CN104777261A - Low temperature gas chromatography system, low temperature gas chromatography method and low temperature gas chromatography device of volatile organic compound in atmosphere - Google Patents
Low temperature gas chromatography system, low temperature gas chromatography method and low temperature gas chromatography device of volatile organic compound in atmosphere Download PDFInfo
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Abstract
The invention discloses a low temperature gas chromatography system, a low temperature gas chromatography method and a low temperature gas chromatography device of a volatile organic compound in atmosphere. The method comprises the steps of collecting a gas sample, and carrying out ozone removal treatment, water removal treatment and enrichment treatment on the collected sample; after the enrichment treatment, separating the sample, and detecting; analyzing the treatment detection result. The low temperature gas chromatography device of the volatile organic compound in the atmosphere adopts a temperature control unit to realize the water removal treatment and the enrichment treatment of the atmospheric sample as well as the low-temperature efficient separation of a single capillary column for low hydrocarbon at the same time. The system, the method and the device are simple and reliable, and can meet various demands for indoor and outdoor atmospheric observation.
Description
Technical field
The present invention relates to stratographic analysis field, volatile organic matter cryogenic gas-chromatography analytic system, method and device in a kind of air.
Background technology
In air, volatile organic matter (VOC) is mainly derived from the use of nature discharge and fossil man's fuel (coal, oil and natural gas).This compounds comprises the organism in a large number with high reaction activity, organic peroxy base can be produced with active specy in air (as OH free radical and ozone etc.) rapid reaction, and organic peroxy base be rich in the air of NOx in city participate in further reaction, produce the ozone mankind and the ecosystem to obvious negative effect.In addition, amount of activated volatile organic matter forms secondary organic aerosol through complex processes such as photooxidation in an atmosphere, can change radiation balance and then affect Global climate change.Because volatile organic matter in air has vital role in the generation of atmospheric ozone and secondary organic aerosol, and there is harm to health in part VOC, the research of atmospheric volatile organic compounds becomes one of hot fields of recent domestic Atmospheric Chemistry research.
Monitoring technology and the method for volatile organic matter in many measure air are developed at present in the world, but existing VOC analytical technology and method mostly have equipment complexity, expensive, operate the low shortcoming of resolution lengthy and tedious and analysis time, have larger gap with the actual demand of atmospheric seeing.Therefore, research upgrades, more simply, more fast, apply the wider VOC sampling analysis method of species and analytical technology, has great importance in atmospheric environment field.
Summary of the invention
The object of the present invention is to provide a kind of simple, reliable, can the volatile organic matter cryogenic gas-chromatography analytic system of continued operation for a long time, method and device.
For achieving the above object, embodiments providing volatile organic matter cryogenic gas-chromatography analytic system in a kind of air, comprising: sampling unit, separation and detecting unit and Signal acquiring and processing unit;
Described sampling unit for gathering gaseous sample, and carries out deozonize process to the gaseous sample collected, except water treatment, and carry out enrichment process to the volatile organic matter in the gaseous sample after process;
Described separation is connected with the output terminal of described sampling unit with the input end of detecting unit, and described separation and detecting unit are used for being separated the volatile organic matter after enrichment process, and detects the volatile organic matter after being separated;
The input end of described signal processing unit is connected with the output terminal of detecting unit with described separation, and described signal processing unit is used for carrying out analyzing and processing to the testing result of described separation and detecting unit.
Preferably, also temperature control unit is comprised;
Described temperature control unit respectively with described sampling unit, be separated and be connected with detecting unit, for described sampling unit, to be separated and detecting unit provides temperature needed for work
The embodiment of the present invention additionally provides volatile organic matter cryogenic gas-chromatography analytical approach in a kind of air, comprises the steps:
Step 1, set up acquisition channel, complete the preliminary work before collection;
Step 2, gather gaseous sample, deozonize process is carried out to the gaseous sample collected, except water treatment, and enrichment process is carried out to the volatile organic matter in the gaseous sample after process;
Step 3, separating treatment is carried out to the volatile organic matter after enrichment process, the volatile organic matter after being separated is detected, and analyzing and processing is carried out to testing result.
Preferably, in step 2 to the detailed process that the volatile organic matter after process in gaseous sample carries out enrichment process be: by the gaseous sample after process by being filled with the enrichment pipe of ketjenblack EC adsorbent, by enrichment pipe refrigeration to less than-90 DEG C.
Preferably, in step 3, separating treatment process carried out to the volatile organic matter after enrichment process as follows:
Enrichment pipe is heated to uniform temperature, makes the volatile organic matter Thermal desorption after enrichment process become gaseous state, then the gaseous volatile organism 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, comprise sampling apparatus, be separated and pick-up unit, temperature control equipment and signal processing apparatus;
The output terminal of described sampling apparatus is connected with the input end of pick-up unit with described separation;
Described separation is connected with the input end of described signal processing apparatus with the output terminal of pick-up unit;
Described temperature control equipment respectively with described sampling apparatus, be separated and be connected with pick-up unit, for described sampling apparatus provides work temperature required with being separated with pick-up unit.
Preferably, described sampling apparatus comprise connect successively deozonize pipe, except water pipe, enrichment pipe;
Described separation and pick-up unit comprise injector, chromatographic column and detecting device, the entrance of described injector is connected with the outlet of described enrichment pipe, and the outlet of described injector is connected with the entrance of described chromatographic column, and the outlet of described chromatographic column is connected with the entrance of described detecting device;
Described temperature control equipment comprises refrigeration machine, described enrichment pipe, except water pipe, chromatographic column, is also equipped with cold-trap unit, and 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 comprises chromatographic work station, and the input end of described chromatographic work station is connected with the output terminal of described detecting device.
Preferably, also comprise the first six-way valve and the second six-way valve, the output terminal of described deozonize pipe is connected with 5 holes of described second six-way valve, the described input end except water pipe is connected with 4 holes of described second six-way valve, the described output terminal except water pipe is connected with 4 holes of described first six-way valve, the input end of described enrichment pipe is connected with 5 holes of described first six-way valve, the output terminal of described enrichment pipe is connected with 2 holes of described first six-way valve, and the input end of described injector is connected with 6 holes of described first six-way valve.
Preferably, also feeder is comprised;
Described feeder comprises Nitrogen source gases and provides the gas occurring source of inflammable gas and combustion-supporting gas for described detecting device;
Described Nitrogen source gases is connected with the input end of the first mass flow controller, the second mass flow controller, the 3rd mass flow controller respectively, and described gas occurring source is connected with the input end of described detecting device;
The output terminal of described first mass flow controller is connected with 1 hole of the first six-way valve, the output terminal of described second mass flow controller is connected with 2 holes of described second six-way valve, and the output terminal of described 3rd mass flow controller is connected with the input end of described detecting device.
Preferably, described temperature control equipment also comprises PID controller, and PID controller is connected with the resistance heating wire be wrapped in outside enrichment pipe and except water pipe and in chromatographic column.
Preferably, described detecting device adopts flame ionization ditector, and described chromatographic column adopts capillary chromatographic column, and described enrichment pipe adopts the stainless-steel tube of internal diameter 2-4mm, long 10-20cm, fills ketjenblack EC adsorbent in enrichment pipe; Describedly the empty glass tube of internal diameter 3-6mm, long 10-20cm or empty Peek is adopted to manage or empty PTFE tube except water pipe and deozonize pipe; Na is added with in described deozonize pipe
2sO
3.
Volatile organic matter cryogenic gas-chromatography analytic system, method and device that the embodiment of the present invention provides, by setting up acquisition channel, deozonize process is carried out to the gaseous sample collected, except water treatment, and to process after gaseous sample in volatile organic matter carry out enrichment process; Sample after enrichment process is separated, detects and further on-line analysis is carried out to testing result, simple, reliable and can continued operation for a long time, the various field observation demand of indoor and outdoor can be met.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme of the embodiment of the present invention, be briefly described to the accompanying drawing used required in embodiment below, be to be understood that, the following drawings illustrate only some embodiment of the present invention, therefore the restriction to scope should be counted as, for those of ordinary skill in the art, under the prerequisite not paying creative work, other relevant accompanying drawings can also be obtained according to these accompanying drawings.
Volatile organic matter cryogenic gas-chromatography analytic system structural representation in the air that Fig. 1 provides for one embodiment of the invention;
Fig. 2 a is volatile organic matter cryogenic gas-chromatography analytical approach process flow diagram in the air that provides of the embodiment of the present invention;
The implementing process schematic diagram of volatile organic matter cryogenic gas-chromatography analytical approach in the air that Fig. 2 b provides for the embodiment of the present invention;
Volatile organic matter cryogenic gas-chromatography analytical equipment structural representation in the air that Fig. 3 provides for one embodiment of the invention;
Volatile organic matter cryogenic gas-chromatography analytical equipment structural representation in the air that Fig. 4 provides for another embodiment of the present invention;
Volatile organic matter cryogenic gas-chromatography analytical equipment first working state structure schematic diagram in the air that Fig. 5 a provides for another embodiment of the present invention;
Volatile organic matter cryogenic gas-chromatography analytical equipment second working state structure schematic diagram in the air that Fig. 5 b provides for another embodiment of the present invention;
Volatile organic matter cryogenic gas-chromatography analytical equipment the 3rd working state structure schematic diagram in the air that Fig. 5 c provides for another embodiment of the present invention;
Fig. 6 a analyzes NMHCs standard spectrogram (0-17.5min) for volatile organic matter cryogenic gas-chromatography in the air that provides in the embodiment of the present invention;
Fig. 6 b analyzes NMHCs standard spectrogram (17.5-31.0min) for volatile organic matter cryogenic gas-chromatography in another air of providing in the embodiment of the present invention.
The concrete meaning of number in the figure is: 11, collecting unit, 12, be separated and detecting unit, 13, signal processing unit, 14, temperature control unit, 101, enrichment pipe, 102, deozonize pipe, 103, except water pipe, 104, 5th solenoid valve, 105, 4th solenoid valve, 106, 4th mass flow controller, 107, sampling pump, 111, first six-way valve, 112, second six-way valve, 201, injector, 202, chromatographic column, 203, detecting device, 301, refrigeration machine, 401, Nitrogen source gases, 402, hydrogen generator, 403, compressed air generator, 404, gas occurring source, 501, first mass flow controller, 502, second mass flow controller, 503, 3rd mass flow controller, 504, 7th mass flow controller, 505, 5th mass flow controller, 506, 6th mass flow controller, 601, first solenoid valve, 602, second solenoid valve, 603, 3rd solenoid valve.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.
The present invention program is understood better in order to make those skilled in the art person, below in conjunction with accompanying drawing in the embodiment of the present invention, technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.The assembly of the embodiment of the present invention describing and illustrate in usual accompanying drawing herein can be arranged with various different configuration and design.Therefore, below to the detailed description of the embodiments of the invention provided in the accompanying drawings and the claimed scope of the present invention of not intended to be limiting, but selected embodiment of the present invention is only represented.Based on embodiments of the invention, the every other embodiment that those skilled in the art obtain under the prerequisite not making creative work, all belongs to the scope of protection of the invention.Also by reference to the accompanying drawings the present invention is described in further detail below by specific embodiment.
In air, volatile organic matter refers to the volatile organic matters such as C2-C12 non-methane hydro carbons (NMHCs), oxygenatedchemicals and halogenated hydrocarbons mostly, and the object of stratographic analysis of the present invention is exactly these volatile organic matters.
Fig. 1 is the volatile organic matter cryogenic gas-chromatography analytic system structural representation that the embodiment of the present invention provides, and system comprises: sampling unit 11, separation and detecting unit 12 and signal processing unit 13.
Sampling unit 11 for gathering gaseous sample, and carries out deozonize process to the gaseous sample collected, except water treatment, and the volatile organic matter in the gaseous sample after process is carried out enrichment process; Be separated with detecting unit 12 for carrying out separating treatment to the volatile organic matter after enrichment process, and the volatile organic matter after being separated is detected; Signal processing unit 13 for receiving the testing result of described separation and detecting unit, and carries out analyzing and processing to testing result.
Because volatile organic content in general atmosphere is very low, in order to meet the testing requirement of detecting device, atmospheric sample needs to carry out enrichment process, for the present invention, can adopt but be not limited to ketjenblack EC as adsorbent, the adsorption effect of ketjenblack EC is best when temperature is less than-90 DEG C, and can realize C2-C12 volatile organic matter 100% catches.But because atmosphere moisture content is usually very large, atmospheric sample easily causes the blocking of enrichment pipe in low temperature enrichment process; Oxygenant in air is (as O
3deng) can react with unsaturated hydrocarbon in enrichment and Thermal desorption process and cause the loss of VOC.Therefore, in order to avoid atmosphere moisture and oxygenant are to the interference of target compound VOC or loss, atmospheric sample needs wherein moisture and oxygenant are removed in gatherer process.In the embodiment of the present invention, first the atmospheric sample (gaseous sample) of collection fills reducing substances Na through one
2sO
3glass tube atmospheric oxidant is removed, secondly, dewater through a cryogenic piping, finally, the VOC in atmospheric sample has the low temperature enrichment pipe of ketjenblack EC adsorbent to complete atmospheric sample gatherer process through adding.The VOC that enrichment pipe gathers is through quickly heating up to about 150 DEG C, the volatilization of VOC can be realized, the VOC of volatilization enters chromatography column successively under the driving of carrier gas and detecting device carries out separation and detection, the response signal of detecting device carries out record by chromatographic work station, and then carries out qualitative and quantitative analysis according to the retention time of VOC calibrating gas and signal intensity.
The volatile organic matter cryogenic gas-chromatography analytic system that the embodiment of the present invention provides, also comprise temperature control unit 14, temperature control unit 14 for meeting described sampling unit 11, to be separated and detecting unit 12 works required temperature conditions, as the chilling temperature except water treatment, adsorption temp during enrichment process, temperature needed during Thermal desorption etc., all realizes by temperature conditioning unit.
In the present embodiment, temperature control unit 14 can adopt but be not limited to refrigeration machine and well heater, is used to provide relevant temperature, and wherein, refrigeration machine and well heater realize the accurate control of temperature by PID controller.
Fig. 2 a is volatile organic matter cryogenic gas-chromatography analytical approach process flow diagram in the air that provides of the embodiment of the present invention, and Fig. 2 b is the schematic diagram of its implementing process.Composition graphs 2a and Fig. 2 b is described, and the method comprises the steps, comprises the steps:
Step S11, set up acquisition channel, complete the preliminary work before collection.Preliminary work in this step includes but not limited to provide the carrier gas of temperature and the flow speed stability meeting gas collecting condition, ensures the leakproofness of passage, the accuracy of measuring flow.
Step S12, gather gaseous sample, deozonize process is carried out to the gaseous sample collected, except water treatment, and enrichment process is carried out to the volatile organic matter in the gaseous sample after process.The detailed process of the volatile organic matter in the gaseous sample after process being carried out to enrichment process is: by the gaseous sample after process by being filled with the enrichment pipe of ketjenblack EC adsorbent, by enrichment pipe refrigeration to less than-90 DEG C, such volatile organic matter will be adsorbed in enrichment pipe.
Step S13, separating treatment is carried out to the volatile organic matter after enrichment process, then the volatile organic matter after being separated is detected, and analyzing and processing is carried out to testing result.Wherein, separating treatment process carried out to the sample after enrichment process as follows: enrichment pipe is heated to uniform temperature, the sample Thermal desorption after enrichment process is made to become gaseous state, then the sample after Thermal desorption is separated by chromatographic column with carrier gas, detected by detecting device after separation, carrying out analyzing and processing to testing result can be completed by softwares such as chromatographic work stations.
See Fig. 3, the embodiment of the present invention additionally provides volatile organic matter cryogenic gas-chromatography analytical equipment in a kind of air, comprises sampling apparatus, is separated and pick-up unit, temperature control equipment and Signal acquiring and processing device;
Sampling apparatus comprise connect successively deozonize pipe 102, except water pipe 103, enrichment pipe 101, sampling pump 107;
Be separated and comprise injector 201 with pick-up unit, chromatographic column 202 and detecting device 203, the entrance of injector 201 is connected with the outlet of described enrichment pipe 101, and the outlet of injector 201 is connected with the entrance of chromatographic column 202, and the outlet of chromatographic column 202 is connected with the entrance of detecting device 203;
Temperature control equipment comprises refrigeration machine, enrichment pipe 101, cold-trap unit set except water pipe 103, chromatographic column 202, and 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, and the input end of chromatographic work station is connected with the output terminal of detecting device.
Its course of work is as follows: atmospheric sample successively through deozonize pipe 102, except water pipe 103, enrichment pipe 101, now target compound (in air volatile organic matter) is concentrated in enrichment pipe 101, remaining gas is discharged by sampling pump 107, complete the collecting work of target compound, target compound becomes gaseous state again by Thermal desorption, then by gaseous target compound along with carrier gas (N
2) enter injector 201, input chromatographic column 202 by injector 201 to be separated, detect finally by detecting device 203, in the present embodiment, detecting device 203 can adopt but be not limited to flame ionization ditector, chromatographic column 202 adopts capillary chromatographic column, enrichment pipe adopts the stainless-steel tube of internal diameter 2-4mm, long 10-20cm, fills ketjenblack EC adsorbent in enrichment pipe; Except water pipe and deozonize pipe adopt the empty glass tube of internal diameter 3-6mm, long 10-20cm or empty Peek to manage or empty PTFE tube; Na is added with in deozonize pipe
2sO
3.
See Fig. 4, Figure 4 shows that volatile organic matter cryogenic gas-chromatography analytical equipment structural representation in the air that another embodiment of the present invention provides, the present embodiment has set up feeder on the basis of a upper embodiment, and feeder comprises Nitrogen source gases 401 and provides the gas occurring source 404 of inflammable gas and combustion-supporting gas for detecting device 203;
Nitrogen source gases 401 is connected with the input end of the first mass flow controller 501, second mass flow controller 502, the 3rd mass flow controller 503 respectively, and gas occurring source 404 is connected with the input end of detecting device 203;
The output terminal of the first mass flow controller 501 is connected with the output terminal of enrichment pipe 101 by the first solenoid valve 601, the output terminal of the second mass flow controller 502 is connected with the output terminal of enrichment pipe 101 by the second solenoid valve 602, and the output terminal of the 3rd mass flow controller 503 is connected with the input end of detecting device 203 by the 3rd solenoid valve 603.
In the present embodiment, the first mass flow controller 501 is used to provide carrier gas.When after the enrichment process that enrichment pipe 101 completes target compound, now target compound is enrichment stage, and be adsorbed in enrichment pipe 101, need to heat target compound, it is made to resolve to gas, now open the first solenoid valve 601, control carrier gas speed by the first mass flow controller 501, make the target compound again resolving to gaseous state along with carrier gas inflow chromatographic column 202.Second mass flow controller 502 is used for blowback, and blowback is in order to heavy constituent in enrichment pipe with except ice crystal emptying in water pipe, and object avoids heavy constituent and water vapor to enter chromatographic column, and one accelerates analysis time, and two extend chromatographic column serviceable life.After the component needed in testing process enters chromatographic column 202 completely, open the second solenoid valve 602, nitrogen flow rate is controlled by the second mass flow controller 502, the flow of nitrogen gas making enrichment pipe 101 and remove in water pipe 103 is controlled by nitrogen flow rate, to gasify at relatively high temperatures and blowback is gone out the heavy constituent in enrichment pipe with except the ice crystal in water pipe, fast cooling prepares enrichment next time.3rd mass flow controller 503 is mainly used in tail and blows, and opens the 3rd solenoid valve 603, increases flow rate of carrier gas further by the 3rd mass flow controller 503, fast sample is blown into detecting device 203 to reach, and avoids peak stretching after post, puies forward highly sensitive object.
See Fig. 5 a, present embodiments provide volatile organic matter cryogenic gas-chromatography analytical equipment first working state structure schematic diagram in another kind of air, the present embodiment and above-described embodiment difference are mainly, the present embodiment realizes the switching of gas circuit by two six-way valves, convenient and reliable, concrete structure is as follows:
The output terminal of deozonize pipe 102 is connected with 5 holes of the second six-way valve 112, except the input end of water pipe 103 is connected with 4 holes of the second six-way valve 112, except the output terminal of water pipe 103 is connected with 4 holes of the first six-way valve 111 by the 5th solenoid valve 104, the input end of enrichment pipe 101 is connected with 5 holes of the first six-way valve 111, the output terminal of enrichment pipe 101 is connected with 2 holes of the first six-way valve 111, the input end of injector 201 is connected with 6 holes of the first six-way valve 111, the output terminal of the first mass flow controller 501 is connected with 1 hole of the first six-way valve 111 by the first solenoid valve 601, the output terminal of the second mass flow controller 502 is connected with 2 holes of the second six-way valve 112 by the second solenoid valve 602, the output terminal of the 3rd mass flow controller 503 is connected with the input end of detecting device 203 by the 3rd solenoid valve 603, in the present embodiment, detecting device 203 adopts 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, 6th mass flow controller 506 is connected with detecting device 203, other structure is same as the previously described embodiments, repeat no more.
The work process of the present embodiment is as follows: step 1, and acquisition channel is set up, and the first six-way valve 111, second six-way valve 112 is pressed the playback of position shown in Fig. 5 a, the 5th solenoid valve 104, the 4th solenoid valve 105 are opened, and complete the data collection and analysis of gas collecting Conditions Temperature.In this step, the cold-trap cell temperature except water pipe 103 is-40 DEG C, and the cold-trap cell temperature outside enrichment pipe 101 is-90 DEG C.
Step 2, gather gaseous sample: open sampling pump 107, sample enters sampling gas circuit through deozonize pipe 102, enter 5 holes of the second six-way valve 112, gone out by 4 holes of the second six-way valve 112, then by entering 4 holes of the first six-way valve 111 after water pipe 103 through the 5th solenoid valve 104, through 5 holes of the first six-way valve 111 out after enter enrichment pipe 101, C2-C12NMHCs, oxygen-bearing organic matter, halogenated hydrocarbons to be attracted in enrichment pipe 101 on adsorbent, other gas enters 2 holes of the first six-way valve 111, 1 hole of the second six-way valve 112 is out entered afterwards by 3 holes of the first six-way valve 111, again by the second six-way valve 112 6 holes out after enter the 4th mass flow controller 106 through the 4th solenoid valve 105, discharged by sampling pump 107.
Step 3, Thermal desorption process is carried out to the sample that step 2 gathers: the 4th solenoid valve 105, 5th solenoid valve 104 cuts out, resistance heating wire's heating outside enrichment pipe 101, 150 DEG C are heated to from-90 DEG C with heating rate 15 DEG C/s, chromatographic column 202 is entered with carrier gas after volatile organic matter Thermal desorption concentrated in enrichment pipe 101 becomes gaseous state, see Fig. 5 b, control the first six-way valve 111, second six-way valve 112 is in position shown in Fig. 5 b, Nitrogen source gases 401 is by being entered by 1 hole of the first six-way valve 111 after the first mass flow controller 501, be connected with enrichment pipe 101 after being gone out by 2 holes of the first six-way valve 111, enter 5 holes of the first six-way valve 111, and enter (fractionated sample is through the 7th mass flowmeter 504 emptying) in chromatographic column 202 by injector 201 after being gone out by 6 holes of the first six-way valve 111, after separation completes, enter detecting device 203 to detect, carry out qualitative by signal processing unit to testing result again, quantitative test.
Step 4, after step 3 completes, the resistance heating wire outside enrichment pipe 101 is heated to 200 DEG C, except the resistance heating wire on water pipe 103 is heated to 100 DEG C, see Fig. 5 c, adjust the first six-way valve 111, second six-way valve 112 is 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, 3 holes of the first six-way valve 111 are out entered afterwards by 1 hole of the second six-way valve 112, through 2 holes of the first six-way valve 111 out after be communicated with enrichment pipe 101, reenter 5 holes of the first six-way valve 111 and gone out by 4 holes of the first six-way valve 111, through entering 4 holes of the second six-way valve 112 after water pipe 103, finally by 3 hole emptying of the second six-way valve 112.After end, the first six-way valve 111, second six-way valve 112 is adjusted to position shown in Fig. 5 a, waits for that new sampling channel is set up.
It should be noted that, the above-mentioned interface about each parts and the first six-way valve, the second six-way valve describes just in order to describe the present invention, and Ying Zhi, also can have other multiple interfaces mode should belong to protection scope of the present invention.
The present embodiment provide air in volatile organic matter cryogenic gas-chromatography analytical equipment can C2-C12NMHCs, oxygen-bearing organic matter and halogenated hydrocarbons in automatic continuous analysis air.In urban environment, gather atmospheric sample by the present embodiment device and carry out online actual detection, after 30min on-line analysis, can to the data analysis collected, and compare with standard model, thus determine the classification of volatile organic matter and its concentration in an atmosphere.As shown in figures 6 a and 6b, the scope that respectively illustrates volatile organic matter cryogenic gas-chromatography in the air of 0-17.5min and 17.5-31.0min analyzes NMHCs standard spectrogram.Wherein, in Fig. 6 a, 1-peak, peak 23 successively: ethene, acetylene, ethane, propylene, propane, isobutane, 1-butylene, butane, Trans-2-butene, cis-2-butene, isopentane, positive amylene, pentane, isoprene, trans-2-amylene, cis-2-amylene, 2,2-dimethylbutane, cyclopentane, 2,3-dimethylbutane, 2-methylpentane, 3-methylpentane, n-hexylene, hexane, in Fig. 6 b, 24-peak, peak 57 is successively: methyl cyclopentane, 2, 4-dimethyl pentane, benzene, cyclohexane, 2-methyl hexane, 2, 3-dimethyl pentane, 3-methyl hexane, 2, 2, 4-trimethylpentane, heptane, methylcyclohexane, 2, 3, 4-trimethylpentane, toluene, 2-methylheptane, 3-methylheptane, octane, ethylbenzene, m-dimethylbenzene, p-dimethylbenzene, styrene, ortho-xylene, nonane, cumene, n-proplbenzene, between ethyltoluene, to ethyltoluene, 1, 3, 5-trimethylbenzene, adjacent ethyltoluene, 1, 2, 4-trimethylbenzene, decane, 1, 2, 3-trimethylbenzene, between diethylbenzene, p-diethylbenzene, undecane, dodecane.
Generally speaking, the present invention has the following advantages: 1. the present invention adopts refrigeration machine to realize super low temperature refrigeration, avoids the drawback using the chiller refrigeration such as liquid nitrogen, can automatic operating for a long time, is convenient to automation mechanized operation from far-off regions; 2. the present invention is adsorbed atmospheric volatile organic compounds by the enrichment pipe be connected on the cold rod of refrigeration machine, online particularly to the absorption of the volatile organic matter of C2-C12 in air; 3. the present invention adopts single capillary chromatographic column can detect the multiple volatile organic matters such as C2-C12NMHCs, oxygenatedchemicals and halogenated hydrocarbons simultaneously; 4. sampling analysis technology of the present invention has online and offline functionality, both can pass through off-line sampling analysis single sample in laboratory, also can be placed in on-the-spot realization and automatically monitors; 5. the present invention is compared with similar commercial instrument, favorable reproducibility, compact stable without the need to liquid nitrogen, time, has low, easy to operate compared with high time resolution, operating cost, can meet the various field observation demand of indoor and outdoor.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a volatile organic matter cryogenic gas-chromatography analytic system in air, is characterized in that, comprising: sampling unit, separation and detecting unit and signal processing unit;
Described sampling unit for gathering gaseous sample, and carries out deozonize process to the gaseous sample collected, except water treatment, and carry out enrichment process to the volatile organic matter in the gaseous sample after process;
Described separation is connected with the output terminal of described sampling unit with the input end of detecting unit, and described separation and detecting unit are used for being separated the volatile organic matter after enrichment process, and detects the volatile organic matter after being separated;
The input end of described signal processing unit is connected with the output terminal of detecting unit with described separation, and described signal processing unit is used for carrying out analyzing and processing to the testing result of described separation and detecting unit.
2. volatile organic matter cryogenic gas-chromatography analytic system in air according to claim 1, is characterized in that, also comprise temperature control unit;
Described temperature control unit respectively with described sampling unit, be separated and be connected with detecting unit, for described sampling unit, to be separated and detecting unit provides temperature needed for work.
3. a volatile organic matter cryogenic gas-chromatography analytical approach in air, is characterized in that, comprise the steps:
Step 1, set up acquisition channel;
Step 2, gather gaseous sample, deozonize process is carried out to the gaseous sample collected, except water treatment, and enrichment process is carried out to the volatile organic matter in the gaseous sample after process;
Step 3, separating treatment is carried out to the volatile organic matter after enrichment process, the volatile organic matter after being separated is detected, and analyzing and processing is carried out to testing result.
4. volatile organic matter cryogenic gas-chromatography analytical approach in air according to claim 3, it is characterized in that, in step 2 to the detailed process that the volatile organic matter after process in gaseous sample carries out enrichment process be: by the gaseous sample after process by being filled with the enrichment pipe of ketjenblack EC adsorbent, by enrichment pipe refrigeration to less than-90 DEG C.
5. in the air according to claim 3 or 4, volatile organic matter cryogenic gas-chromatography analytical approach, is characterized in that, carries out separating treatment process as follows in step 3 to the volatile organic matter after enrichment process:
Enrichment pipe is heated to uniform temperature, makes the volatile organic matter Thermal desorption after enrichment process become gaseous state, then the gaseous volatile organism after Thermal desorption is separated by chromatographic column with carrier gas.
6. a volatile organic matter cryogenic gas-chromatography analytical equipment in air, is characterized in that, comprises sampling apparatus, is separated and pick-up unit, temperature control equipment and signal processing apparatus;
The output terminal of described sampling apparatus is connected with the input end of pick-up unit with described separation;
Described separation is connected with the input end of described signal processing apparatus with the output terminal of pick-up unit;
Described temperature control equipment respectively with described sampling apparatus, be separated and be connected with pick-up unit.
7. volatile organic matter cryogenic gas-chromatography analytical equipment in air according to claim 6, is characterized in that, described sampling apparatus comprise connect successively deozonize pipe, except water pipe, enrichment pipe;
Described separation and pick-up unit comprise injector, chromatographic column and detecting device, the entrance of described injector is connected with the outlet of described enrichment pipe, and the outlet of described injector is connected with the entrance of described chromatographic column, and the outlet of described chromatographic column is connected with the entrance of described detecting device;
Described temperature control equipment comprises refrigeration machine, described enrichment pipe, except water pipe, chromatographic column, is also equipped with cold-trap unit, and each cold-trap unit is connected with refrigeration machine, is equipped with resistance heating wire in each cold-trap unit;
Described signal processing apparatus comprises chromatographic work station, and the input end of described chromatographic work station is connected with the output terminal of described detecting device.
8. volatile organic matter cryogenic gas-chromatography analytical equipment in air according to claim 7, it is characterized in that, also comprise the first six-way valve and the second six-way valve, the output terminal of described deozonize pipe is connected with 5 holes of described second six-way valve, the described input end except water pipe is connected with 4 holes of described second six-way valve, the described output terminal except water pipe is connected with 4 holes of described first six-way valve, the input end of described enrichment pipe is connected with 5 holes of described first six-way valve, the output terminal of described enrichment pipe is connected with 2 holes of described first six-way valve, the input end of described injector is connected with 6 holes of described first six-way valve.
9. volatile organic matter cryogenic gas-chromatography analytical equipment in air according to claim 8, is characterized in that, also comprise feeder;
Described feeder comprises Nitrogen source gases and provides the gas occurring source of inflammable gas and combustion-supporting gas for described detecting device;
Described Nitrogen source gases is connected with the input end of the first mass flow controller, the second mass flow controller, the 3rd mass flow controller respectively, and described gas occurring source is connected with the input end of described detecting device;
The output terminal of described first mass flow controller is connected with 1 hole of the first six-way valve, the output terminal of described second mass flow controller is connected with 2 holes of described second six-way valve, and the output terminal of described 3rd mass flow controller is connected with the input end of described detecting device.
10. volatile organic matter cryogenic gas-chromatography analytical equipment in the air according to any one of claim 7 to 9, it is characterized in that, described detecting device adopts flame ionization ditector, described chromatographic column adopts capillary chromatographic column, described enrichment pipe adopts the stainless-steel tube of internal diameter 2-4mm, long 10-20cm, is filled with ketjenblack EC adsorbent in enrichment pipe; Describedly the empty glass tube of internal diameter 3-6mm, long 10-20cm or empty Peek is adopted to manage or empty PTFE tube except water pipe and deozonize pipe; Na is added with in described deozonize pipe
2sO
3.
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