CN104777261B - In air, volatile organic matter cryogenic gas-chromatography analyzes system, method and device - Google Patents
In air, volatile organic matter cryogenic gas-chromatography analyzes system, method and device Download PDFInfo
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- CN104777261B CN104777261B CN201510170602.6A CN201510170602A CN104777261B CN 104777261 B CN104777261 B CN 104777261B CN 201510170602 A CN201510170602 A CN 201510170602A CN 104777261 B CN104777261 B CN 104777261B
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Abstract
The invention discloses volatile organic matter cryogenic gas-chromatography in a kind of air and analyze system, method and device, described method includes gathering gaseous sample, the sample collected carries out deodorization oxygen process, except water process and enrichment process；Sample after enrichment processes is carried out separating treatment and detects；Analyzing and processing testing result.Described device uses temperature conditioning unit to realize atmospheric sample except the purpose that water processes, the efficient cryogenic of low hydrocarbon is separated by enrichment process with single capillary post simultaneously.The present invention is simple, reliable, can meet the various demand of indoor and outdoor atmospheric seeing.
Description
Technical field
The present invention relates to chromatography field, in particular to volatile organic matter low-temperature gaseous phase color in a kind of air
Spectral analysis system, method and device.
Background technology
In air, volatile organic matter (VOC) is mainly derived from nature discharge and fossil man's fuel (coal, oil and sky
So gas) use.This compounds comprises the Organic substance in a large number with high reaction activity, can be with active specy in air (such as OH
Free radical and ozone etc.) fast reaction produces organic peroxy base, and organic peroxy base is further in city is rich in the air of NOx
Participate in reaction, produce the ozone that the mankind and ecosystem are had obvious negative effect.Additionally, amount of activated volatile organic matter
Form secondary organic aerosol through complex processes such as photooxidation in an atmosphere, radiation balance can be changed and then affect global climate
Change.Owing in air, volatile organic matter has important function in the generation of atmospheric ozone and secondary organic aerosol, and
And part VOC exists harm to health, the research of atmospheric volatile organic compounds becomes recent domestic Atmospheric Chemistry and grinds
One of hot fields studied carefully.
Have been developed in monitoring technology and the method for volatile organic matter in many measure air at present in the world, but existing
VOC analytical technology and method have that equipment is complicated, expensive, it is lengthy and tedious to operate and the low shortcoming of resolution analysis time mostly,
Actual demand with atmospheric seeing has bigger gap.Therefore, research renewal, simpler, more rapid, the application wider array of VOC of species
Sampling analysis method and analytical technology, have great importance in atmospheric environment field.
Summary of the invention
It is an object of the invention to provide a kind of simple, reliable, the low wet of volatile organic matter that can operate continuously for a long time
Chromatographic system, method and device.
For reaching above-mentioned purpose, embodiments provide volatile organic matter cryogenic gas-chromatography in a kind of air and divide
Analysis system, including: sampling unit, separation and detector unit and Signal acquiring and processing unit；
Described sampling unit is used for gathering gaseous sample, and the gaseous sample collected carries out deodorization oxygen process, except water
Process, and the volatile organic matter in the gaseous sample after processing is carried out enrichment process；
Described separation is connected with the outfan of the input of detector unit with described sampling unit, and described separation is single with detection
Unit is for separating the volatile organic matter after enrichment processes, and examines the volatile organic matter after separating
Survey；
The input of described signal processing unit is connected with the described outfan separated with detector unit, described signal processing
Unit is for being analyzed processing to the testing result of described separation Yu detector unit.
Preferably, temperature control unit is also included；
Described temperature control unit respectively with described sampling unit, separate and be connected with detector unit, for described sampling unit,
Temperature needed for separation and detector unit offer work
The embodiment of the present invention additionally provides volatile organic matter cryogenic gas-chromatography in a kind of air and analyzes method, including such as
Lower step:
Step 1, set up acquisition channel, complete the preparation before gathering；
Step 2, gather gaseous sample, the gaseous sample collected is carried out deodorization oxygen process, processes, and to process except water
After gaseous sample in volatile organic matter carry out enrichment process；
Step 3, to through enrichment process after volatile organic matter carry out separating treatment, to separate after volatility organic
Thing detects, and is analyzed testing result processing.
Preferably, the volatile organic matter in gaseous sample after processing is carried out the detailed process of enrichment process by step 2
For: will process after gaseous sample by being filled with the enrichment pipe of ketjenblack EC adsorbent, by enrichment pipe refrigeration to-90 DEG C with
Under.
Preferably, step 3 carries out separating treatment process to the volatile organic matter after enrichment processes as follows:
Enrichment pipe is heated to uniform temperature so that the volatile organic matter Thermal desorption after enrichment processes becomes gaseous state,
Then the gaseous volatile Organic substance after Thermal desorption is separated by chromatographic column with carrier gas.
Present invention also offers volatile organic matter cryogenic gas-chromatography analytical equipment in a kind of air, including sampling cartridge
Put, separate and detect device, temperature control equipment and signal processing apparatus；
The outfan of described sampling apparatus is connected with the described input separated and detect device；
Described separation is connected with the input of described signal processing apparatus with the outfan of detection device；
Described temperature control equipment respectively with described sampling apparatus, separate and detect device and be connected, for described sampling apparatus
Temperature required with detection device offer work with separating.
Preferably, described sampling apparatus include being sequentially connected with except ozonizer, except water pipe, enrichment pipe；
Described separation includes injector, chromatographic column and detector with detection device, and the entrance of described injector is with described
The outlet of enrichment pipe connects, and the outlet of described injector is connected with the entrance of described chromatographic column, the outlet of described chromatographic column and institute
The entrance stating detector connects；
Described temperature control equipment includes refrigeration machine, described enrichment pipe, is also equipped with cold-trap list in addition to water pipe, chromatographic column
Unit, each cold-trap unit is all connected with refrigeration machine, is equipped with resistance heating wire in each cold-trap unit；
Described signal processing apparatus includes chromatographic work station, and the input of described chromatographic work station is defeated with described detector
Go out end to connect.
Preferably, the first six-way valve and the second six-way valve, the described outfan except ozonizer and the described 2nd 6 are also included
5 holes of logical valve connect, and described are connected with 4 holes of described second six-way valve except the input of water pipe, described except the outfan of water pipe
Being connected with 4 holes of described first six-way valve, the input of described enrichment pipe is connected with 5 holes of described first six-way valve, described richness
The outfan of collector is connected with 2 holes of described first six-way valve, the input of described injector and 6 holes of described first six-way valve
Connect.
Preferably, feeder is also included；
Described feeder includes Nitrogen source gases and provides the gas of fuel gas and combustion-supporting gas to send out for described detector
Source of students；
Described Nitrogen source gases respectively with the first mass flow controller, the second mass flow controller, the 3rd mass flow
The input of controller connects, and described gas occurring source is connected with the input of described detector；
The outfan of described first mass flow controller and 1 hole of the first six-way valve connect, described second mass flow
The outfan of controller is connected with 2 holes of described second six-way valve, and the outfan of described 3rd mass flow controller is with described
The input of detector connects.
Preferably, described temperature control equipment also includes PID controller, and PID controller outward and is removed with being wrapped in enrichment pipe
Resistance heating wire outside water pipe and in chromatographic column connects.
Preferably, described detector uses flame ionization ditector, and described chromatographic column uses capillary chromatographic column, institute
State in enrichment pipe uses internal diameter 2-4mm, the stainless steel tube of long 10-20cm, enrichment pipe and fill ketjenblack EC adsorbent；Described remove
Water pipe and except ozonizer uses internal diameter 3-6mm, the empty glass tubing of long 10-20cm or empty Peek pipe or empty PTFE tube；Described deodorization
It is added with Na in oxygen pipe2SO3。
The volatile organic matter cryogenic gas-chromatography that the embodiment of the present invention provides analyzes system, method and device, by building
Vertical acquisition channel, carries out deodorization oxygen process, processes except water the gaseous sample collected, and in the gaseous sample after processing
Volatile organic matter carries out enrichment process；Sample after enrichment processes is separated, detects and carries out testing result
Further on-line analysis, simple, reliable and can operate continuously for a long time, indoor and outdoor various field observation demand can be met.
Accompanying drawing explanation
In order to be illustrated more clearly that the technical scheme of the embodiment of the present invention, below by embodiment required use attached
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, and it is right to be therefore not construed as
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to according to this
A little accompanying drawings obtain other relevant accompanying drawings.
In the air that Fig. 1 provides for one embodiment of the invention, volatile organic matter cryogenic gas-chromatography is analyzed system structure and is shown
It is intended to；
Fig. 2 a is that in the air that the embodiment of the present invention provides, volatile organic matter cryogenic gas-chromatography analyzes method flow diagram；
In the air that Fig. 2 b provides for the embodiment of the present invention, volatile organic matter cryogenic gas-chromatography analyzes the enforcement of method
Process schematic representation；
In the air that Fig. 3 provides for one embodiment of the invention, volatile organic matter cryogenic gas-chromatography analytical equipment structure is shown
It is intended to；
Volatile organic matter cryogenic gas-chromatography analytical equipment structure in the air that Fig. 4 provides for another embodiment of the present invention
Schematic diagram；
Volatile organic matter cryogenic gas-chromatography analytical equipment in the air that Fig. 5 a provides for another embodiment of the present invention
One working state structure schematic diagram；
Volatile organic matter cryogenic gas-chromatography analytical equipment in the air that Fig. 5 b provides for another embodiment of the present invention
Two working state structure schematic diagrams；
Volatile organic matter cryogenic gas-chromatography analytical equipment in the air that Fig. 5 c provides for another embodiment of the present invention
Three working state structure schematic diagrams；
Fig. 6 a analyzes NMHCs mark for volatile organic matter cryogenic gas-chromatography in an air of offer in the embodiment of the present invention
Quasi-spectrogram (0-17.5min)；
Fig. 6 b analyzes NMHCs for volatile organic matter cryogenic gas-chromatography in another air of offer in the embodiment of the present invention
Standard spectrogram (17.5-31.0min).
In figure, the concrete meaning of label is: 11, collecting unit, 12, separate and detector unit, 13, signal processing unit,
14, temperature control unit, 101, enrichment pipe, 102, except ozonizer, 103, except water pipe, the 104, the 5th electromagnetic valve, the 105, the 4th electricity
Magnet valve, the 106, the 4th mass flow controller, 107, sampling pump, the 111, first six-way valve, the 112, second six-way valve, 201, sample introduction
Device, 202, chromatographic column, 203, detector, 301, refrigeration machine, 401, Nitrogen source gases, 402, hydrogen generator, 403, compressed air
Generator, 404, gas occurring source, the 501, first mass flow controller, the 502, second mass flow controller, the 503, the 3rd
Mass flow controller, the 504, the 7th mass flow controller, the 505, the 5th mass flow controller, the 506, the 6th mass flow
Controller, the 601, first electromagnetic valve, the 602, second electromagnetic valve, the 603, the 3rd electromagnetic valve.
Detailed description of the invention
It should be noted that in the case of not conflicting, the embodiment in the application and the feature in embodiment can phases
Combination mutually.Describe the present invention below with reference to the accompanying drawings and in conjunction with the embodiments in detail.
In order to make those skilled in the art be more fully understood that the present invention program, below in conjunction with attached in the embodiment of the present invention
Figure, is clearly and completely described the technical scheme in the embodiment of the present invention, it is clear that described embodiment is only this
Invent a part of embodiment rather than whole embodiments.Generally herein described in accompanying drawing and the embodiment of the present invention that illustrates
Assembly can arrange with various different configurations and design.Therefore, enforcement to the present invention provided in the accompanying drawings below
The detailed description of example is not intended to limit the scope of claimed invention, but is merely representative of the selected enforcement of the present invention
Example.Based on embodiments of the invention, it is all that those skilled in the art are obtained on the premise of not making creative work
Other embodiments, broadly fall into the scope of protection of the invention.Below by specific embodiment and combine accompanying drawing the present invention is done into
The detailed description of one step.
In air volatile organic matter mostly refer to C2-C12 non-methane hydro carbons (NMHCs), oxygenatedchemicals and
The volatile organic matters such as halogenated hydrocarbons, the object of chromatography of the present invention is exactly these volatile organic matters.
Fig. 1 is that the volatile organic matter cryogenic gas-chromatography that the embodiment of the present invention provides analyzes system structure schematic diagram, is
System includes: sampling unit 11, separation and detector unit 12 and signal processing unit 13.
Sampling unit 11 is used for gathering gaseous sample, and the gaseous sample collected is carried out deodorization oxygen process, except water at
Reason, and will process after gaseous sample in volatile organic matter carry out enrichment process；Separate with detector unit 12 for warp
Cross the volatile organic matter after enrichment processes and carry out separating treatment, and the volatile organic matter after separating is detected；Signal
Processing unit 13 is for receiving the testing result of described separation and detector unit, and is analyzed testing result processing.
Owing in general atmosphere, volatile organic content is the lowest, in order to meet the testing requirement of detector, atmospheric sample
Needs carry out enrichment process, for the present invention, can use but be not limited to ketjenblack EC as adsorbent, the suction of ketjenblack EC
Attached effect is best when temperature is less than-90 DEG C, can realize 100% capture of C2-C12 volatile organic matter.But, due to air
Middle moisture is the biggest, and atmospheric sample is easily caused the blocking of enrichment pipe in low temperature enrichment process；Oxidation in air
Agent is (such as O3Deng) can react with unsaturated hydrocarbon during enrichment and Thermal desorption and cause the loss of VOC.Cause
This, in order to avoid atmosphere moisture and oxidant are to the interference of target compound VOC or loss, atmospheric sample is in gatherer process
Need wherein moisture and oxidant are removed.In the embodiment of the present invention, atmospheric sample (gaseous sample) the first warp of collection
Cross one and fill reducing substances Na2SO3Glass tubing atmospheric oxidant is removed, secondly, enter through a cryogenic piping
Row is except water, and finally, the VOC in atmospheric sample has the low temperature enrichment pipe of ketjenblack EC adsorbent to complete atmospheric sample to adopt through adding
Collection process.The VOC that enrichment pipe is gathered, through quickly heating up to about 150 DEG C, can realize the volatilization of VOC, and the VOC of volatilization is carrying
Sequentially entering chromatography column under the driving of gas and detector separates and detects, the response signal of detector passes through chromatograph work
Carry out record as station, and then the retention time and signal intensity according to VOC calibrating gas carries out qualitative and quantitative analysis.
The volatile organic matter cryogenic gas-chromatography that the embodiment of the present invention provides analyzes system, also includes temperature control unit
14, temperature control unit 14 for meeting described sampling unit 11, separating and work required temperature conditions with detector unit 12, as
The chilling temperature processed except water, adsorption temp when enrichment processes, temperature needed during Thermal desorption etc., all can pass through temperature control list
Unit realizes.
In the present embodiment, temperature control unit 14 can use but be not limited to refrigeration machine and heater, is used for providing corresponding temperature
Degree, wherein, refrigeration machine and heater can realize the accurate control of temperature by PID controller.
Fig. 2 a is that in the air that the embodiment of the present invention provides, volatile organic matter cryogenic gas-chromatography analyzes method flow diagram,
Fig. 2 b is the schematic diagram of its implementing process.Illustrating in conjunction with Fig. 2 a and Fig. 2 b, the method comprises the steps, including walking as follows
Rapid:
Step S11, set up acquisition channel, complete the preparation before gathering.Preparation in this step include but not
It is limited to provide and meets temperature and the carrier gas of flow speed stability of gas collecting condition, ensure the seal of passage, measure flow
Accuracy.
Step S12, gather gaseous sample, the gaseous sample collected is carried out deodorization oxygen process, processes, and to place except water
The volatile organic matter in gaseous sample after reason carries out enrichment process.To the volatile organic matter in the gaseous sample after processing
The detailed process carrying out enrichment process is: the gaseous sample after processing is by being filled with the enrichment of ketjenblack EC adsorbent
Pipe, by enrichment pipe refrigeration to less than-90 DEG C, such volatile organic matter will adsorb in enrichment pipe.
Step S13, the volatile organic matter after enrichment processes is carried out separating treatment, then to the volatility after separating
Organic substance detects, and is analyzed testing result processing.Wherein, the sample after enrichment processes is carried out at separation
Reason process is as follows: enrichment pipe is heated to uniform temperature so that the sample Thermal desorption after enrichment processes becomes gaseous state, then will
Sample after Thermal desorption is separated by chromatographic column with carrier gas, is detected by detector after separation, carries out testing result point
Analysis is processed and can be completed by softwares such as chromatographic work stations.
Seeing Fig. 3, the embodiment of the present invention additionally provides volatile organic matter cryogenic gas-chromatography analysis dress in a kind of air
Put, including sampling apparatus, separate and detect device, temperature control equipment and Signal acquiring and processing device；
Sampling apparatus include being sequentially connected with except ozonizer 102, except water pipe 103, enrichment pipe 101, sampling pump 107；
Separate and include injector 201, chromatographic column 202 and detector 203 with detection device, the entrance of injector 201 with
The outlet of described enrichment pipe 101 connects, and the outlet of injector 201 is connected with the entrance of chromatographic column 202, the outlet of chromatographic column 202
It is connected with the entrance of detector 203；
Temperature control equipment includes refrigeration machine, enrichment pipe 101, cold-trap list set in addition to water pipe 103, chromatographic column 202
Unit, each cold-trap unit is connected with refrigeration machine, is also equipped with resistance heating wire in each cold-trap unit；
Signal processing apparatus includes but not limited to chromatographic work station, the input of chromatographic work station and the outfan of detector
Connect.
Its work process is as follows: atmospheric sample sequentially passes through except ozonizer 102, except water pipe 103, enrichment pipe 101, now mesh
Mark compound (volatile organic matter in air) is concentrated in enrichment pipe 101, and remaining gas can be discharged by sampling pump 107, complete
Becoming the collecting work of target compound, target compound can become gaseous state, then by gaseous target chemical combination again by Thermal desorption
Thing is along with carrier gas (N2) enter injector 201, injector 201 input chromatographic column 202 and separate, device 203 the most after testing
Detection, in the present embodiment, detector 203 can use but is not limited to flame ionization ditector, and chromatographic column 202 uses capillary tube
Chromatographic column, enrichment pipe fills ketjenblack EC adsorbent in using internal diameter 2-4mm, the stainless steel tube of long 10-20cm, enrichment pipe；
Except water pipe and except ozonizer uses internal diameter 3-6mm, the empty glass tubing of long 10-20cm or empty Peek pipe or empty PTFE tube；Deodorization oxygen
Na it is added with in pipe2SO3。
See Fig. 4, Fig. 4 and show volatile organic matter cryogenic gas-chromatography in the air that another embodiment of the present invention provides
Analytical equipment structural representation, the present embodiment is additionally arranged feeder on the basis of a upper embodiment, and feeder includes nitrogen
Gas the source of the gas 401 and gas occurring source 404 of fuel gas and combustion-supporting gas is provided for detector 203；
Nitrogen source gases 401 respectively with first mass flow controller the 501, second mass flow controller the 502, the 3rd mass
The input of flow controller 503 connects, and gas occurring source 404 is connected with the input of detector 203；
The outfan of the first mass flow controller 501 is connected by the outfan of the first electromagnetic valve 601 with enrichment pipe 101
Connecing, the outfan of the second mass flow controller 502 is connected with the outfan of enrichment pipe 101 by the second electromagnetic valve 602, and the 3rd
The outfan of mass flow controller 503 is connected with the input of detector 203 by the 3rd electromagnetic valve 603.
In the present embodiment, the first mass flow controller 501 is used for providing carrier gas.When enrichment pipe 101 completes targeted
After the enrichment of compound processes, now target compound is enrichment stage, and absorption is in enrichment pipe 101, needs target chemical combination
Thing heats so that it is resolves to gas, now opens the first electromagnetic valve 601, controls carrier gas by the first mass flow controller 501
Speed so that again resolve to the target compound of gaseous state along with carrier gas inflow chromatographic column 202.Second mass flow controller
502 are used for blowback, and blowback is in order to heavy constituent in enrichment pipe with except ice crystal emptying in water pipe, it is therefore an objective to avoid heavy constituent and water
Steam enters chromatographic column, and one accelerates analysis time, and two extend chromatographic column service life.The component needed during detection
After chromatographic column 202, open the second electromagnetic valve 602, control nitrogen stream by the second mass flow controller 502
Speed, controls to make enrichment pipe 101 and except the nitrogen in water pipe 103 flows by nitrogen flow rate, the heavy constituent in enrichment pipe with remove
Ice crystal in water pipe gasifies at relatively high temperatures and blowback is gone out, and fast cooling prepares to be enriched with next time.3rd mass flow control
Device 503 processed is mainly used in tail and blows, and opens the 3rd electromagnetic valve 603, increases carrier gas further by the 3rd mass flow controller 503
Flow velocity, to reach quickly to be blown into by sample detector 203, it is to avoid peak stretching after post, puies forward highly sensitive purpose.
See Fig. 5 a, present embodiments provide in another kind of air volatile organic matter cryogenic gas-chromatography analytical equipment the
One working state structure schematic diagram, the present embodiment part unlike the embodiments above essentially consists in, and the present embodiment passes through two six
Logical valve realizes the switching of gas circuit, and convenient and reliable, concrete structure is as follows:
Except the outfan of ozonizer 102 and 5 holes of the second six-way valve 112 connect, except the input and the two or six of water pipe 103
4 holes of logical valve 112 connect, except the outfan of water pipe 103 is connected with 4 holes of the first six-way valve 111 by the 5th electromagnetic valve 104,
The input of enrichment pipe 101 and 5 holes of the first six-way valve 111 connect, the outfan of enrichment pipe 101 and the 2 of the first six-way valve 111
Hole connects, and the input of injector 201 and 6 holes of the first six-way valve 111 connect, the output of the first mass flow controller 501
End is connected by 1 hole of the first electromagnetic valve 601 with the first six-way valve 111, and the outfan of the second mass flow controller 502 passes through
Second electromagnetic valve 602 is connected with 2 holes of the second six-way valve 112, and the outfan of the 3rd mass flow controller 503 is by the 3rd electricity
Magnet valve 603 is connected with the input of detector 203, and in the present embodiment, detector 203 uses flame ionization ditector, gas
Occurring source is made up of hydrogen generator 402 and compressed air generator 403, respectively by the 5th mass flow controller 505, the
Six mass flow controllers 506 are connected with detector 203, and other structure is same as the previously described embodiments, repeats no more.
The work process of the present embodiment is as follows: step 1, and acquisition channel is set up, by first six-way valve the 111, second six-way valve
112 position playback as shown in Fig. 5 a, the 5th electromagnetic valve the 104, the 4th electromagnetic valve 105 is opened, and completes the number of gas collecting Conditions Temperature
According to collection analysis.In this step, the cold-trap cell temperature in addition to water pipe 103 is-40 DEG C, the cold-trap unit outside enrichment pipe 101
Temperature is-90 DEG C.
Step 2, gathers gaseous sample: open sampling pump 107, and sample, through entering sampling gas circuit except ozonizer 102, enters second
5 holes of six-way valve 112, are gone out by 4 holes of the second six-way valve 112, then by except entering through the 5th electromagnetic valve 104 after water pipe 103
4 holes of the first six-way valve 111, through the first six-way valve 111 5 holes out after enter enrichment pipe 101, C2-C12NMHCs, oxygen-containing have
Machine thing, halogenated hydrocarbons are attracted in enrichment pipe 101 internal adsorption agent, and other gas enters 2 holes of the first six-way valve 111, by first
3 holes of six-way valve 111 enter 1 hole of the second six-way valve 112 the most afterwards, then by 6 holes of the second six-way valve 112 out after through the 4th electricity
Magnet valve 105 enters the 4th mass flow controller 106, sampling pump 107 discharge.
Step 3, the sample gathering step 2 carries out Thermal desorption process: the 4th electromagnetic valve the 105, the 5th electromagnetic valve 104 closes
Close, the resistance heating wire's heating outside enrichment pipe 101, be heated to 150 DEG C with 15 DEG C/s of heating rate from-90 DEG C, in enrichment pipe 101
The volatile organic matter Thermal desorption concentrated enters chromatographic column 202 with carrier gas after becoming gaseous state, sees Fig. 5 b, controls the first six-way valve
111, the second six-way valve 112 is in position shown in Fig. 5 b, Nitrogen source gases 401 by after the first mass flow controller 501 by the
1 hole of one six-way valve 111 enters, 2 holes of the first six-way valve 111 be connected with enrichment pipe 101 after going out, and enters the 5 of the first six-way valve 111
Hole, and entered in chromatographic column 202 that (fractionated sample is through the 7th mass after being gone out by 6 holes of the first six-way valve 111 by injector 201
Effusion meter 504 is vented), after having separated, enter detector 203 and detect, then carried out determining to testing result by signal processing unit
Property, quantitative analysis.
Step 4, the resistance heating wire outside enrichment pipe 101 is heated to 200 DEG C after completing by step 3, except the electricity on water pipe 103
Resistance heater strip is heated to 100 DEG C, sees Fig. 5 c, adjusts first six-way valve the 111, second six-way valve 112 and be in position shown in Fig. 5 c,
The nitrogen that nitrogen air supply source 401 provides enters 2 holes of the second six-way valve 112 after crossing the second mass flow controller 502, by the two or six
1 hole of logical valve 112 enters 3 holes of the first six-way valve 111 the most afterwards, through the first six-way valve 111 2 holes out after with enrichment pipe
101 connections, reenter 5 holes of the first six-way valve 111 and are gone out by 4 holes of the first six-way valve 111, entering second after except water pipe 103
4 holes of six-way valve 112, finally by 3 hole emptying of the second six-way valve 112.By first six-way valve the 111, second six-way valve after end
112 are adjusted to position shown in Fig. 5 a, wait that new sampling channel is set up.
It should be noted that above-mentioned about each parts and the first six-way valve, the second six-way valve interface narration simply in order to
The present invention is described, it should be appreciated that, other multiple interfaces mode also can be had all should to belong to protection scope of the present invention.
In what the present embodiment provided air, volatile organic matter cryogenic gas-chromatography analytical equipment can automatic continuous analysis
C2-C12NMHCs, oxygen-bearing organic matter and halogenated hydrocarbons in air.In urban environment, big gas sample is gathered by the present embodiment device
Product carry out the most actually detected, after 30min on-line analysis, can be analyzed the data collected, and and standard sample
Product compare, so that it is determined that the classification of volatile organic matter and its concentration in an atmosphere.As shown in figures 6 a and 6b, show respectively
Show that scope volatile organic matter cryogenic gas-chromatography in the air of 0-17.5min and 17.5-31.0min analyzes NMHCs mark
Quasi-spectrogram.Wherein, in Fig. 6 a, 1-peak, peak 23 successively: ethylene, acetylene, ethane, propylene, propane, iso-butane, 1-butylene, fourth
Alkane, Trans-2-butene, cis-2-butene, isopentane, n-pentene, pentane, isoprene, trans-2-amylene, cis-2-amylene, 2,2-bis-
Methybutane, Pentamethylene., 2,3-dimethylbutanes, 2-methylpentane, 3-methylpentane, n-hexylene, hexane；In Fig. 6 b, peak 24-
Peak 57 is successively: methyl cyclopentane, 2,4-dimethyl pentanes, benzene, hexamethylene, 2-methyl hexane, 2,3-dimethyl pentanes, 3-first
Base hexane, pure isooctane, heptane, hexahydrotoluene, 2,3,4-trimethylpentanes, toluene, 2-methyl heptane, 3-first
Base heptane, octane, ethylbenzene, meta-xylene, p-xylene, styrene, ortho-xylene, nonane, cumene, n-proplbenzene,
Ethyltoluene, to ethyltoluene, 1，3，5-trimethyl-benzene, adjacent ethyltoluene, 1，2，4-trimethylbenzene, decane, 1,2,3-front three
Base benzene, a diethylbenzene, p-diethylbenzene, hendecane, dodecane.
Generally speaking, the invention have the advantages that 1. present invention use refrigeration machine to realize super low temperature refrigeration, it is to avoid make
By the drawback of the chiller refrigeration such as liquid nitrogen, can automatic operating for a long time, it is simple to remote districts automation mechanized operation；2. the present invention is led to
Cross the enrichment pipe being connected on the cold rod of refrigeration machine atmospheric volatile organic compounds to be adsorbed online, particularly to C2-in air
The absorption of the volatile organic matter of C12；3. the present invention uses single capillary chromatographic column can detect C2-C12NMHCs simultaneously, contain
The multiple volatile organic matter such as oxygen compound and halogenated hydrocarbons；Sampling analysis technology the most of the present invention has online and offline functionality, both
Can be at laboratory by off-line sampling analysis single sample, it is possible to be placed in on-the-spot realization and automatically monitor；5. the present invention is with similar
Commercial instrument is compared, it is not necessary to liquid nitrogen, time is stable, favorable reproducibility, compact, have relatively high time resolution, operating cost
Low, easy to operate, indoor and outdoor various field observation demand can be met.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, that is made any repaiies
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (4)
1. in an air, volatile organic matter cryogenic gas-chromatography analyzes method, it is characterised in that comprise the steps:
Step 1, set up acquisition channel；
Step 2, gather gaseous sample, the gaseous sample collected is carried out deodorization oxygen process, except water process, and to process after
Volatile organic matter in gaseous sample carries out enrichment process；
Step 3, to through enrichment process after volatile organic matter carry out separating treatment, to separate after volatile organic matter enter
Row detection, and be analyzed testing result processing；
The detailed process that volatile organic matter in gaseous sample after processing carries out in step 2 enrichment process is: after processing
Gaseous sample by being filled with the enrichment pipe of ketjenblack EC adsorbent, by enrichment pipe refrigeration to-90 DEG C；
Reached-90 DEG C of described enrichment pipe are jointly to be acted on by the cold-trap unit of the cold rod of refrigeration machine and enrichment pipe reaching；
The cold rod of described refrigeration machine is connected with enrichment pipe, chromatographic column, cold-trap unit except water pipe simultaneously；
Step 3 carries out separating treatment process to the volatile organic matter after enrichment processes as follows:
Enrichment pipe is heated to uniform temperature so that the volatile organic matter Thermal desorption after enrichment processes becomes gaseous state, then
Gaseous volatile Organic substance after Thermal desorption is separated by chromatographic column with carrier gas；
Described gaseous volatile Organic substance after Thermal desorption carried out separation with carrier gas by chromatographic column include:
Use single capillary chromatographic column that the gaseous volatile Organic substance after Thermal desorption is separated；
The initial temperature of described single capillary chromatographic column, is jointly to be acted on by the cold-trap unit of the cold rod of refrigeration machine and chromatographic column
Reach-60 DEG C.
2. volatile organic matter cryogenic gas-chromatography analytical equipment in an air, it is characterised in that include sampling apparatus, separation
With detection device, temperature control equipment and signal processing apparatus；
The outfan of described sampling apparatus is connected with the described input separated and detect device；
Described separation is connected with the input of described signal processing apparatus with the outfan of detection device；
Described temperature control equipment respectively with described sampling apparatus, separate and detect device and be connected；
Described sampling apparatus include being sequentially connected with except ozonizer, except water pipe, enrichment pipe；
Described separation includes injector, chromatographic column and detector, the entrance of described injector and described enrichment with detection device
The outlet of pipe connects, and the outlet of described injector is connected with the entrance of described chromatographic column, the outlet of described chromatographic column and described inspection
The entrance surveying device connects；
Described temperature control equipment includes refrigeration machine, described enrichment pipe, is also equipped with cold-trap unit in addition to water pipe, chromatographic column, respectively
Cold-trap unit is connected with refrigeration machine, is equipped with resistance heating wire in each cold-trap unit；
Described signal processing apparatus includes the outfan of chromatographic work station, the input of described chromatographic work station and described detector
Connect；
Also include that the first six-way valve and the second six-way valve, the described outfan except ozonizer connect with 5 holes of described second six-way valve
Connect, described be connected with 4 holes of described second six-way valve except the input of water pipe, the described outfan except water pipe and the described 1st
4 holes of logical valve connect, and the input of described enrichment pipe is connected with 5 holes of described first six-way valve, the outfan of described enrichment pipe
Being connected with 2 holes of described first six-way valve, the input of described injector is connected with 6 holes of described first six-way valve.
Volatile organic matter cryogenic gas-chromatography analytical equipment in air the most according to claim 2, it is characterised in that also
Including feeder；
Described feeder includes Nitrogen source gases and provides fuel gas and the gas occurring source of combustion-supporting gas for described detector；
Described Nitrogen source gases controls with the first mass flow controller, the second mass flow controller, the 3rd mass flow respectively
The input of device connects, and described gas occurring source is connected with the input of described detector；
The outfan of described first mass flow controller and 1 hole of the first six-way valve connect, and described second mass flow controls
The outfan of device is connected with 2 holes of described second six-way valve, the outfan of described 3rd mass flow controller and described detection
The input of device connects.
4., according to volatile organic matter cryogenic gas-chromatography analytical equipment in the air described in any one of Claims 2 or 3, it is special
Levying and be, described detector uses flame ionization ditector, and described chromatographic column uses capillary chromatographic column, described enrichment pipe
Use internal diameter 2-4mm, the stainless steel tube of long 10-20cm, in enrichment pipe, be filled with ketjenblack EC adsorbent；Described except water pipe and
Except ozonizer uses internal diameter 3-6mm, the empty glass tubing of long 10-20cm or empty Peek pipe or empty PTFE tube；Described except in ozonizer
It is added with Na2SO3。
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| CN105043846A (en) * | 2015-09-01 | 2015-11-11 | 武汉市天虹仪表有限责任公司 | Volatile organic compound sample gas trapping system and method |
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| CN105353056B (en) * | 2015-12-11 | 2018-01-30 | 华电智控（北京）技术有限公司 | Volatile organic matter on-line monitoring system |
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| CN113804810A (en) * | 2020-06-15 | 2021-12-17 | 浙江科技学院 | Chromatographic separation column and method for detecting VOCs gas chromatography |
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| US5321984A (en) * | 1992-11-12 | 1994-06-21 | Graseby Holdings Corporation | Automatic sample control cart |
| CN102043022B (en) * | 2009-10-21 | 2013-07-24 | 中国石油化工股份有限公司 | System for analyzing reducing sulfide in atmosphere |
| CN202256359U (en) * | 2011-09-16 | 2012-05-30 | 武汉市天虹仪表有限责任公司 | On-line volatile organic compound analyzer |
| CN102375041B (en) * | 2011-09-16 | 2015-03-04 | 武汉市天虹仪表有限责任公司 | Online volatile organic matter analyzer and using method thereof |
| CN204495779U (en) * | 2015-04-10 | 2015-07-22 | 中国科学院生态环境研究中心 | Volatile organic matter cryogenic gas-chromatography analytical equipment in air |
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