CN103499662B - Sampling analysis device and sampling analysis method for atmosphere volatile organic compounds - Google Patents
Sampling analysis device and sampling analysis method for atmosphere volatile organic compounds Download PDFInfo
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- CN103499662B CN103499662B CN201310438314.5A CN201310438314A CN103499662B CN 103499662 B CN103499662 B CN 103499662B CN 201310438314 A CN201310438314 A CN 201310438314A CN 103499662 B CN103499662 B CN 103499662B
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Abstract
The invention discloses a sampling analysis device for atmosphere volatile organic compounds. The sampling analysis device comprises a low-temperature environmental box and an atmosphere sampler, wherein low-temperature cold trap devices are arranged in the low-temperature environmental box and comprise a first cold trap, a second cold trap and a third cold trap, the first cold trap comprises a first condensation pipe and a first semiconductor chilling plate set, and a first heating wire is wound on the first condensation pipe; the second cold trap comprises a second condensation pipe and a second semiconductor chilling plate set, and a second heating wire is wound on the second condensation pipe; the third cold trap comprises a third condensation pipe and a third semiconductor chilling plate set. The invention further discloses a sampling analysis method for the atmosphere volatile organic compounds. The sampling analysis device and the sampling analysis method can meet requirements on the online monitoring of the contents of the volatile organic compounds and can be used for automatically detecting the contents of the atmosphere volatile organic compounds in an on-site and online manner.
Description
Technical field
The present invention relates to atmospheric environment checkout equipment technical field, specifically, relate to a kind of atmospheric volatile organic compounds sampling analysis device and sampling and analyzing method.
Background technology
The volatility contained in air, there is the harm such as teratogenesis, carcinogenic, mutagenesis mostly, and be the important arch-criminal of the phenomenons such as atmospheric photochemistry harm, greenhouse effect, therefore in order to the timely Inspect and control of the pollution level of air, atmospheric volatile organic compounds content is carried out to detecting in real time seems becomes more and more important, especially on-line monitoring is carried out to volatile organic content and become more and more important.At present, atmospheric volatile organic compounds is detected complete mainly through stratographic analysis.Because the volatile organic matter kind in air is many, and concentration is low, must carry out enrichment concentration (namely the micro substance in atmospheric being become solid-state reduced volume), just can reach the requirement that analytical instrument detects.And for carrying out on-line monitoring to volatile organic content, require higher to concentration systems, following condition should be reached: do not consume cold-producing medium, enrichment desorption rate is fast, to shorten the analytical cycle of monitoring automatically.
At present, the device concentrated for laboratory volatile organic matter condensation generally uses liquid nitrogen refrigerating, namely directly liquid nitrogen is sprayed in the evaporator of cold-trap outside, utilizes liquid nitrogen vaporization to absorb heat and freezes.Such as, propose a kind of cryotrap in Chinese patent CN101337135, solve the consumption problem of condensing agent, and shorten concentration time.But the method liquid nitrogen consumption is large, refrigeration cost is higher, and liquid nitrogen field is changed simultaneously, and store difficulty, and analytical cycle is long, for operation and maintenance brings very big inconvenience, therefore it is not suitable for continuous on-line monitoring.And at present generally use poriness adsorbent in cryotrap in technology, Rapid Thermal desorb again after cryosorption is carried out to volatile organic matter, in this process, is easy to produce cross pollution and " memory effect ".Therefore, current condensation enrichment facility and condensation method for concentration can not meet the needs to volatile organic content on-line monitoring.In addition, use poriness adsorbent volatile organic matter, desorption time is long, and whole analytical cycle is lengthened, and easily between different sample analysis, produces cross-contamination issue.Have again, in air, volatile organic matter is of a great variety, when needing to use gas chromatograph to analyze the volatile organic content in air, Water demand tens kinds and even hundreds of kind carbon containing class material, the many uses of current gas chromatograph have the gas chromatograph of a capillary separation column, because single capillary column is to all volatile organic matter poor selectivity in air, cause separation efficiency low, the capillary column that general need are long more than 60m, the separation completely to material could be realized, cause and require that system sample introduction pressure requirements is high, the shortcomings such as analytical cycle is long.
Summary of the invention
First technical matters to be solved by this invention is: provide a kind of and do not consume cold-producing medium, enrichment desorption rate is fast and analytical cycle is short atmospheric volatile organic compounds sampling analysis device.
Second technical matters to be solved by this invention is: provide a kind of and do not consume cold-producing medium, enrichment desorption rate is fast and analytical cycle is short atmospheric volatile organic compounds sampling and analyzing method.
For solving above-mentioned first technical matters, technical scheme of the present invention is: a kind of atmospheric volatile organic compounds sampling analysis device, comprising:
Environmental chamber at low temperature, described environmental chamber at low temperature is connected with compressor, cryotrap device is provided with in described environmental chamber at low temperature, described cryotrap device comprises the first cold-trap, the second cold-trap and the 3rd cold-trap, described first cold-trap comprises the first condenser pipe and the first semiconductor chilling plate group, and described first condenser pipe is wound with the first heater strip; Described second cold-trap comprises the second condenser pipe and the second semiconductor chilling plate group, and described second condenser pipe is wound with the second heater strip; Described 3rd cold-trap comprises the 3rd condenser pipe and the 3rd semiconductor chilling plate group, and described 3rd condenser pipe is wound with the 3rd 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, second end of described first multiport valve is connected with carrier gas source of the gas, and the three-terminal link of described first multiport valve is to the entrance point of described first condenser pipe;
The endpiece of described first condenser pipe is connected to the first end of the second multiport valve, and the second end of described second multiport valve is connected with the entrance point of described second condenser pipe, and the 3rd end of described second multiport valve is connected with the entrance point of described 3rd condenser pipe;
The endpiece of described second condenser pipe is connected to the first end of the 3rd multiport valve, and the second end of described 3rd multiport valve is connected with blowback source of the gas, and the three-terminal link of described 3rd multiport valve is to the first chromatographic detection input end;
The endpiece of described 3rd condenser pipe is connected to the first end of the 4th multiport valve, and the second end of described 4th multiport valve is connected with described blowback source of the gas, and the three-terminal link of described 4th multiport valve is to the second chromatographic detection input end.
Preferably, the first refrigeration cavity, the second refrigeration cavity and the 3rd refrigeration cavity is provided with in described environmental chamber at low temperature; Described first condenser pipe and described first heater strip are arranged in described first refrigeration cavity, described second condenser pipe and described second heater strip are arranged in described second refrigeration cavity, and described 3rd condenser pipe and described 3rd heater strip are arranged in described 3rd refrigeration cavity.
Preferably, be also connected with semipermeable partition between the 3rd end of described second multiport valve and the entrance point of described 3rd condenser pipe except water pipe, described semipermeable partition removes water pipe outer cover and is provided with drying tube.
Preferably, described semipermeable partition removes between the endpiece of water pipe and the entrance point of described 3rd condenser pipe and is also connected with pressure valve.
Preferably, described first semiconductor chilling plate group comprises the semiconductor chilling plate of electrical connection that two or more fits together and in parallel, described second semiconductor chilling plate group comprise more than three fit together and the semiconductor chilling plate of electrical connection in parallel, described 3rd semiconductor chilling plate group comprises the semiconductor chilling plate of electrical connection that two or more fits together and in parallel.
Preferably, the outside of described first refrigeration cavity, described second refrigeration cavity and described 3rd refrigeration cavity is enclosed with heat-insulating material respectively.
Preferably, described first condenser pipe, described second condenser pipe and described 3rd condenser pipe are stainless steel condenser pipe.
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%.
For solving above-mentioned second technical matters, technical scheme of the present invention is: a kind of atmospheric volatile organic compounds sampling and analyzing method, comprises the following steps:
A. first environmental chamber at low temperature is started, it is made to be in refrigerating state, the first refrigeration cavity and the first condenser pipe is made to reach the low temperature of-40 DEG C to-50 DEG C, make the second refrigeration cavity and the second condenser pipe reach the low temperature of-145 DEG C to-155 DEG C, make the 3rd refrigeration cavity and the 3rd condenser pipe reach the low temperature of-55 DEG C to-65 DEG C;
B. atmospheric volatile organic compounds is after air sampler sampling, control the first multiport valve and the second multiport valve, air sampler is communicated with environmental chamber at low temperature, first condenser pipe is communicated with the second condenser pipe, atmospheric sample is quantitatively sent in environmental chamber at low temperature by mass flowmeter, first enters the first refrigeration cavity and carries out condensation, in atmospheric sample containing six carbon atom and above volatile organic compounds and moisture, first be condensed in the first condenser pipe, change into solid-state; In atmospheric sample containing five carbon atoms and following volatile organic matter enter be converted in the second condenser pipe solid-state; And other gas in air, be not condensed into solid-state, and directly emptying by the 3rd multiport valve;
C. to be sampledly aequum is reached, after balance a period of time, control the first multiport valve, control the second multiport valve, the gas disconnecting mass flowmeter and the first condenser pipe flows, and the first condenser pipe is communicated with the 3rd 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 50 DEG C, and control the first multiport valve, carrier gas source of the gas is communicated with the first condenser pipe; 50 DEG C are heated in first condenser pipe, now, water is in liquid state, and other is condensed in the volatile organic components in the first condenser pipe, transfer in gas phase after being heated to 50 DEG C of gasifications, and purged by carrier gas source of the gas and enter the 3rd condenser pipe and carry out cryogenic condensation and concentrate, carrier gas is emptying by the 4th multiport valve;
Minute d.5-10 after, close the second multiport valve and pressure valve, open the 3rd heater strip on the 3rd condenser pipe, the 3rd condenser pipe is made to be heated to 50 DEG C, volatile organic matter now in the 3rd condenser pipe all changes gaseous state into, and be loaded into the second chromatograph by carrier gas source of the gas and carry out detection and analyze, complete the detection analysis containing six carbon atom and above volatile organic compounds in atmospheric sample;
E. simultaneously, after quantitative set by reaching at sampling quantity, control the first multiport valve and the second multiport valve, open the second heater strip on the second condenser pipe, make temperature increase in the second condenser pipe to 50 DEG C, make the solid-state volatile organic matter in the second condenser pipe change gaseous state into, and be loaded into the first chromatograph by carrier gas source of the gas and carry out detection and analyze, complete the detection analysis containing five carbon atoms and following volatile organic matter in atmospheric sample;
F. after completing said process, stop the refrigerating state of environmental chamber at low temperature, open the first heater strip, the second heater strip and the 3rd heater strip, the first condenser pipe, the second condenser pipe and the 3rd condenser pipe temperature is made to be elevated to 300 DEG C, control the first multiport valve, the second multiport valve, the 3rd multiport valve and the 4th multiport valve, blowback source of the gas is communicated with the second condenser pipe and the 3rd condenser pipe, and is communicated with the first condenser pipe, carry out blowback cleaning, purge gas is emptying by the first multiport valve;
G. after blowback process completes, close the first heater strip, the second heater strip and the 3rd heater strip, and reopen environmental chamber at low temperature and make it be in refrigerating state, make the first refrigeration cavity, second refrigeration cavity and the 3rd refrigeration cavity reach set temperature, for next time sampling and condensation concentration ready.
Preferably, further comprising the steps of between step b and step c:
B1. the first multiport valve is controlled, control the second multiport valve, the gas disconnecting mass flowmeter and the first condenser pipe flows, make the first condenser pipe and semipermeable partition except cross current, opening pressure valve makes semipermeable partition remove in water pipe to keep certain malleation, opens the first heater strip in the first refrigeration cavity, makes the temperature of the first condenser pipe in the first refrigeration cavity be raised to 50 DEG C, and control the first multiport valve, carrier gas source of the gas is communicated with the first condenser pipe; 50 DEG C are heated in first condenser pipe, now, water is in liquid state, and other is condensed in the volatile organic components in the first condenser pipe, transfer in gas phase after being heated to 50 DEG C of gasifications, and purged into semipermeable partition except dewatering further in water pipe by carrier gas source of the gas, carrier gas is emptying by the second multiport valve.
After have employed technique scheme, the invention has the beneficial effects as follows:
1. due to atmospheric volatile organic compounds sampling analysis device of the present invention and sampling and analyzing method, employing be semiconductor refrigerating technology, and semiconductor refrigerating technology utilizes the paltie effect of semiconductor material to freeze, and does not need cold-producing medium, direct refrigeration after energising.Semiconductor refrigerating has can the advantage 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 volatile organic content on-line monitoring.Therefore atmospheric volatile organic compounds sampling analysis device of the present invention and the sampling and analyzing method of this Refrigeration Technique is applied, overcome traditional cryogenic condensation device owing to needing liquid nitrogen refrigerating and poriness adsorbent and the defect existed: liquid nitrogen consumption is large, refrigeration cost is higher, liquid nitrogen field is changed simultaneously, stores difficulty; Poriness adsorbent heat desorption rate is slow, and component is residual high, and required purge time is long, thus causes the shortcomings such as analytical cycle length, can be used for the online automatic detection on the spot of atmospheric volatile organic compounds content.In addition, atmospheric volatile organic compounds sampling analysis device of the present invention in the course of the work, by the switch control rule of the first multiport valve, the second multiport valve, the 3rd multiport valve and the 4th multiport valve and the setting of the first cold-trap, the second cold-trap and the 3rd cold-trap different temperatures, make to carry out detection analysis containing six carbon atom and above volatile organic matter by entering the second chromatograph after the first cold-trap and the 3rd cold-trap in air.And remaining volatile organic matter carries out detection analysis by entering the first chromatograph after the second cold-trap in air, and this setting can adopt capillary column of different nature and dissimilar detecting device to the first and second chromatographs, add the responsiveness of whole analytic system to heterogeneity volatile organic matter.
2., owing to being also connected with semipermeable partition between the 3rd end of described second multiport valve and the entrance point of described 3rd condenser pipe except water pipe, described semipermeable partition is provided with drying tube except water pipe outer cover.Therefore atmospheric volatile organic compounds sampling analysis device of the present invention and sampling and analyzing method combine with semi-permeable water removal techniques by segmentation condensation is concentrated, the six carbon atom that contains in air is made to remove water pipe to the volatile organic matter containing 12 carbon atoms through semipermeable partition, further removing moisture wherein, maximum possible eliminate moisture on stratographic analysis impact, the result detecting analysis after making it enter the second chromatograph is more accurate.
3. because the first condenser pipe in the present invention, the second condenser pipe and the 3rd condenser pipe all adopt stainless steel condenser pipe, therefore in condensation process, component directly condensation on stainless-steel pipe, but not condensation on traditional poriness sorbing material, " memory " effect avoiding cross pollution between different analytical cycle and system of maximum possible.
4. because atmospheric volatile organic compounds sampling analysis device of the present invention and sampling and analyzing method use highly purified inert gas to carry out blowback to the first condenser pipe, the second condenser pipe and the 3rd condenser pipe, and not containing poriness sorbing material in condenser pipe, purging speed is fast, drastically increase thermal desorption speed, in a short period of time can the self-cleaning of completion system, shorten analytical cycle.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described:
Fig. 1 is the principle schematic of atmospheric volatile organic compounds sampling analysis device of the present invention and sampling and analyzing method;
In figure: 1, environmental chamber at low temperature; 2, the first refrigeration cavity; 21, the first condenser pipe; 22, the first heater strip; 3, the first semiconductor chilling plate group; 4, the second refrigeration cavity; 41, the second condenser pipe; 42, the second heater strip; 5, the second semiconductor chilling plate group; 6, the 3rd refrigeration cavity; 61, the 3rd condenser pipe; 62, the 3rd heater strip; 7, the 3rd semiconductor chilling plate group; 8, air sampler; 9, mass flowmeter; 10, the first multiport valve; 11, carrier gas source of the gas; 12, the second multiport valve; 13, the 3rd multiport valve; 14, the 4th multiport valve; 15, blowback source of the gas; 16, the first chromatograph; 17, the second chromatograph; 18, compressor; 19, semiconductor chilling plate; 20, semipermeable partition is except water pipe; 30, drying tube; 40, pressure valve.
Embodiment
Fig. 1 is the principle schematic of atmospheric volatile organic compounds sampling analysis device of the present invention and sampling and analyzing method, with reference to Fig. 1, atmospheric volatile organic compounds sampling analysis device of the present invention, comprise environmental chamber at low temperature 1 and air sampler 8, air sampler 8 has dedusting function.
Environmental chamber at low temperature 1 is connected with compressor, cryotrap device is provided with in environmental chamber at low temperature 1, cryotrap device comprises the first cold-trap, the second cold-trap and the 3rd cold-trap, first cold-trap comprises on the first condenser pipe 21 and the first semiconductor chilling plate group 3, first condenser pipe 21 and is wound with the first heater strip 22; Second cold-trap comprises on the second condenser pipe 41 and the second semiconductor chilling plate group 5, second condenser pipe 41 and is wound with the second heater strip 42; 3rd cold-trap comprises on the 3rd condenser pipe 61 and the 3rd semiconductor chilling plate group the 7, three condenser pipe 61 and is wound with the 3rd heater strip 62.Wherein, the first condenser pipe 21, second condenser pipe 41 and the 3rd condenser pipe 61 all adopt stainless steel material to make, and inside surface is through Passivation Treatment.Therefore in condensation process, component directly condensation on stainless-steel pipe, but not condensation on traditional poriness sorbing material, thermal desorption speed is fast, and " memory " effect avoiding cross pollution and system of maximum possible.
The output terminal of air sampler 8 is connected to the input end of mass flowmeter 9, the output terminal of mass flowmeter 9 is connected to the first end of the first multiport valve 10, second end of the first multiport valve 10 is connected with the entrance point of three-terminal link to the first condenser pipe 21 of carrier gas source of the gas 11, first multiport valve 10.
The endpiece of the first condenser pipe 21 is connected to the first end of the second multiport valve 12, and the second end of the second multiport valve 12 is connected with the entrance point of the second condenser pipe 41, and the 3rd end of the second multiport valve 12 is connected with the entrance point of the 3rd condenser pipe 61.In the present embodiment, semipermeable partition is also connected with except water pipe 20 between 3rd end of the second multiport valve 12 and the entrance point of the 3rd condenser pipe 61, the outside that semipermeable partition removes water pipe 20 is also arranged with drying tube 30, and semipermeable partition removes between the endpiece of water pipe 20 and the entrance point of the 3rd condenser pipe 61 and is also connected with pressure valve 40.It is Nafion semi-permeable film that semipermeable partition removes water pipe 20, water is by the semi-permeable membranous wall infiltration of Nafion, and evaporation subsequently enters in surrounding air, and we call this process " pervaporation ", serve the function dewatered, the moist gradient inside and outside pipe drives whole process.And pressure valve 40 maintains in Nafion semipermeable partition pipe and operationally keeps certain malleation.Nafion semipermeable partition pipe is made to serve good water removal effect to the volatile organic matter in air.
The endpiece of the second condenser pipe 41 is connected to the first end of the 3rd multiport valve 13, and the second end of the 3rd multiport valve 13 is connected with blowback source of the gas 15, and the three-terminal link of the 3rd multiport valve 13 is to the detection input end of the first chromatograph 16.Atmospheric volatile organic compounds sampling analysis device of the present invention and sampling and analyzing method use highly purified inert gas to carry out blowback to the first condenser pipe, the second condenser pipe and the 3rd condenser pipe, purging speed is fast, drastically increase thermal desorption speed, in a short period of time can the self-cleaning of completion system, shorten analytical cycle.
The endpiece of the 3rd condenser pipe 61 is connected to the first end of the 4th multiport valve 14, and the second end of the 4th multiport valve 14 is connected with blowback source of the gas 15, and the three-terminal link of the 4th multiport valve 14 is to the detection input end of the second chromatograph 17.
First chromatograph 16 and the second chromatograph 17 are two independently chromatograph analytic systems, in-built capillary column of different nature.First chromatograph 16 and the second chromatograph 17 are gas chromatograph or gas chromatograph-mass spectrometer.
The first refrigeration cavity 2, second refrigeration cavity 4 and the 3rd refrigeration cavity 6 is provided with in environmental chamber at low temperature 1; First condenser pipe 21 and the first heater strip 22 are arranged in the first refrigeration cavity 2, and the second condenser pipe 41 and the second heater strip 42 are arranged in the second refrigeration cavity 4; 3rd condenser pipe 61 and the 3rd heater strip 62 are arranged in the 3rd refrigeration cavity 6.In the present embodiment, according to the needs of volatile organic matter condensing temperature, first semiconductor chilling plate group 3 comprises the semiconductor chilling plate 19 of electrical connection that two or more fits together and in parallel, second semiconductor chilling plate group 5 comprise electrical connection that quantity more than three fits together and in parallel semiconductor chilling plate the 19, three semiconductor chilling plate group 7 comprise the semiconductor chilling plate 19 of electrical connection that two or more fits together and in parallel.Wherein, by the first semiconductor cooling sheet group 3 processed for the first refrigeration cavity 2 provides refrigeration, by the second semiconductor chilling plate group 5 for the second refrigeration cavity 4 provides refrigeration, by the 3rd semiconductor chilling plate group 7 for the 3rd refrigeration cavity 6 provides refrigeration.
In the present embodiment, the outside of the first refrigeration cavity 2, second refrigeration cavity 4 and the 3rd refrigeration cavity 6 is enclosed with heat-insulating material respectively.First multiport valve 10, second multiport valve 12, the 3rd multiport valve 13 and the 4th multiport valve 14 are various way solenoid valve.First condenser pipe 21, second condenser pipe 41 and the 3rd condenser pipe 61 are straight shape, snakelike or spiral wound.
Carrier gas source of the gas 11 and blowback source of the gas 15 are the inert gas that purity is greater than 99.9%.In the present embodiment, carrier gas source of the gas 11 and blowback source of the gas 15 are the helium that purity is greater than 99.9%.Certainly, other inert gas can also be adopted.Wherein, the meaning of carrier gas: in vapor-phase chromatography, mobile phase is gas, is called carrier gas.The effect of carrier gas enters chromatographic column together with certain flow velocity carrier band gaseous sample or the sample gas after gasification to be separated, again each component after separated is loaded into detecting device to detect, finally flow out condenser system emptying or collection, carrier gas has been carrier band effect and has not substantially participated in centrifugation.
The sampling and analyzing method of atmospheric volatile organic compounds sampling analysis device of the present invention is adopted to comprise the following steps:
A. first environmental chamber at low temperature 1 is started, it is made to be in refrigerating state, the first refrigeration cavity 2 and the first condenser pipe 21 is made to reach the low temperature of-40 DEG C to-50 DEG C, make the second refrigeration cavity 4 and the second condenser pipe 41 reach the low temperature of-145 DEG C to-155 DEG C, make the 3rd refrigeration cavity 6 and the 3rd condenser pipe 61 reach the low temperature of-55 DEG C to-65 DEG C;
B. atmospheric volatile organic compounds is after air sampler 8 is sampled, control the first multiport valve 10 and the second multiport valve 12, air sampler 8 is communicated with environmental chamber at low temperature 1, first condenser pipe 21 is communicated with the second condenser pipe 41, atmospheric sample is quantitatively sent in environmental chamber at low temperature 1 by mass flowmeter 9, first enter the first refrigeration cavity 2 and carry out condensation, the boiling point containing six carbon atom and above volatile organic compounds and moisture in atmospheric sample is higher, first be condensed in the first condenser pipe 21, change into solid-state; And the volatile organic matter that boiling point is lower, mainly containing five carbon atoms and following compound, other volatile organic components such as formaldehyde, methyl alcohol and methane that especially in air, content is higher, enter be converted in the second condenser pipe 41 solid-state; And other permanent gases in air, such as nitrogen, oxygen etc., because boiling point is lower, be not condensed into solid-state, and directly emptying by the 3rd multiport valve 13;
C. to be sampledly aequum is reached, after balance a period of time, control the first multiport valve 10, control the second multiport valve 12, the gas disconnecting mass flowmeter 9 and the first condenser pipe 21 flows, make the first condenser pipe 21 with semipermeable partition except water pipe 20 is communicated with, opening pressure valve 40 makes semipermeable partition remove in water pipe 20 to keep certain malleation, open the first heater strip 22 in the first refrigeration cavity 2, the temperature of the first condenser pipe 21 in the first refrigeration cavity 1 is made to be raised to 50 DEG C, and control the first multiport valve 10, carrier gas source of the gas 11 is communicated with the first condenser pipe 21; 50 DEG C are heated in first condenser pipe 21, now, water is in liquid state, vapour pressure is very low, and other is condensed in the volatile organic components in the first condenser pipe 21, transfer in gas phase after being heated to 50 DEG C of gasifications, and purged into semipermeable partition except dewatering further in water pipe 20 by carrier gas source of the gas 11, then enter the 3rd condenser tube 61 carry out cryogenic condensation concentrate, carrier gas is emptying by the 4th multiport valve 14;
Minute d.5-10 after, close the second multiport valve 12 and pressure valve 40, open the 3rd heater strip 62 on the 3rd condenser pipe 61, the 3rd condenser pipe 61 is made to be heated to 50 DEG C, volatile organic matter now in the 3rd condenser pipe 61 all changes gaseous state into, and be loaded into the second chromatograph 17 by carrier gas source of the gas 11 and carry out detection and analyze, complete the detection analysis containing six carbon atom and above volatile organic compounds in atmospheric sample;
E. simultaneously, after quantitative set by reaching at sampling quantity, control the first multiport valve 10 and the second multiport valve 12, open the second heater strip 42 on the second condenser pipe 41, make temperature increase in the second condenser pipe 41 to 50 DEG C, make the solid-state volatile organic matter in the second condenser pipe 41 change gaseous state into, and be loaded into the first chromatograph 16 by carrier gas source of the gas 11 and carry out detection and analyze, complete the detection analysis containing five carbon atoms and following volatile organic matter in atmospheric sample;
F. after completing said process, stop the refrigerating state of environmental chamber at low temperature 1, open the first heater strip 22, second heater strip 42 and the 3rd heater strip 62, the first condenser pipe 21, second condenser pipe 41 and the 3rd condenser pipe 61 temperature is made to be elevated to 300 DEG C, control the first multiport valve 10, second multiport valve 12, the 3rd multiport valve 13 and the 4th multiport valve 14, blowback source of the gas 15 is communicated with the second condenser pipe 41 and the 3rd condenser pipe 61, and be communicated with the first condenser pipe 21, carry out blowback cleaning, purge gas is emptying by the first multiport valve 10;
G. after blowback process completes, close the first heater strip 22, second heater strip 42 and the 3rd heater strip 62, and reopen environmental chamber at low temperature 1 and make it be in refrigerating state, make first refrigeration cavity 2, second freeze cavity 4 and the 3rd refrigeration cavity 6 reach set temperature, for next time sampling and condensation concentration ready.
As can be seen from the above-mentioned course of work of atmospheric volatile organic compounds sampling analysis device of the present invention and sampling and analyzing method, atmospheric volatile organic compounds sampling analysis device of the present invention, what adopt is semiconductor refrigerating technology, and semiconductor refrigerating technology utilizes the paltie effect of semiconductor material to freeze, do not need cold-producing medium, directly freeze after energising.Semiconductor refrigerating has can the advantage 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.Meanwhile, the condenser pipe that patent of the present invention adopts is the stainless-steel tube of hollow, does not need to fill traditional poriness sorbing material; The refrigeration system of this technology can meet the needs to volatile organic matter on-line real time monitoring.Therefore the atmospheric volatile organic compounds sampling analysis device of the present invention of this Refrigeration Technique is applied, overcome the defect existed owing to needing liquid nitrogen refrigerating of traditional cryogenic condensation device: liquid nitrogen consumption is large, refrigeration cost is higher, and liquid nitrogen field is changed simultaneously, stores difficulty; Meanwhile, the stainless-steel tube thermal desorption speed of hollow is fast, purges easily, makes the cleaning systems time short, shorten the analytical test cycle, can be used for the online automatic detection on the spot of atmospheric volatile organic compounds content.
In addition, atmospheric volatile organic compounds sampling analysis device of the present invention in the course of the work, by the switch control rule of the first multiport valve 10, second multiport valve 12, the 3rd multiport valve 13 and the 4th multiport valve 14 and the setting of the first cold-trap, the second cold-trap and the 3rd cold-trap different temperatures, make to carry out detection analysis containing six carbon atom and above volatile organic matter by entering the second chromatograph 17 after the first cold-trap and the 3rd cold-trap in air.And remaining volatile organic matter carries out detection analysis by entering the first chromatograph 16 after the second cold-trap in air.This shows, enter two chromatographs after volatile organic matter in air can be divided into two classes by atmospheric volatile organic compounds sampling analysis device of the present invention and sampling and analyzing method respectively and carry out detection analysis, and two chromatographs can adopt chromatographic column of different nature and dissimilar detecting device, improve the responsiveness of chromatograph to different volatile organic matter, and improve detection analysis precision.
Atmospheric volatile organic compounds sampling analysis device of the present invention and sampling and analyzing method combine with semi-permeable water removal techniques by segmentation condensation is concentrated, make in air containing six carbon atom and above volatile organic matter when semipermeable partition is except water pipe 20, further removing moisture wherein, eliminate the impact of moisture on stratographic analysis, detect the result analyzed after making it enter the second chromatograph 17 more accurate.
The above is the citing of best mode for carrying out the invention, and the part wherein do not addressed in detail is the common practise of those of ordinary skill in the art.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. an atmospheric volatile organic compounds sampling analysis device, is characterized in that, comprising:
Environmental chamber at low temperature, described environmental chamber at low temperature is connected with compressor, cryotrap device is provided with in described environmental chamber at low temperature, described cryotrap device comprises the first cold-trap, the second cold-trap and the 3rd cold-trap, described first cold-trap comprises the first condenser pipe and the first semiconductor chilling plate group, and described first condenser pipe is wound with the first heater strip; Described second cold-trap comprises the second condenser pipe and the second semiconductor chilling plate group, and described second condenser pipe is wound with the second heater strip; Described 3rd cold-trap comprises the 3rd condenser pipe and the 3rd semiconductor chilling plate group, and described 3rd condenser pipe is wound with the 3rd 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, second end of described first multiport valve is connected with carrier gas source of the gas, and the three-terminal link of described first multiport valve is to the entrance point of described first condenser pipe;
The endpiece of described first condenser pipe is connected to the first end of the second multiport valve, and the second end of described second multiport valve is connected with the entrance point of described second condenser pipe, and the 3rd end of described second multiport valve is connected with the entrance point of described 3rd condenser pipe;
The endpiece of described second condenser pipe is connected to the first end of the 3rd multiport valve, and the second end of described 3rd multiport valve is connected with blowback source of the gas, and the three-terminal link of described 3rd multiport valve is to the first chromatographic detection input end;
The endpiece of described 3rd condenser pipe is connected to the first end of the 4th multiport valve, and the second end of described 4th multiport valve is connected with described blowback source of the gas, and the three-terminal link of described 4th multiport valve is to the second chromatographic detection input end.
2. atmospheric volatile organic compounds sampling analysis device as claimed in claim 1, is characterized in that: be provided with the first refrigeration cavity, the second refrigeration cavity and the 3rd refrigeration cavity in described environmental chamber at low temperature; Described first condenser pipe and described first heater strip are arranged in described first refrigeration cavity, described second condenser pipe and described second heater strip are arranged in described second refrigeration cavity, and described 3rd condenser pipe and described 3rd heater strip are arranged in described 3rd refrigeration cavity.
3. atmospheric volatile organic compounds sampling analysis device as claimed in claim 1, it is characterized in that: be also connected with semipermeable partition between the 3rd end of described second multiport valve and the entrance point of described 3rd condenser pipe except water pipe, described semipermeable partition removes water pipe outer cover and is provided with drying tube.
4. atmospheric volatile organic compounds sampling analysis device as claimed in claim 3, is characterized in that: described semipermeable partition removes between the endpiece of water pipe and the entrance point of described 3rd condenser pipe and is also connected with pressure valve.
5. atmospheric volatile organic compounds sampling analysis device as claimed in claim 1, it is characterized in that: described first semiconductor chilling plate group comprises the semiconductor chilling plate of electrical connection that two or more fits together and in parallel, described second semiconductor chilling plate group comprise more than three fit together and the semiconductor chilling plate of electrical connection in parallel, described 3rd semiconductor chilling plate group comprises the semiconductor chilling plate of electrical connection that two or more fits together and in parallel.
6. atmospheric volatile organic compounds sampling analysis device as claimed in claim 2, is characterized in that: the outside of described first refrigeration cavity, described second refrigeration cavity and described 3rd refrigeration cavity is enclosed with heat-insulating material respectively.
7. atmospheric volatile organic compounds sampling analysis device as claimed in claim 1, is characterized in that: described first condenser pipe, described second condenser pipe and described 3rd condenser pipe are stainless steel condenser pipe.
8. the atmospheric volatile organic compounds sampling analysis device as described in any one of claim 1 to 7, 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. adopt the sampling and analyzing method of atmospheric volatile organic compounds sampling analysis device according to claim 1, it is characterized in that, comprise the following steps:
A. first environmental chamber at low temperature is started, it is made to be in refrigerating state, the first refrigeration cavity and the first condenser pipe is made to reach the low temperature of-40 DEG C to-50 DEG C, make the second refrigeration cavity and the second condenser pipe reach the low temperature of-145 DEG C to-155 DEG C, make the 3rd refrigeration cavity and the 3rd condenser pipe reach the low temperature of-55 DEG C to-65 DEG C;
B. atmospheric volatile organic compounds is after air sampler sampling, control the first multiport valve and the second multiport valve, air sampler is communicated with environmental chamber at low temperature, first condenser pipe is communicated with the second condenser pipe, atmospheric sample is quantitatively sent in environmental chamber at low temperature by mass flowmeter, first enters the first refrigeration cavity and carries out condensation, in atmospheric sample containing six carbon atom and above volatile organic compounds and moisture, first be condensed in the first condenser pipe, change into solid-state; In atmospheric sample containing five carbon atoms and following volatile organic matter enter be converted in the second condenser pipe solid-state; And other gas in air, be not condensed into solid-state, and directly emptying by the 3rd multiport valve;
C. to be sampledly aequum is reached, after balance a period of time, control the first multiport valve, control the second multiport valve, the gas disconnecting mass flowmeter and the first condenser pipe flows, and the first condenser pipe is communicated with the 3rd 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 50 DEG C, and control the first multiport valve, carrier gas source of the gas is communicated with the first condenser pipe; 50 DEG C are heated in first condenser pipe, now, water is in liquid state, and other is condensed in the volatile organic components in the first condenser pipe, transfer in gas phase after being heated to 50 DEG C of gasifications, and purged by carrier gas source of the gas and enter the 3rd condenser pipe and carry out cryogenic condensation and concentrate, carrier gas is emptying by the 4th multiport valve;
Minute d.5-10 after, close the second multiport valve and pressure valve, open the 3rd heater strip on the 3rd condenser pipe, the 3rd condenser pipe is made to be heated to 50 DEG C, volatile organic matter now in the 3rd condenser pipe all changes gaseous state into, and be loaded into the second chromatograph by carrier gas source of the gas and carry out detection and analyze, complete the detection analysis containing six carbon atom and above volatile organic compounds in atmospheric sample;
E. simultaneously, after quantitative set by reaching at sampling quantity, control the first multiport valve and the second multiport valve, open the second heater strip on the second condenser pipe, make temperature increase in the second condenser pipe to 50 DEG C, make the solid-state volatile organic matter in the second condenser pipe change gaseous state into, and be loaded into the first chromatograph by carrier gas source of the gas and carry out detection and analyze, complete the detection analysis containing five carbon atoms and following volatile organic matter in atmospheric sample;
F. after completing said process, stop the refrigerating state of environmental chamber at low temperature, open the first heater strip, the second heater strip and the 3rd heater strip, the first condenser pipe, the second condenser pipe and the 3rd condenser pipe temperature is made to be elevated to 300 DEG C, control the first multiport valve, the second multiport valve, the 3rd multiport valve and the 4th multiport valve, blowback source of the gas is communicated with the second condenser pipe and the 3rd condenser pipe, and is communicated with the first condenser pipe, carry out blowback cleaning, purge gas is emptying by the first multiport valve;
G. after blowback process completes, close the first heater strip, the second heater strip and the 3rd heater strip, and reopen environmental chamber at low temperature and make it be in refrigerating state, make the first refrigeration cavity, second refrigeration cavity and the 3rd refrigeration cavity reach set temperature, for next time sampling and condensation concentration ready.
10. the sampling and analyzing method of atmospheric volatile organic compounds sampling analysis device as claimed in claim 9, is characterized in that, further comprising the steps of between step b and step c:
B1. the first multiport valve is controlled, control the second multiport valve, the gas disconnecting mass flowmeter and the first condenser pipe flows, make the first condenser pipe and semipermeable partition except cross current, opening pressure valve makes semipermeable partition remove in water pipe to keep certain malleation, opens the first heater strip in the first refrigeration cavity, makes the temperature of the first condenser pipe in the first refrigeration cavity be raised to 50 DEG C, and control the first multiport valve, carrier gas source of the gas is communicated with the first condenser pipe; 50 DEG C are heated in first condenser pipe, now, water is in liquid state, and other is condensed in the volatile organic components in the first condenser pipe, transfer in gas phase after being heated to 50 DEG C of gasifications, and purged into semipermeable partition except dewatering further in water pipe by carrier gas source of the gas, carrier gas is emptying by the second multiport valve.
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