal trap two, four-way valve two A position, V7(COM is connected with NC) and pump two (on); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a six A position of a twelve-way valve, an eight A position of the six-way valve, an MS detection component and an FID detection component

The flow direction of the gas in the step B1.5 is as follows in sequence: the air sample is sequentially as follows: the six-position valve I5, the four-way valve II A, the ten-way valve III A, the ten-way valve IV, the twelve-way valve IV, the ten-way valve IV, the V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and the pump I (on); the nitrogen gas is sequentially as follows: MFC three (off); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a six A position of a twelve-way valve, an eight A position of the six-way valve, an MS detection component and an FID detection component

The flow direction of the gas in the step B2.1 is as follows in sequence: the air sample is sequentially as follows: a first 5-position six-position valve, a second B-position four-way valve, a second water removing trap, a third B-position ten-way valve, a fourth B-position ten-way valve, a sixth A-position twelve-way valve, a ninth B-position ten-way valve, V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and a first pump (on); the nitrogen gas is sequentially as follows: MFC three (off); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven A position of a six-way valve, a five A position of a twelve-way valve, an eight B position of a six-way valve, an MS detection component and an FID detection component

The flow direction of the gas in the step B2.2 is as follows in sequence: the air sample is sequentially as follows: a first 5-position six-position valve, a second B-position four-way valve, a second water removing trap, a third B-position ten-way valve, a fourth B-position ten-way valve, a sixth A-position twelve-way valve, a ninth B-position ten-way valve, V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and a first pump (on); the nitrogen gas is sequentially as follows: MFC three (off); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a five B position of a twelve-way valve, an eight B position of a six-way valve, an MS detection component and an FID detection component

The flow direction of the gas in the step B2.3 is as follows in sequence: the air sample is sequentially as follows: a first 5-position six-position valve, a second B-position four-way valve, a second water removing trap, a third B-position ten-way valve, a fourth B-position ten-way valve, a sixth A-position twelve-way valve, a ninth B-position ten-way valve, V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and a first pump (on); the nitrogen gas is sequentially as follows: MFC three (on), V3 (on), V4(COM is connected with NO), ten-way valve nine B position, twelve-way valve five A position, ten-way valve four B position, ten-way valve three B position, water removing trap one, four-way valve two B position, V7(COM is connected with NC) and pump two (on); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a five A position of a twelve-way valve, an eight B position of a six-way valve, an MS detection component and an FID detection component

The flow direction of the gas in the step B2.4 is as follows in sequence: the air sample is sequentially as follows: a first 5-position six-position valve, a second B-position four-way valve, a second water removing trap, a third B-position ten-way valve, a fourth B-position ten-way valve, a sixth A-position twelve-way valve, a ninth B-position ten-way valve, V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and a first pump (on); the nitrogen gas is sequentially as follows: MFC three (on), V3 (on), V5(COM is connected with NO), ten-way valve nine B position, twelve-way valve five A position, ten-way valve four B position, ten-way valve three B position, water removing trap one, four-way valve two B position, V7(COM is connected with NC) and pump two (on); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a five A position of a twelve-way valve, an eight B position of a six-way valve, an MS detection component and an FID detection component

The flow direction of the gas in the step B2.5 is as follows in sequence: the air sample is sequentially as follows: a first 5-position six-position valve, a second B-position four-way valve, a second water removing trap, a third B-position ten-way valve, a fourth B-position ten-way valve, a sixth A-position twelve-way valve, a ninth B-position ten-way valve, V1 (on), V2 (on), MFC I (on), MFC II (on), V6(COM is connected with NC), and a first pump (on); the nitrogen gas is sequentially as follows: MFC three (off); helium gas is sequentially as follows: a GC sample inlet (FID), a GC sample inlet (MS), a seven B position of a six-way valve, a five A position of a twelve-way valve, an eight B position of a six-way valve, an MS detection component and an FID detection component

The gas flow direction in the calibration step is consistent with the air sample flow direction, and only the first six-position valve is switched from the No. 5 position to the No. 3 position.

The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.