CN103439153A - Atmosphere volatile organic compound condensation and concentration sampling device and method - Google Patents
Atmosphere volatile organic compound condensation and concentration sampling device and method Download PDFInfo
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Abstract
The invention discloses an atmosphere volatile organic compound condensation and concentration sampling device which comprises a low-temperature environmental cabinet and an atmosphere sampler, wherein a low-temperature cold trap device is arranged in the low-temperature environmental cabinet, and comprises a first-stage cold trap and a second-stage cold trap, the first-stage cold trap comprises a first condensation pipe and a first semiconductor chilling plate group, a first heating wire is wound on the first condensation pipe, the second-stage cold trap comprises a second condensation pipe and a second semiconductor chipping plate group, and a second heating wire is wound on the second condensation pipe. The invention also discloses an atmosphere volatile organic compound condensation and concentration sampling method. The atmosphere volatile organic compound condensation and concentration sampling device and method disclosed by the invention are capable of meeting the demand on online automatic monitoring of the content of a volatile organic compound, and can be used in on-site online automatic monitoring of the content of the atmosphere volatile organic compound.
Description
Technical field
The present invention relates to atmospheric environment checkout equipment technical field, specifically, relate to the concentrated sampler of a kind of atmospheric volatile organic compounds condensation and sampling method.
Background technology
The volatile organic matter contained in atmosphere, mostly there is the harm such as teratogenesis, carcinogenic, mutagenesis, and be the important arch-criminal of the phenomenons such as atmospheric photochemistry harm, greenhouse effect, therefore for the monitoring in time of the pollution level to atmosphere and control, volatile organic content in atmosphere is carried out to detecting in real time seems becomes more and more important, volatile organic content is carried out to on-line monitoring especially in the wild and become more and more important.At present, the volatile organic matter in atmosphere is detected and mainly completes by stratographic analysis.Because the volatile organic matter kind in atmosphere is more, and concentration is low, must carry out the enrichment concentration, just can reach the requirement that analytical instrument detects.And, for concerning the volatile organic content online auto monitoring, concentration systems is had relatively high expectations, should reach following condition: do not consume cold-producing medium, the enrichment desorption rate is fast, in order to shorten the analytical cycle of monitoring automatically.
At present, the device concentrated for laboratory volatile organic matter condensation generally used liquid nitrogen refrigerating, directly liquid nitrogen sprayed in the evaporator of cold-trap outside, utilizes liquid nitrogen vaporization to absorb heat and freezed.For example in Chinese patent CN101337135, propose a kind of cryotrap, solved the consumption problem of condensing agent, and shortened concentration time.But the method liquid nitrogen consumption is large, the refrigeration cost is higher, and the liquid nitrogen field is changed simultaneously, store difficulty, and analytical cycle is long, and for operation and maintenance brings very big inconvenience, so it is not suitable for the continuous on-line monitoring in field.And at present in technology, in cryotrap, generally use the poriness adsorbent, volatile organic matter is carried out to Rapid Thermal desorb again after cryosorption, in this process, be easy to produce cross pollution and " memory effect ".Therefore, current condensation enrichment facility and condensation method for concentration can not meet the needs to the volatile organic content on-line monitoring.In addition, use poriness adsorbent adsorbing volatilizing organic matter, desorption time is long, whole analytical cycle is lengthened, and easily between different sample analysis, produce cross-contamination issue.
Summary of the invention
First technical matters to be solved by this invention is: a kind of cold-producing medium, concentrated sampler of the enrichment desorption rate is fast and analytical cycle is short atmospheric volatile organic compounds condensation of not consuming is provided.
Second technical matters to be solved by this invention is: a kind of cold-producing medium, the enrichment desorption rate is fast and analytical cycle is short atmospheric volatile organic compounds condensation concentration sampling method of not consuming is provided.
For solving above-mentioned first technical matters, technical scheme of the present invention is: a kind of atmospheric volatile organic compounds cryogenic condensation enrichment facility comprises:
Environmental chamber at low temperature, described environmental chamber at low temperature is connected with compressor, be provided with the cryotrap device in described environmental chamber at low temperature, described cryotrap device comprises first order cold-trap and second level cold-trap, described first order cold-trap comprises the first condenser pipe and the first semiconductor chilling plate group, on described the first condenser pipe, is wound with the first heater strip; Described second level cold-trap comprises the second condenser pipe and the second semiconductor chilling plate group, on described the second condenser pipe, is wound with the second heater strip;
Air sampler, the output terminal of described air sampler is connected to the input end of mass flowmeter, the output terminal of described mass flowmeter is connected to the first end of the first multiport valve, the second end of described the first multiport valve is connected with the carrier gas source of the gas, and the 3rd end of described the first multiport valve is connected to the entrance point of described the first condenser pipe;
The endpiece of described the first condenser pipe is connected with the entrance point of described the second condenser pipe, the endpiece of described the second condenser pipe is connected to the first end of the second multiport valve, the second end of described the second multiport valve is connected with the blowback source of the gas, and the 3rd end of described the second multiport valve is connected to chromatographic detection input end.
Preferably, be provided with the first refrigeration cavity and the second refrigeration cavity in described environmental chamber at low temperature; Described the first condenser pipe and described the first heater strip are arranged in described the first refrigeration cavity, and described the second condenser pipe and described the second heater strip are arranged in described the second refrigeration cavity.
Preferably, described the first semiconductor chilling plate group comprises the semiconductor chilling plate be electrically connected to that fit together more than two and in parallel, and described the second semiconductor chilling plate group comprises the semiconductor chilling plate be electrically connected to that fit together more than three and in parallel.
Preferably, described the first refrigeration cavity and described the second refrigeration cavity are enclosed with respectively heat-insulating material.
Preferably, described the first condenser pipe and described the second condenser pipe are the stainless steel condenser pipe.
Preferably, described air sampler is the air sampler with dedusting function.
Preferably, described the first multiport valve and described the second multiport valve are various way solenoid valve.
Preferably, described carrier gas source of the gas and described blowback source of the gas are the inert gas that purity is greater than 99.9%.
Preferably, described chromatograph is gas chromatograph or gas chromatograph-mass spectrometer.
For solving above-mentioned second technical matters, technical scheme of the present invention is: a kind of atmospheric volatile organic compounds cryogenic condensation concentration sampling method comprises the following steps:
A. at first start environmental chamber at low temperature, make it in refrigerating state, make the first refrigeration cavity and the first condenser pipe reach the low temperature of-40 ℃ to-50 ℃, make the second refrigeration cavity and the second condenser pipe reach the low temperature of-145 ℃ to-155 ℃;
B. atmospheric volatile organic compounds is after the air sampler sampling, open the first multiport valve, air sampler is communicated with environmental chamber at low temperature, atmospheric sample is quantitatively sent in environmental chamber at low temperature by mass flowmeter, at first enter the first refrigeration cavity and carry out condensation, being condensed in the first condenser pipe containing six carbon atom and above compound and moisture in atmospheric sample, change into liquid or solid-state; Containing five carbon atoms and following compound, enter in the second condenser pipe and be converted into liquid state or solid-state in atmospheric sample, and other gas in atmosphere is not condensed into liquid state or solid-state, and directly emptying by the second multiport valve;
C. after sampling reaches aequum, control the first multiport valve, disconnect the gas flow of mass flowmeter and the first condenser pipe, open the first heater strip in the first refrigeration cavity, make the temperature of the first condenser pipe in the first refrigeration cavity be raised to 10 ℃, and control the first multiport valve, the carrier gas source of the gas is communicated with the first condenser pipe; Be heated to 10 ℃ in the first condenser pipe, now, water is in liquid state; and other are condensed in the volatile organic matter component in the first condenser pipe; become gas phase after heating and gasifying, and by the carrier gas source of the gas, it is purged to carry out cryogenic condensation into the second condenser pipe concentrated, carrier gas is emptying by the second multiport valve;
D.5-10 minute after; open the second heater strip on the second condenser pipe; make the second condenser pipe be heated to 30-40 ℃; control the second multiport valve; the second condenser pipe is communicated with chromatograph; now volatile organic matter constitutional changes are gaseous state, and carry it into chromatograph by the carrier gas source of the gas and carry out the quantitative test measurement;
E. after completing said process; stop the refrigerating state of environmental chamber at low temperature; open the first heater strip and the second heater strip; make the first condenser pipe and the second condenser pipe temperature be elevated to 300 ℃; control the second multiport valve, the blowback source of the gas is communicated with the second condenser pipe, carry out the blowback cleaning; running time is 5-10 minute, and purge gas is emptying by the first multiport valve;
F., after the blowback process completes, close the first heater strip and the second heater strip.
After having adopted technique scheme, the invention has the beneficial effects as follows:
1. due to the concentrated sampler of atmospheric volatile organic compounds condensation of the present invention and sampling method, employing be semiconductor refrigerating technology, and semiconductor refrigerating technology utilizes the paltie effect refrigeration of semiconductor material, does not need cold-producing medium, after energising, directly freezes.But semiconductor refrigerating has the advantages such as continuous cooling, fast, the shockproof noise of refrigerating speed, life-span be long, convenient for installation and maintenance, can also realize accurate refrigeration, automatic controlling system process of refrigerastion easy to use.The refrigeration system of this technology can meet in the wild the needs to the volatile organic content on-line monitoring.Therefore apply the concentrated sampler of atmospheric volatile organic compounds condensation of the present invention of this Refrigeration Technique, overcome traditional cryogenic condensation device due to the defect that needs liquid nitrogen to exist: the liquid nitrogen consumption is large, the refrigeration cost is higher, the liquid nitrogen field is changed simultaneously, store difficulty, can be used for the online automatic detection on the spot of atmospheric volatile organic compounds content.
2. be the stainless steel condenser pipe due to the first condenser pipe in the present invention and the second condenser pipe.Therefore in condensation process, directly condensation on stainless-steel pipe of component, but not condensation on traditional sorbing material, thermal desorption speed is fast, has shortened analytical test week period interval, and maximum possible avoided cross pollution and memory effect.
The accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described:
Fig. 1 is the principle schematic of the concentrated sampler of atmospheric volatile organic compounds condensation of the present invention;
In figure: 1, environmental chamber at low temperature; 2, the first refrigeration cavity; 3, the first condenser pipe; 4, the first heater strip; 5, the first semiconductor chilling plate group; 6, the second refrigeration cavity; 7, the second condenser pipe; 8, the second heater strip; 9, the second semiconductor chilling plate group; 10, air sampler; 11, mass flowmeter; 12, the first multiport valve; 13, carrier gas source of the gas; 14, the second multiport valve; 15; The blowback source of the gas; 16, chromatograph; 17, compressor; 18, semiconductor chilling plate.
Embodiment
Fig. 1 is the principle schematic of the concentrated sampler of atmospheric volatile organic compounds condensation of the present invention, with reference to Fig. 1, atmospheric volatile organic compounds condensation of the present invention concentrates sampler, comprises environmental chamber at low temperature 1 and air sampler 10, and air sampler 10 has dedusting function.
Environmental chamber at low temperature 1 is connected with compressor, be provided with the cryotrap device in environmental chamber at low temperature 1, the cryotrap device comprises first order cold-trap and second level cold-trap, and first order cold-trap comprises on the first condenser pipe 3 and the first semiconductor chilling plate group 5, the first condenser pipes 3 and is wound with the first heater strip 4; Second level cold-trap comprises on the second condenser pipe 7 and the second semiconductor chilling plate group 9, the second condenser pipes 7 and is wound with the second heater strip 8.Wherein, the first condenser pipe 3 and the second condenser pipe 7 all adopt stainless steel material to make, and inside surface is through Passivation Treatment.Therefore in condensation process, directly condensation on stainless-steel pipe of component, but not condensation on traditional sorbing material, thermal desorption speed is fast, has shortened analytical cycle, and maximum possible avoided cross pollution and memory effect.
The output terminal of air sampler 10 is connected to the input end of mass flowmeter 11, the output terminal of mass flowmeter 11 is connected to the first end of the first multiport valve 12, the 3rd end that the second end of the first multiport valve 12 is connected with carrier gas source of the gas 13, the first multiport valves 12 is connected to the entrance point of the first condenser pipe 3.
The endpiece of the first condenser pipe 3 is connected with the entrance point of the second condenser pipe 7, the endpiece of the second condenser pipe 7 is connected to the first end of the second multiport valve 14, the 3rd end that the second end of the second multiport valve 14 is connected with blowback source of the gas 15, the second multiport valves 14 is connected to the detection input end of chromatograph 16.Chromatograph 16 is gas chromatograph or gas chromatograph-mass spectrometer.
Be provided with the first refrigeration cavity 2 and the second refrigeration cavity 6 in environmental chamber at low temperature 1; The first condenser pipe 3 and the first heater strip 4 are arranged in the first refrigeration cavity 2, and the second condenser pipe 7 and the second heater strip 8 are arranged in the second refrigeration cavity 6.In the present embodiment, needs according to condensing temperature, the first semiconductor chilling plate group 5 comprise semiconductor chilling plate 18, the second semiconductor chilling plate groups 9 that are electrically connected to that fit together more than two and in parallel comprise that more than three, fit together and in parallel be electrically connected to semiconductor chilling plate 18.Wherein, by the first semiconductor cooling sheet group 5 processed, for the first refrigeration cavity 2, provide refrigeration, by the second semiconductor chilling plate group 9, for the second refrigeration cavity 6, provide refrigeration.
In the present embodiment, the first refrigeration cavity 2 and the second refrigeration cavity 6 are enclosed with respectively heat-insulating material.The first multiport valve 12 and the second multiport valve 14 are various way solenoid valve.The first condenser pipe and the second condenser pipe are straight shape, snakelike or spirality.
Carrier gas source of the gas and blowback source of the gas are the inert gas that purity is greater than 99.9%.In the present embodiment, carrier gas source of the gas and blowback source of the gas are the helium that purity is greater than 99.9%.Certainly, also can adopt other inert gas.Wherein, the meaning of carrier gas: in vapor-phase chromatography, mobile phase is gas, is called carrier gas.The effect of carrier gas is to enter together chromatographic column with certain flow velocity carrier band gaseous sample or the sample gas after gasification to be separated, again each component after separated being written into to detecting device is detected, finally flow out condenser system emptying or collection, carrier gas has been carrier band effect and do not participate in centrifugation.
In the present embodiment, utilize the course of work of the concentrated sampler of atmospheric volatile organic compounds condensation of the present invention to be:
A. at first start environmental chamber at low temperature 1, make it in refrigerating state, make the first refrigeration cavity 2 and the first condenser pipe 3 reach the low temperature of-40 ℃ to-50 ℃; Make the second refrigeration cavity 6 and the second condenser pipe 7 reach the low temperature of-145 ℃ to-155 ℃;
B. atmospheric volatile organic compounds is after air sampler 10 samplings, open the first multiport valve 12, air sampler 10 is communicated with environmental chamber at low temperature 1, atmospheric sample quantitatively sends in environmental chamber at low temperature 1 by mass flowmeter 11, at first enter the first refrigeration cavity 2 and carry out condensation, higher containing six carbon atom and above compound and moisture boiling point in atmospheric sample, at first be condensed in the first condenser pipe 3, changes into liquid or solid-state; And the lower volatile organic matter of boiling point; mainly containing five carbon atoms and following compound; especially other volatile organic matters such as formaldehyde, methyl alcohol and methane that in atmosphere, content is higher; enter in the second condenser pipe 7 and be converted into liquid state or solid-state; and other permanent gases in atmosphere, such as nitrogen, oxygen etc., because boiling point is lower; be not condensed into liquid state or solid-state, and directly emptying by the second multiport valve 14;
C. after sampling reaches aequum, control the first multiport valve 12, disconnect the gas flow of mass flowmeter 11 and the first condenser pipe 3, open the first heater strip 4 in the first refrigeration cavity 2, make the temperature of the first condenser pipe 3 in the first refrigeration cavity 2 be raised to fast 10 ℃, and control the first multiport valve 12, carrier gas source of the gas 13 is communicated with the first condenser pipe 3; Be heated to 10 ℃ in the first condenser pipe 3; now; water is in liquid state; vapour pressure is very low; and other are condensed in the volatile organic matter component in the first condenser pipe 3; become gas phase after heating and gasifying, and by the carrier gas of carrier gas source of the gas 13, it is purged to carry out cryogenic condensation into the second condenser pipe 7 concentrated, carrier gas is emptying by the second multiport valve 14;
D.5-10 minute after; open the second heater strip 8 on the second condenser pipe 7; make the second condenser pipe 7 be heated to 30-40 ℃; control the second multiport valve 14; the second condenser pipe 7 is communicated with chromatograph 16; now volatile organic matter constitutional changes are gaseous state, and carry it into chromatograph 16 by carrier gas source of the gas 13 and carry out the quantitative test measurement;
E. after completing said process; stop the refrigerating state of environmental chamber at low temperature 1; open the first heater strip 4 and the second heater strip 8; make the first condenser pipe 3 and the second condenser pipe 7 temperature be elevated to 300 ℃; control the second multiport valve 14, blowback source of the gas 15 is communicated with the second condenser pipe 7, carry out the blowback cleaning; running time is 5-10 minute, and purge gas is emptying by the first multiport valve 12;
F. after the blowback process completes, close the first heater strip 4 and the second heater strip 8, and again make environmental chamber at low temperature 1 in refrigerating state, make the first refrigeration cavity 2 and the second refrigeration cavity 6 reach design temperature, for sampling ready next time.
From the above-mentioned course of work of the concentrated sampler of atmospheric volatile organic compounds condensation of the present invention, can find out, atmospheric volatile organic compounds condensation of the present invention concentrates sampler, what adopt is semiconductor refrigerating technology, and semiconductor refrigerating technology utilizes the paltie effect refrigeration of semiconductor material, do not need cold-producing medium, directly freeze after energising.But semiconductor refrigerating has the advantages such as continuous cooling, fast, the shockproof noise of refrigerating speed, life-span be long, convenient for installation and maintenance, can also realize accurate refrigeration, automatic controlling system process of refrigerastion easy to use.The refrigeration system of this technology can meet the needs to the volatile organic content on-line real time monitoring.Therefore apply the concentrated sampler of atmospheric volatile organic compounds condensation of the present invention of this Refrigeration Technique, overcome traditional cryogenic condensation device due to the defect that needs liquid nitrogen refrigerating to exist: the liquid nitrogen consumption is large, the refrigeration cost is higher, the liquid nitrogen field is changed simultaneously, store difficulty, can be used for the online automatic detection on the spot of atmospheric volatile organic compounds content.In addition, condenser pipe of the present invention is that thermal desorption speed is fast, has shortened the analytical test cycle not containing the stainless-steel tube of poriness sorbing material, and maximum possible avoided cross pollution and memory effect.
The above is giving an example of best mode for carrying out the invention, and the part of wherein not addressing in detail is those of ordinary skills' common practise.Protection scope of the present invention is as the criterion with the content of claim, and any equivalent transformation carried out based on technology enlightenment of the present invention, also within protection scope of the present invention.
Claims (10)
1. the concentrated sampler of atmospheric volatile organic compounds condensation, is characterized in that, comprising:
Environmental chamber at low temperature, described environmental chamber at low temperature is connected with compressor, be provided with the cryotrap device in described environmental chamber at low temperature, described cryotrap device comprises first order cold-trap and second level cold-trap, described first order cold-trap comprises the first condenser pipe and the first semiconductor chilling plate group, on described the first condenser pipe, is wound with the first heater strip; Described second level cold-trap comprises the second condenser pipe and the second semiconductor chilling plate group, on described the second condenser pipe, is wound with the second heater strip;
Air sampler, the output terminal of described air sampler is connected to the input end of mass flowmeter, the output terminal of described mass flowmeter is connected to the first end of the first multiport valve, the second end of described the first multiport valve is connected with the carrier gas source of the gas, and the 3rd end of described the first multiport valve is connected to the entrance point of described the first condenser pipe;
The endpiece of described the first condenser pipe is connected with the entrance point of described the second condenser pipe, the endpiece of described the second condenser pipe is connected to the first end of the second multiport valve, the second end of described the second multiport valve is connected with the blowback source of the gas, and the 3rd end of described the second multiport valve is connected to chromatographic detection input end.
2. the concentrated sampler of atmospheric volatile organic compounds condensation as claimed in claim 1, is characterized in that: be provided with the first refrigeration cavity and the second refrigeration cavity in described environmental chamber at low temperature; Described the first condenser pipe and described the first heater strip are arranged in described the first refrigeration cavity, and described the second condenser pipe and described the second heater strip are arranged in described the second refrigeration cavity.
3. atmospheric volatile organic compounds condensation as claimed in claim 1 concentrates sampler, it is characterized in that: described the first semiconductor chilling plate group comprises the semiconductor chilling plate be electrically connected to that fit together more than two and in parallel, and described the second semiconductor chilling plate group comprises the semiconductor chilling plate be electrically connected to that fit together more than three and in parallel.
4. atmospheric volatile organic compounds condensation as claimed in claim 2 concentrates sampler, it is characterized in that: described the first refrigeration cavity and described the second refrigeration cavity are enclosed with respectively heat-insulating material.
5. atmospheric volatile organic compounds condensation as claimed in claim 1 concentrates sampler, and it is characterized in that: described the first condenser pipe and described the second condenser pipe are the stainless steel condenser pipe.
6. atmospheric volatile organic compounds condensation as claimed in claim 1 concentrates sampler, and it is characterized in that: described air sampler is the air sampler with dedusting function.
7. atmospheric volatile organic compounds condensation as claimed in claim 1 concentrates sampler, and it is characterized in that: described the first multiport valve and described the second multiport valve are various way solenoid valve.
8. atmospheric volatile organic compounds condensation as described as claim 1 to 7 any one concentrates sampler, and it is characterized in that: described carrier gas source of the gas and described blowback source of the gas are the inert gas that purity is greater than 99.9%.
9. atmospheric volatile organic compounds condensation as claimed in claim 8 concentrates sampler, and it is characterized in that: described chromatograph is gas chromatograph or gas chromatograph-mass spectrometer.
10. adopt the sampling method of the concentrated sampler of atmospheric volatile organic compounds condensation claimed in claim 1, it is characterized in that, comprise the following steps:
A. at first start environmental chamber at low temperature, make it in refrigerating state, make the first refrigeration cavity and the first condenser pipe reach the low temperature of-40 ℃ to-50 ℃, make the second refrigeration cavity and the second condenser pipe reach the low temperature of-145 ℃ to-155 ℃;
B. atmospheric volatile organic compounds is after the air sampler sampling, open the first multiport valve, air sampler is communicated with environmental chamber at low temperature, atmospheric sample is quantitatively sent in environmental chamber at low temperature by mass flowmeter, at first enter the first refrigeration cavity and carry out condensation, being condensed in the first condenser pipe containing six carbon atom and above compound and moisture in atmospheric sample, change into liquid or solid-state; Containing five carbon atoms and following compound, enter in the second condenser pipe and be converted into liquid state or solid-state in atmospheric sample, and other gas in atmosphere is not condensed into liquid state or solid-state, and directly emptying by the second multiport valve;
C. after sampling reaches aequum, control the first multiport valve, disconnect the gas flow of mass flowmeter and the first condenser pipe, open the first heater strip in the first refrigeration cavity, make the temperature of the first condenser pipe in the first refrigeration cavity be raised to 10 ℃, and control the first multiport valve, the carrier gas source of the gas is communicated with the first condenser pipe; Be heated to 10 ℃ in the first condenser pipe, now, water is in liquid state; and other are condensed in the volatile organic matter component in the first condenser pipe; become gas phase after heating and gasifying, and by the carrier gas source of the gas, it is purged to carry out cryogenic condensation into the second condenser pipe concentrated, carrier gas is emptying by the second multiport valve;
D.5-10 minute after; open the second heater strip on the second condenser pipe; make the second condenser pipe be heated to 30-40 ℃; control the second multiport valve; the second condenser pipe is communicated with chromatograph; now volatile organic matter constitutional changes are gaseous state, and carry it into chromatograph by the carrier gas source of the gas and carry out the quantitative test measurement;
E. after completing said process; stop the refrigerating state of environmental chamber at low temperature; open the first heater strip and the second heater strip; make the first condenser pipe and the second condenser pipe temperature be elevated to 300 ℃; control the second multiport valve, the blowback source of the gas is communicated with the second condenser pipe, carry out the blowback cleaning; running time is 5-10 minute, and purge gas is emptying by the first multiport valve;
F., after the blowback process completes, close the first heater strip and the second heater strip.
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| CN105300785A (en) * | 2015-10-23 | 2016-02-03 | 北京捷思达仪分析仪器研发中心 | Thermal desorption instrument and sample desorption method for gas chromatograph |
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| CN115267029A (en) * | 2022-07-26 | 2022-11-01 | 上海正帆科技股份有限公司 | Low-temperature enrichment method for trace gas chromatographic analysis |
| CN116399652A (en) * | 2023-06-09 | 2023-07-07 | 江苏新锐环境监测有限公司 | Volatile organic compound sampling detection method |
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