CN102297878B - Electronic nose system for rapid detection of pollution of volatile chlorinated hydrocarbons - Google Patents
Electronic nose system for rapid detection of pollution of volatile chlorinated hydrocarbons Download PDFInfo
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- CN102297878B CN102297878B CN201110130429.9A CN201110130429A CN102297878B CN 102297878 B CN102297878 B CN 102297878B CN 201110130429 A CN201110130429 A CN 201110130429A CN 102297878 B CN102297878 B CN 102297878B
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- 238000000034 method Methods 0.000 claims abstract description 10
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- 238000003860 storage Methods 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 6
- 238000011010 flushing procedure Methods 0.000 claims abstract description 5
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- 238000001035 drying Methods 0.000 claims description 10
- 150000008282 halocarbons Chemical class 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
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- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical group C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 1
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
An electronic nose system for rapid detection of pollution of volatile chlorinated hydrocarbons. The electronic nose system comprises a gas chamber gas passage unit which comprises a gas pipe, a pump, a magnetic valve, a conversion joint and a gas chamber and can finish processes of gas collection, detection, flushing and the like through controlling states of the magnetic valve and the pump, a gas pretreatment unit which is arranged in front of a gas inlet of the gas chamber gas passage unit and is utilized for removing moisture and interfering substances, a sensor unit which is arranged in the gas chamber and is utilized for acquisition of gas response signals, an embedded system which is arranged outside the gas chamber and is utilized for automatic control of the whole electronic nose system and processing, display and storage of signals, and a system housing which comprises an external casing, buttons, a mainboard, a display screen, a power supply module and the like and is utilized for providing power and data monitoring real-time display for the whole electronic nose system. The whole electronic nose system is controlled by the embedded system and has the advantages of low power dissipation, small volume, light weight, convenience of carrying, and effect of realization of online environmental monitoring.
Description
Technical field
The present invention relates to the fast detecting electric nasus system that volatile chlorinated hydrocarbon pollutes in the environment such as a kind of soil, water and air, specially refer to a kind of smart electronics nasus system that volatility chloro-alkenes and chloralkane in the environment is carried out the selectivity analyzing and testing.
Background technology
Volatile chlorinated hydrocarbon class material is industrial chemicals and the organic solvent of using always, and use has a large capacity and a wide range, high volatility, stable performance and have multiple poisonous effect.Volatile chlorinated hydrocarbon is easy to cause environmental pollutions such as atmosphere, soil and water body in that the method for producing, use, store and handle in the disposal process is improper, causes health risk.
Gas chromatographic technique is used in the detection of volatile chlorinated hydrocarbon usually.Gas chromatograph can carry out multianalysis to the pollutant composition, to the pollutant levels accurate quantification, but its instrument and equipment costs an arm and a leg, testing cost is higher, need to be equipped with the professional, complicated operation, being formulated into the result data analysis from titer needs the time very long, can't satisfy the requirement of fast detecting and on-line real time monitoring when a large amount of sample on-the-spot test.Therefore, the detection technique of volatile chlorinated hydrocarbon fast simple to operate, with low cost, portable becomes an important research direction.
China patent application CN 200810010884.3 and CN 200810013549.9 disclose respectively with the glow discharge under the atmospheric pressure, the vacuum-ultraviolet light ion mobility spectrometry as ionization source, are used for halogenated hydrocarbon compound is discerned and detected.But because ion mobility spectrometry resolution is bad, the range of linearity is narrow, and it is bigger that sensitivity is influenced by the capture means, and instrument is vulnerable to pollute, and has limited it and has promoted the use of.
In recent years, the gas sensor kind is on the increase, and is that the detection by electronic nose technology of main devices has also had large development with the gas sensor.Electronic Nose is a kind of instrument to mammalian sense of smell system simulations such as the mankind, by the hardware circuit that gas circuit reasonable in design and sensor array signal are handled, in conjunction with the software of optimizing, can discern simple or complicated smell.At present existing several commercial Electronic Nose emerge, but all exists cost an arm and a leg, bulky shortcoming, and focus mostly in the food inspection field, the Electronic Nose research that is applied to the environmental gas detection is then less.
Chinese invention patent CN 200310108469.9 discloses the gas sensor array of a kind of sensing chamber internal contamination, constitute a sensor array by several indium tin than different indium and tin oxide film gas sensors, each sensor makes this sensor array improve greatly the selectivity of gas to the response difference of gas.It can differentiate several frequently seen indoor polluted gas such as comprising benzene,toluene,xylene, formaldehyde easily.But it is a sensor array, form can on-line monitoring whole system; Only be applicable to and differentiate common indoor polluted gas, the applicability of volatile chlorinated hydrocarbon is not introduced; Can't realize quantitative measurement, to chaff interference also not research.
Chinese invention patent CN 200310108469.9 discloses a kind of sensing material that detects halogenated hydrocarbons, and sensing material is the aryl on platinum, 2-phenylpyridine part and the phenyl or advances an oligomer that is built into or a polymkeric substance by aryl, also comprises the derivant of aryl.Realize detection by the variation that detects the luminescent material fluorescence intensity to volatile halogenated hydrocarbons.Can realize detection by the compound of synthetic different coordinating groups to different halogenated hydrocarbons.But only introduced the detection of planting gas to single, not to mixed gas distinguish, analyzing and testing; The eliminating of disturbing is not research also; Be the exploitation of sensing material, do not form the whole system of on-line monitoring.
Summary of the invention
The objective of the invention is to solve the fast detecting and the on-line monitoring problem of volatile chlorinated hydrocarbon gas in the environment, little, in light weight, the anti-interference volatile chlorinated hydrocarbon gas detection of a kind of volume electric nasus system is provided.
For achieving the above object, the invention provides a kind of smart electronics nasus system that detects volatile chlorinated hydrocarbon, it comprises:
Air chamber gas circuit unit is made up of tracheae, pump, solenoid valve, X-over and air chamber, finishes processes such as gas production, detection, flushing by the state of control pump and solenoid valve;
The gas pretreatment unit, be located at the air intake opening of air chamber gas circuit unit before, be used for removing the moisture and the interfering material of sample;
Sensor unit is located at described air chamber inside, is used to gather the gas response signal;
Embedded system is located at described air chamber outside, is used for automatic control and signal Processing, demonstration and the storage of whole system;
System shell is made up of exterior case, button, mainboard, display screen and power module etc., shows in real time for total system provides electricity consumption and data monitoring.
Described gas pretreatment unit comprises moisture removal device and chaff interference removal device; Described moisture removal device has been filled the drying tube of drying agent such as anhydrous sodium sulfate, magnesium chloride for the 1-2 root; Described chaff interference removal device is made of 1-2 root halogenated hydrocarbons separator tube at least.
Described sensor unit comprises sensor array and sensor modulate circuit, wherein said sensor array has at least: be mainly used in the PID sensor that the volatile chlorinated hydrocarbon gas concentration is carried out quantitative test, be mainly used in the gas sensor that extracts smell " finger print information ", be mainly used in the Temperature Humidity Sensor that sensor environment of living in is monitored; Wherein the PID sensor is generally 1-3, and gas sensor 2-6, temperature and humidity sensing 1-2.
The quantity of described PID sensor is 1 when above, by ionogenic volatile chlorinated hydrocarbon under quantitative this energy of the response of low-yield PID sensor, by the quantitative only volatile chlorinated hydrocarbon of ability ionization under this high-energy of the response difference of high-energy PID sensor and low-yield PID sensor, thus the quantitative volatile chlorinated hydrocarbon of difference; Described gas sensor is that 1 or 1 are when above, by response characteristic or same volatile chlorinated hydrocarbon response characteristic on different sensors qualitative the distinguish volatile chlorinated hydrocarbon of different volatile chlorinated hydrocarbons on same sensor.
Described embedded system by system control core, touch-control and display circuit, signal circuit, signal storage circuit is formed; Place air chamber gas circuit unit, gas pretreatment unit, sensor unit, embedded system in the described system shell, and be furnished with the handle that is convenient for carrying.
The tracheae of described air chamber gas circuit unit and air chamber are all by the very little polytetrafluoroethylmaterial material of volatile organic matter absorption is made.
The present invention proposes the electric nasus system of volatile chlorinated hydrocarbon gas in a kind of new testing environment, this electric nasus system is by installing gas drying process device and gas separator tube additional before air chamber, effectively removed the interference of moisture and other organic gas to detecting, the gas sensor qualitative detection is combined with PID sensor detection by quantitative, can differentiate rapidly and detection by quantitative volatility chloro-alkenes and chloralkane in the environment.
The invention has the advantages that: whole system is controlled by embedded system, and is low in energy consumption, and volume is little, in light weight, easy to carry; Contain the dried unit, removed the influence of moisture the sensor response; Before air chamber, connect the halogenated hydrocarbons separative element, removed of the interference of other organic gas detecting; Utilize gas sensor that volatile chlorinated hydrocarbon is carried out qualitative detection; Utilize the PID sensor of different-energy that chloro-alkenes and chloralkane are carried out qualitative and detection by quantitative; Native system can be differentiated rapidly and detection by quantitative for volatile chlorinated hydrocarbon in the environment.
Description of drawings
Fig. 1 is the technical solution of the present invention synoptic diagram;
Fig. 2 is an air-channel system synoptic diagram of the present invention;
Fig. 3 is the concentration-response curve of methenyl choloride on electric nasus system;
Fig. 4 is the concentration-response curve on the triclene electric nasus system;
Fig. 5 is the response change curve of volatile chlorinated hydrocarbon vacuum desorption process in the simulating pollution soil.
Embodiment
The present invention will be described in detail below in conjunction with accompanying drawing:
With reference to accompanying drawing 1, volatile chlorinated hydrocarbon detection by electronic nose system comprises: one is mainly used in the air chamber gas circuit unit 1 of connection and pilot-gas circulation, one be mainly used in remove the moisture that contains in the environmental gas and interfering material gas pretreatment unit 2, one sensor unit 3, that mainly gas signal is converted into electric signal is mainly used in the embedded control system 4 of control and Signal Processing, demonstration and the storage of total system.One is mainly used in and places 1,2,3,4 and comprise the shell 5 of mainboard, display screen, button and power module.In accompanying drawing 1, also comprise gas 6 to be measured and training sample 7.
Air chamber gas circuit of the present invention unit is made up of tracheae, pump, solenoid valve, X-over and air chamber, and required sensor is installed in the air chamber, finishes processes such as gas production, detection, flushing by the state that changes pump and solenoid valve.Wherein tracheae and air chamber are made by polytetrafluoroethylmaterial material, have reduced the absorption of organic gas in the gentle chamber interior walls of tracheal wall greatly, have improved the accuracy of testing result.
Gas pretreatment unit of the present invention is made up of gas drying tube and gas separator tube.The drying agent of filling in the gas drying tube is anhydrous sodium sulfate, magnesium chloride etc., can make up as required.The gas separator tube is the halogenated hydrocarbons separator tube that U.S. Hua Rui company produces, and can filter halogenated hydrocarbon gas and adsorbs other organic gas, can connect one or more as required.
Sensor unit of the present invention is made up of sensor array and sensor modulate circuit.Sensor array places in the air chamber, comprise: be mainly used in the PID sensor that gas concentration is carried out quantitative test, be mainly used in the gas sensor that extracts smell " finger print information ", be mainly used in the Temperature Humidity Sensor that sensor environment is detected: wherein the PID sensor is generally 2, have different photoionization energy, gas is carried out selective fixed component analysis; Gas sensor carries out qualitative identification more than or equal to 2 to sample gas; Temperature Humidity Sensor is generally 1, also can monitor the drying tube treatment effect in the time of detecting sensor working environment humiture.Modulate circuit carries out filtering, processing and amplifying to the gas signal of gathering.
PID sensor of the present invention uses 2 usually, and energy is respectively 10.6 eV and 11.7 eV.The ionization potential of volatility chloro-alkenes is all below 10 eV, energy is that the PID sensor of 10.6 eV and 11.7 eV can both carry out ionization detection to it, and the ionization potential of volatility chloralkane is all more than 11 eV, and having only energy is that the PID sensor of 11.7 eV could be to its ionization detection.Therefore can distinguish and distinguish quantitative measurement volatility chloro-alkenes and volatility chloralkane according to the PID sensor response actual conditions of two kinds of different-energies.
Embedded control system of the present invention by embedded system control core, touch-control and display circuit, signal circuit, signal storage circuit is formed.Embedded control system mainly finish pattern-recognition, data storage, demonstration and to the control of seat in the plane, pump valve down and in case of necessity with data transmission to the PC workstation.
With reference to accompanying drawing 2, system gas route gas 8 to be measured, flushing gas 9, drying tube 10, halogenated hydrocarbons separator tube 11, air chamber 12, air pump 13, tail gas treating unit 14, T-valve 15 are formed.
Below in conjunction with embodiment the present invention is further described, will helps the understanding of the present invention.
Embodiment 1(air pollution detects)
Sensor array is formed: the PID sensor energy is 10.6 eV, and U.S. BASELINE company produces; Gas sensor is the TGS2602(S1 of Japanese FIGARO company), TGS2600(S2), TGS2620(S3).Use the GASTEC standard gas generating apparatus, the anemostat that different organic volatile solvents are housed is put into the gas diffusion chamber of constant temperature simultaneously, make carrier gas, prepare the mixing organic gas of variable concentrations as detecting gas by changing the carrier gas flow with high pure air.Open the air pump 13 of 0.5 L/min flow, earlier T-valve 15 is switched to and gather high pure air 9 rinse-systems and gather baseline, treat that the steady back of baseline switch three-way valve to acquisition testing gas 8 enters gas drying tube 10, separator tube 11, air chamber 12 successively, switch three-way valve is to gathering high pure air 9 rinse-systems after the extraction response signal graph.Accompanying drawing 3,4 is respectively methenyl choloride, the triclene concentration-response curve on electric nasus system.As can be seen from the figure different sensors is different to the response of identical volatile chlorinated hydrocarbon, and also inequality with the response of a kind of volatile chlorinated hydrocarbon on different sensors.Therefore, according to different sensors can be qualitative to the response characteristic of different volatile chlorinated hydrocarbon class materials or sxemiquantitative distinguish the kind of volatile chlorinated hydrocarbon, in conjunction with the response of PID sensor it is carried out detection by quantitative simultaneously.
Embodiment 2(soil vacuum extraction effect monitoring)
Sensor array is formed identical with embodiment 1.At soil remediation vacuum extraction scene, gather the soil gas of extracting out 8 at the extracting well head with the air pump 13 of 0.5 L/min flow and enter gas drying tube 10, separator tube 11, air chamber 12 successively, extract response signal graph.Reach the control total system by the timing switch valve and realize monitoring automatically, gathered a secondary data every 1 hour and draw extracting time and response curve.Accompanying drawing 5 is the response change curve of volatile chlorinated hydrocarbon vacuum extraction desorption process in the simulating pollution soil.As can be seen from the figure, in the vacuum extraction starting stage, the volatile chlorinated hydrocarbon pollution concentration is bigger in the soil, the response voltage value is higher, along with the variation response of extracting time reduce very fast, and along with the growth of desorption time, volatile chlorinated hydrocarbon concentration is more and more littler, respond also more and more forr a short time, increase each sensor response with the extracting time to the end and change stable until trend more and more slowly.Simultaneously, it can also be seen that from figure the PID sensor response of 10.6 eV is less, and comparatively fast reach stable, illustrate that volatility chloro-alkenes concentration is less in this soil, and desorption rate is also very fast.And the response of other three sensors is all a lot of greatly than PID, illustrate that volatility chloralkane concentration is bigger in this soil, and desorption rate is also a lot of slowly than the volatility chloro-alkenes.Whole response change process is identical with the concentration change process of gas chromatography (GC) monitoring, illustrate that this electric nasus system can be used for monitoring the on-the-spot vacuum extraction process of soil pollution, provide reference for optimizing vacuum extraction method and extracting time, so that obtain optimization process effect and minimum processing cost.
Embodiment 3 contaminated wastewaters detect
Claims (4)
1. the electric nasus system that pollutes of a fast detecting volatile chlorinated hydrocarbon, it comprises:
Air chamber gas circuit unit (1) is made up of tracheae, pump, solenoid valve, X-over and air chamber, finishes gas production, detection, flushing process by the state of control pump and solenoid valve;
Gas pretreatment unit (2), be located at the air intake opening of air chamber gas circuit unit (1) before, be used for removing the moisture and the interfering material of sample;
Sensor unit (3) is located at described air chamber inside, is used to gather the gas response signal;
Embedded system (4) is located at described air chamber outside, is used for automatic control and signal Processing, demonstration and the storage of whole system;
System shell (5) is made up of exterior case, button, mainboard, display screen and power module, shows in real time for total system provides electricity consumption and data monitoring;
Described gas pretreatment unit (2) comprises moisture removal device and chaff interference removal device; Described moisture removal device has been filled the drying tube of anhydrous sodium sulfate, magnesium chloride drying agent for the 1-2 root; Described chaff interference removal device is made of 1-2 root halogenated hydrocarbons separator tube at least;
Described sensor unit (3) comprises sensor array and sensor modulate circuit, wherein said sensor array has at least: be mainly used in the PID sensor that the volatile chlorinated hydrocarbon gas concentration is carried out quantitative test, be mainly used in the gas sensor that extracts smell " finger print information ", be mainly used in the Temperature Humidity Sensor that sensor environment of living in is monitored; Wherein the PID sensor is generally 1-3, and gas sensor 2-6, temperature and humidity sensing 1-2.
2. the electric nasus system that fast detecting volatile chlorinated hydrocarbon according to claim 1 pollutes, the quantity that it is characterized in that described PID sensor is 1 when above, by ionogenic volatile chlorinated hydrocarbon under quantitative this energy of the response of low-yield PID sensor, by the quantitative only volatile chlorinated hydrocarbon of ability ionization under this high-energy of the response difference of high-energy PID sensor and low-yield PID sensor, thus the quantitative volatile chlorinated hydrocarbon of difference; Described gas sensor is that 2 or 2 are when above, by response characteristic or same volatile chlorinated hydrocarbon response characteristic on different sensors qualitative the distinguish volatile chlorinated hydrocarbon of different volatile chlorinated hydrocarbons on same sensor.
3. the electric nasus system that fast detecting volatile chlorinated hydrocarbon according to claim 1 pollutes is characterized in that described embedded system (4) is made up of system's control core, touch-control and display circuit, signal circuit, signal storage circuit; Place air chamber gas circuit unit (1), gas pretreatment unit (2), sensor unit (3), embedded system (4) in the described system shell (5), and be furnished with the handle that is convenient for carrying.
4. the electric nasus system that fast detecting volatile chlorinated hydrocarbon according to claim 1 pollutes is characterized in that the tracheae of described air chamber gas circuit unit (1) and air chamber all make by volatile organic matter is adsorbed very little polytetrafluoroethylmaterial material.
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| CN201110130429.9A CN102297878B (en) | 2011-05-19 | 2011-05-19 | Electronic nose system for rapid detection of pollution of volatile chlorinated hydrocarbons |
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