CN107764806A - A kind of device and method of quick detection TOVC - Google Patents
A kind of device and method of quick detection TOVC Download PDFInfo
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- CN107764806A CN107764806A CN201711145896.2A CN201711145896A CN107764806A CN 107764806 A CN107764806 A CN 107764806A CN 201711145896 A CN201711145896 A CN 201711145896A CN 107764806 A CN107764806 A CN 107764806A
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
- G01N21/766—Chemiluminescence; Bioluminescence of gases
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The present invention relates to a kind of device of quick detection TOVC, including plasma generator, ozone generator and catalytic luminescence sensing device, the plasma generator is provided with sample air inlet and sample gas outlet, the ozone generator is provided with ozone outlet, the catalytic luminescence sensing device includes the chemiluminescence reactor and photodetector for being internally provided with catalyst, respectively with being connected in chemiluminescence reactor, the photodetector detects the catalytic luminescence signal sent in chemiluminescence reactor for the sample air inlet and ozone outlet.The invention further relates to a kind of method of quick detection TOVC.The device of quick detection TOVC of the present invention disclosure satisfy that quick, sensitive, easy TVOC detection demands.
Description
Technical field
The present invention relates to chemical detection analysis technical field, and in particular to a kind of quick detection total volatile organism
Device and method.
Background technology
Volatile organic contaminant (VOC) refers to that saturated vapour pressure is less than 260 DEG C more than 70.9Pa or boiling point at room temperature
Organic matter, TOVC (TVOC) are the summations of various volatile organic contaminants, including benzene homologues, alkane
Class, olefines, halogenated hydrocarbon, esters, ketone aldehydes and other volatile organic matters.Pollution sources are essentially from fuel outside TVOC rooms
Burning and communications and transportation, indoor pollution source essentially from construction material such as artificial board, plastic plate, foam heat insulating material etc.,
Ornament materials such as coating, paint and adhesive.Volatile organic matter has excitant, teratogenesis, carcinogenicity, mutagenicity, no
Skin and mucous membrane can be only directly affected, acute lesion is produced to human body, the function of digestive system can be also influenceed, appetite occurs not
Shake, the symptom such as nausea, or even central nervous system function can also be influenceed, the symptom such as dizzy, drowsiness, powerless, uncomfortable in chest occur, to people
Body health causes serious threat.Moreover, volatile organic matter can also cause atmosphere pollution, soil pollution, water pollution etc.,
Destroy ecological environment.Therefore, the detection strengthened to total volatile organism is significant.
China《Code for indoor environmental pollution control of civil building engineering》(GB 50325-2001) can define room air
The standard method of middle TVOC detections：Using the TVOC in Tenax-TA pipe enriched aiies, gas chromatograph is entered after Thermal desorption,
Using capillary chromatography post separation, detected with fid detector.To what is identified in chromatogram between n-hexane and hexadecane
All compounds are quantified, and the concentration of unidentified VOC is calculated with the response coefficient of toluene.The method
Detection limit is low, preci-sion and accuracy is good, and shortcoming is that time-consuming, and one sample of analysis about needs to spend 1h, and is not easy to realize in real time
On-line monitoring.Also emerged in recent years some TVOC new detecting methods for example GC-MS, high performance liquid chromatography, from
Sub- chromatography, fluorescent spectrometry etc., Thin film, although these large-scale precision instruments can carry out standard comprehensively to compound
True analysis, but instrument costly, complex operation is time-consuming longer and is not easy to realize on-line analysis, limit its application.Gas
Body sensor due to relatively cheap, easy to operate with simple in construction, small volume, cost, can the characteristic such as real time on-line monitoring,
Application in detection TVOC is paid attention to.Develop easy TVOC detection means, realize the TVOC of testing sample quick survey
It is fixed, it is significant.
Catalytic luminescence refers to be produced chemiluminescent phenomenon, catalytic reaction by catalysis oxidation when molecule passes through catalyst surface
Optical sensor need to only consume testing sample and oxidant (being typically the oxygen in air) in continuous mode, it is not necessary to external examination
Agent, and instrument and equipment is simple, analyze speed is fast, real-time online detection can be achieved, in recent years in the quick of volatile organic matter
Detection field is widely applied.Oxygen (weak oxidant) in conventional catalytic luminescence sensor generally use air is oxygen
Agent, use has the catalyst of specificly-response for sensing element to certain or certain class compound, realizes certain or certain class
The detection of compound, but the type of compounds detected is limited, it is impossible to meet TVOC testing requirements.
The content of the invention
The defects of for prior art, always waved it is an object of the present invention to provide a kind of quick detection based on catalytic luminescence
The device of hair property organic compound (TVOC), the device disclosure satisfy that quick, sensitive, easy TVOC detection demands.
The technical scheme that the present invention takes is as follows：
A kind of device of quick detection TOVC, including plasma generator, ozone generator and
Catalytic luminescence sensing device, the plasma generator are provided with sample air inlet and sample gas outlet, the ozone generator
Provided with ozone outlet, the catalytic luminescence sensing device includes the chemiluminescence reactor for being internally provided with catalyst and light inspection
Device is surveyed, the sample air inlet and ozone outlet in chemiluminescence reactor respectively with connecting, the photodetector detectionization
Learn the catalytic luminescence signal sent in luminescence-producing reaction room.
Wherein, the effect of plasma generator is by the compound in electrion activated sample, by some difficult oxygen
The compound " smashing " of change is easy to the progress of subsequent catalyst redox reaction；The effect of ozone generator is existed in real time for reaction
Line provides ozone gas as strong oxidizer；Chemiluminescence reactor in catalytic luminescence sensing device carries for redox reaction
For suitable reaction environment, its internal catalyst reaction set occurs, and photodetector is anti-for detecting chemiluminescence
Answer indoor catalytic luminescence signal.
When detecting the TVOC in sample, ozone of the sample gas after plasma generator with ozone generator supply
Mixing, enter back into chemiluminescence reactor and redox reaction occurs in catalyst surface, catalytic luminescence caused by reaction is believed
Number detected by photodetector, by the concentration that object to be measured in sample can be drawn to catalytic luminescence signal analysis.
Because catalytic luminescence is produced by redox reaction, the oxidant in reaction system detects sensitive to catalytic luminescence
Degree has material impact, and existing most of catalytic luminescence detection method uses the oxygen in air to make oxidant, oxygen
Oxidability is relatively low, limits its detectable object range.The present invention utilizes lower temperature plasma technology activated reactant, makes
After some difficult oxidized compounds generate easily oxidized compound through plasma " activation smashes ", and low temperature plasma can also be
Continuous catalytic luminescence reaction provides OH, O3, O isoreactivity oxidation components.Meanwhile the present invention further utilizes ozone generator
The ozone strong oxidizing agent of real-time online offer is provided for catalytic luminescence.Compared with prior art, the present invention is remarkably improved catalysis
The sensitivity of luminous detection, so as to realize that the rapid sensitive of variety classes VOC detects, on the other hand it can incite somebody to action
It is combined with chromatographic separation device, the new chromatographic detector as a versatility.
The present invention carries out activation by using plasma generator and ozone generator provides ozone strong oxidizing agent, promotes
The progress of redox reaction, the effect of enhanced sensitivity to the detection of organic compound catalytic luminescence is improved, it is anti-with reference to photodetector detection
The catalytic luminescence signal answered, realizes quick, sensitive, easy detection.Quick detection general volatile of the present invention is organic
The structure of the device of compound is simple, easy to operate, detection is quick, on-line checking, high sensitivity can be achieved, and outer indoors can examine
The TVOC surveyed in air ambient, has wide range of applications.
Further, the catalytic luminescence sensing device also includes temperature controller and optically filtering piece；The chemistry hair
Light reaction room is the quartz glass tube with reaction air inlet and reaction gas outlet, and it is built-in with heating element heater, the heating unit
Part surface is connected covered with the nano material as catalyst, the temperature controller with heating element heater；The optically filtering piece
It is arranged between photodetector and quartz glass tube, the photodetector is photomultiplier, is coaxially disposed with optically filtering piece.
Further, the plasma generator is dielectric barrier discharge low-temperature plasma generator, including electric discharge
Electrode and high voltage power supply, the sparking electrode by the quartz ampoule as insulating medium layer, the copper core being placed in inside the quartz ampoule and
Axially in parallel, the high voltage power supply difference of the copper wire composition being uniformly looped around outside the quartz ampoule, the copper core and quartz ampoule
It is connected with copper core and copper wire；The one end open of the quartz ampoule is the sample air inlet, and another end opening is that the sample goes out
Gas port.
Further, using oxygen as source of the gas, it is connected the ozone generator by polyfluortetraethylene pipe with oxygen source,
Real-time online produces ozone and is passed through via ozone outlet in chemiluminescence reactor.
Further, the device of the quick detection TOVC also includes sampling pump and glass three-way
Pipe, the sample outlet of the sampling pump and the sample air inlet of plasma generator connect, the plasma generator
Sample gas outlet is connected with the Single port of glass three-way pipe, and the ozone outlet of the ozone generator is another with glass three-way pipe
Single port connects, the remaining port of the reaction air inlet and glass three-way pipe of quartz glass tube in the catalytic luminescence sensing device
Connection.
Further, the catalyst of the heater element surface covering is titanium dioxide nano material.
Another object of the present invention is to provide a kind of side of quick detection TOVC based on catalytic luminescence
Method, this method comprise the following steps：By testing sample after high voltage electric field discharge activation, mixed with strong oxidizer ozone, so
Redox reaction occurs in catalyst surface afterwards, then by being detected and analyzed to catalytic luminescence signal caused by reaction,
Draw the concentration of object to be measured in testing sample.
Further, methods described is detected using the device of above-mentioned quick detection TOVC,
Specifically include following steps：
(1) heating element heater that surface sintering has titanium dioxide nano material is warming up to 300 ± 5 by temperature controller
DEG C, insulation is cooled to 205 ± 5 DEG C in 10 minutes to activate titanium dioxide nano material, then by heating element heater；Or by titanium dioxide
Titanium nano material is configured to suspension with deionized water, is uniformly applied to clean heater element surface, then heating element heater is installed
In in quartz glass tube, heater element surface is then warming up to 300 ± 5 DEG C by temperature controller and is incubated 10 minutes, is burnt
Layer of titanium dioxide nano material is tied as catalyst, heater element surface is then cooled to 205 ± 5 DEG C；
(2) standard sample that various concentrations are prepared in sampler bag is standby；
(3) open ozone generator real-time online and ozone is provided, open the high voltage power supply of plasma generator；
(4) sample in sampler bag is introduced in plasma generator with sampling pump and activated, the sample after activation
It is mixed into ozone in chemiluminescence reactor, redox reaction occurs on titanium dioxide nano material surface, it is caused
Catalytic luminescence signal is detected by photodetector after the light splitting of optically filtering piece and records luminous intensity, then is obtained through data processing
The linear equation of target concentration to be measured and luminous intensity；
(5) by step (4) detection testing sample, the luminous intensity for then detecting photodetector substitutes into step (4) institute
Obtain in linear equation, obtain the concentration of object to be measured in testing sample.
The titanium dioxide nano material of heater element surface sintering will not be consumed in detection process as catalyst, because
This is reusable.If it was found that the activity decrease of catalyst, can remove absorption in catalyst surface by high-temperature calcination catalyst
Impurity, with activated catalyst, ensure its catalytic activity, or sinter one layer of catalyst in heater element surface again.
Further, in step (4), the flow velocity for controlling sampling pump introducing sample is 0.9L/min, controls ozone generator
The flow velocity of ozone supply is 0.3L/min, and it is 205-210 DEG C to control the reaction temperature in chemiluminescence reactor, optically filtering piece
Catalytic luminescence signal is divided to be detected after 425nm wavelength by photodetector.
Further, the device of the quick detection TOVC and chromatographic separation device are combined, treated
Test sample product are directly entered in the device of the quick detection TOVC after chromatographic separation device separates
Row detection.
Both the device of the quick detection TOVC can be used alone by the present invention, realize in sample not
With the detection of compound overall characteristic signal, itself and chromatographic separation device can be also combined, as new chromatographic detector, realized
The detection one by one of each target components in sample.
In order to more fully understand and implement, the invention will now be described in detail with reference to the accompanying drawings.
Brief description of the drawings
Fig. 1 is the structure chart of the device of the quick detection TOVC of the present invention, the solid arrow in figure
Direction is gas flow direction, and dotted arrow direction is catalytic luminescence signal transmission direction；
Wherein, 1. sampling pump；2. plasma generator；3. ozone generator；4. catalytic luminescence sensing device；5. glass
Three-way pipe；20. sparking electrode；21. high voltage power supply；40. chemiluminescence reactor；41. temperature controller；42. optically filtering piece；
43. photodetector；44. heating element heater；45. nano material；A. sample air inlet；B. sample gas outlet；C. ozone outlet.
Fig. 2 is benzene homologues, alkane derivative, halogenated hydrocarbon compound, alkenes compounds respectively in differential responses bar
The chemiluminescence signal comparison diagram of part, a in figure1、a2、a3、a4、a5、b1、b2、b3、b4、c1、c2、c3、c4、d1、d2、d3、d4Respectively
It is corresponding to represent under the IV reaction condition of embodiment 1, detect toluene, ortho-xylene, paraxylene, meta-xylene, styrene,
Propane, n-hexane, normal heptane, normal octane, monochloro methane, dichloromethane, dichloroethanes, butyl bromide, isobutene, double penta
Alkene, laurene, the luminous intensity cylindricality of the alcohol of 1- octenes -3.
Fig. 3 is alcohol compound, aldehyde compound, ketone compounds, ester type compound respectively under the conditions of differential responses
Chemiluminescence signal comparison diagram, the e in figure1、e2、e3、e4、f1、f2、f3、f4、g1、g2、g3、g4、h1、h2、h3、h4Correspond to respectively
Represent under the IV reaction condition of embodiment 1, detect methanol, normal propyl alcohol, n-hexyl alcohol, sec-butyl alcohol, formaldehyde, acetaldehyde, propionic aldehyde, just
Butyraldehyde, acetone, 2 pentanone, 3- octanones, cyclopentanone, ethyl acetate, butyl acetate, n-caproic acid ethyl ester, ethyl butyrate it is luminous strong
Spend cylindricality.
Fig. 4 is toluene signal to noise ratio at different temperatures and the curve map of luminous intensity.
Fig. 5 is toluene signal to noise ratio at different wavelengths and the curve map of luminous intensity.
Fig. 6 (A) is toluene luminous intensity and the graph of relation of ozone flow velocity, and Fig. 6 (B) is toluene luminous intensity and sampling
The graph of relation of flow rate pump.
Fig. 7 is the working curve diagram of toluene concentration and chemiluminescence intensity relation.
Fig. 8 be using apparatus of the present invention as chromatographic detector, the methanol obtained, ethanol, normal propyl alcohol, ethyl acetate；
N-butanol, ethyl butyrate, butyl acetate, the chromatogram of the mixture of ethyl hexanoate.
Embodiment
Referring to Fig. 1, its structure chart for the device of the quick detection TOVC of the present invention.
The device of the quick detection TOVC includes sampling pump 1, plasma generator 2, ozone
Generator 3, catalytic luminescence sensing device 4 and glass three-way pipe 5.The sampling pump 1 is connected with plasma generator 2, described
Plasma generator 2 and ozone generator 3 are connected by glass three-way pipe 5 with catalytic luminescence sensing device 4 respectively.
Specifically, the sampling pump 1 is used to introduce the sample into plasma generator 2, and it is provided with sample outlet.
The plasma generator 2 is dielectric barrier discharge low-temperature plasma generator, including the He of sparking electrode 20
High voltage power supply 21.The sparking electrode 20 by the quartz ampoule (long 8.0cm, diameter 1.5cm) as insulating medium layer, be placed in the stone
Copper core inside English pipe and the copper wire composition being uniformly looped around outside the quartz ampoule, the copper core and quartz ampoule it is axially in parallel,
The high voltage power supply 21 is connected with copper core and copper wire respectively.The one end open of the quartz ampoule is sample air inlet a, and the other end is opened
Mouth is sample gas outlet b.
The ozone generator 3 is provided with gas source inlet and ozone outlet c, and it is using oxygen as source of the gas, the gas source inlet
It is connected by polyfluortetraethylene pipe with oxygen source.Ozone is via ozone outlet caused by the real-time online of ozone generator 3
Mouth c is supplied in catalytic luminescence sensing device 4.
The catalytic luminescence sensing device 4 includes chemiluminescence reactor 40, temperature controller 41, the and of optically filtering piece 42
Photodetector 43.
The chemiluminescence reactor 40 is the quartz glass tube with reaction air inlet and reaction gas outlet, and it is built-in with
Heating element heater 44.The surface of heating element heater 44 is covered with the nano material 45 as catalyst, further, the heating unit
Part 44 can be the electrical heating elements such as ceramic heating bar, ceramic heating core, stainless steel heating rod, and the catalyst of its surface covering is
Sinter the titanium dioxide nano material 45 formed.
The temperature controller 41 is connected with heating element heater 44, for regulating and controlling the temperature of heating element heater 44.
The photodetector 43 is located at outside quartz glass tube, anti-for detecting the redox in chemiluminescence reactor 40
Should caused catalytic luminescence signal.The optically filtering piece 42 is arranged between photodetector 43 and quartz glass tube.The light
Detector 43 is specially photomultiplier, and it is coaxially disposed with optically filtering piece 42.
The sampling pump 1, plasma generator 2, ozone generator 3, catalytic luminescence sensing device 4 and glass three-way pipe
5 specific annexation is：The sample outlet of the sampling pump 1 is connected with the sample air inlet a of plasma generator 2, institute
The sample gas outlet b for stating plasma generator 2 is connected with the Single port of glass three-way pipe 5, the ozone of the ozone generator 3
Gas outlet c is connected with the another port of glass three-way pipe 5, in the catalytic luminescence sensing device 4 reaction of quartz glass tube enter
Gas port is connected with the remaining port of glass three-way pipe 5.
During the device work of the quick detection TOVC, sampling pump 1 is by gaseous sample through over-sampling
Outlet, sample air inlet a are introduced in the quartz ampoule of plasma generator 2, by sample after discharge activation in high voltage electric field
Product gas outlet b enters in glass three-way pipe 5, is mixed with the ozone discharged from ozone outlet c, then senses and fill by catalytic luminescence
Put 4 reaction air inlet to enter in the quartz glass tube as chemiluminescence reactor 40, then on heating element heater 44
Redox reaction occurs for the surface of titanium dioxide nano material 45, is finally discharged from the reaction gas outlet of quartz glass tube.Reaction
Caused catalytic luminescence signal is detected and recorded by photodetector 43 after the light splitting of optically filtering piece 42.
Detected using the device of the quick detection TOVC, specifically include following steps：
(1) about 0.2g titanium dioxide nano materials are taken, deionized water is added, stirs and be configured to suspension, are uniformly applied
It is installed in the clean surface of heating element heater 44, then by heating element heater 44 in quartz glass tube, seals complete rear opening temperature control
Device 41 processed simultaneously adjusts its heating voltage, the surface temperature of heating element heater 44 is risen to 300 ± 5 DEG C and is incubated 10 minutes, sinters one layer
Titanium dioxide nano material 45 is used as catalyst, and the surface temperature of heating element heater 44 then is down into 205 ± 5 DEG C.
(2) standard sample that various concentrations are prepared in polytetrafluoroethylene (PTFE) sampler bag is standby.
(3) open the real-time online of ozone generator 3 and ozone is provided, open the high voltage power supply 21 of plasma generator 2.
(4) sample in polytetrafluoroethylene (PTFE) sampler bag is introduced in plasma generator 2 with sampling pump 1 and activated,
Sample after activation is mixed into chemiluminescence reactor 40 with ozone, is aoxidized on the surface of titanium dioxide nano material 45
Reduction reaction, caused catalytic luminescence signal are detected by photodetector 43 after the light splitting of optically filtering piece 42 and recorded luminous strong
Degree, then obtain target concentration to be measured and the linear equation of luminous intensity through data processing.
(5) by step (4) detection testing sample, the luminous intensity for then detecting photodetector 43 substitutes into step (4)
In gained linear equation, the concentration of object to be measured in testing sample is obtained.
When further, using toluene as detection object of reference, from the optically filtering piece 42 that wavelength is 425nm, by sampling pump 1
The flow rate set for introducing sample is 0.9L/min, is 0.3L/min by the flow rate set of the ozone supply of ozone generator 3, same to time control
Reaction temperature in chemiluminescence reactor 40 processed is 205-210 DEG C.
After the surface sintered titanium dioxide nano material 45 of heating element heater 44, titanium dioxide nano material 45 exists as catalyst
It will not be consumed in detection process, it is reusable.Therefore step (1) can be replaced：Opening temperature controller 41 adjusts surface sintering
The heating element heater 44 for having titanium dioxide nano material 45 is warming up to 205 ± 5 DEG C；Or opening temperature controller 41 adjusts surface
The heating element heater that sintering has titanium dioxide nano material is warming up to 300 ± 5 DEG C, is incubated 10 minutes to activate nano titania material
Material, then heating element heater is cooled to 205 ± 5 DEG C.
With reference to specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
The present embodiment have chosen different types of organic compound, and checking apparatus of the present invention are to organic compound catalytic luminescence
The effect of enhanced sensitivity of detection.
Totally 8 major class is investigated, total 33 kinds of organic compounds include as research object, these materials：Benzene homologues, alcohols
Compound, alkane derivative, aldehyde compound, ketone compounds, alkenes compounds, ester type compound, halogenated hydrocarbon chemical combination
Catalytic luminescence signal of the thing under 4 kinds of reaction conditions.Step is as follows：Take about 0.2g titanium dioxide nano material, addition go from
Sub- water, stir in suspension, it is uniformly applied on heating element heater.Heating element heater is placed in quartz glass tube, it is close
After envelope is complete, opening temperature controller, its heating voltage is adjusted, adjust the surface temperature of heating element heater to 205 ± 5 DEG C.Then,
Catalytic luminescence signal is detected under following 4 kinds of reaction conditions respectively：
I. ozone generator and plasma generator power supply are closed, i.e., using oxygen as oxidant, organic compound is not
Through detecting catalytic luminescence signal under the conditions of plasma active.It is 250mg/m that concentration, which is respectively configured,3Toluene, ortho-xylene, right
Dimethylbenzene, meta-xylene, styrene, methanol, normal propyl alcohol, n-hexyl alcohol, sec-butyl alcohol, propane, n-hexane, normal heptane, normal octane, first
Aldehyde, acetaldehyde, propionic aldehyde, n-butanal, acetone, 2 pentanone, 3- octanones, cyclopentanone, isobutene, dipentene, laurene, 1- octenes -3
Alcohol, ethyl acetate, butyl acetate, n-caproic acid ethyl ester, ethyl butyrate, monochloro methane, dichloromethane, dichloroethanes, butyl bromide
Testing sample is introduced in chemiluminescence reactor, treated as testing sample, sampling pump by gas respectively with 0.9L/min flow velocity
When compound in test sample product passes through the titanium dioxide nano material of heater element surface, it is anti-to be oxidized by oxygen generation catalytic luminescence
Should, caused catalytic luminescence signal is detected after the light splitting of optically filtering piece by photodetector.
Ii. ozonizer power supply is closed, plasma generator power supply is opened, i.e., using oxygen as oxidant, organises
Compound is through detecting catalytic luminescence signal under the conditions of plasma active.It is 250mg/m that concentration, which is respectively configured,3Above-mentioned 33 kinds of chemical combination
Testing sample is introduced into plasma generator by thing gas respectively as testing sample, sampling pump with 0.9L/min flow velocity
Row activation, the testing sample after activation are entered back into chemiluminescence reactor, and the compound in testing sample passes through heating element heater
During the titanium dioxide nano material on surface, it is oxidized by oxygen and catalytic luminescence reaction occurs, caused catalytic luminescence signal passes through light
Detected after learning filter plate light splitting by photodetector.
Iii. open ozonizer power supply, close plasma generator power supply, i.e., it is organic using ozone as oxidant
Compound is without detection catalytic luminescence signal under the conditions of plasma active.It is 250mg/m that concentration, which is respectively configured,3Above-mentioned 33 kinds
Testing sample is introduced chemiluminescence reactor by chemical compound gas respectively as testing sample, sampling pump with 0.9L/min flow velocity
It is interior, when the compound in testing sample passes through the titanium dioxide nano material of heater element surface, it is catalyzed by ozone oxidation
Luminescence-producing reaction, caused catalytic luminescence signal are detected after the light splitting of optically filtering piece by photodetector.
Iv. ozone generator and plasma generator power supply are opened simultaneously, i.e., using ozone as oxidant, organic compound
Thing is through detecting catalytic luminescence signal under the conditions of plasma active.It is 250mg/m that concentration, which is respectively configured,3Above-mentioned 33 kinds of compounds
Testing sample is introduced into plasma generator and carried out as testing sample, sampling pump by gas respectively with 0.9L/min flow velocity
Activation, the testing sample after activation are entered back into chemiluminescence reactor, and the compound in testing sample passes through heating element heater table
During the titanium dioxide nano material in face, catalytic luminescence reaction is occurred by ozone oxidation, caused catalytic luminescence signal passes through optics
Detected after filter plate light splitting by photodetector.
Obtained catalytic luminescence signal is detected under above-mentioned 4 kinds of reaction conditions as shown in Figures 2 and 3.From Fig. 2 and Fig. 3,
Under i reaction conditions, extremely weak catalytic luminescence signal is only able to detect, or even luminous signal can not be detected；Bar is reacted in II
Under part, catalytic luminescence has obtained the enhancing of relatively low multiple；Under III reaction condition, stronger catalytic luminescence letter can be detected
Number, and under IV reaction condition, the catalytic luminescence signal of different compounds is significantly increased, i.e., different compounds are produced
Catalytic luminescence response has been given birth to, can be by Sensitive Detection.The above results explanation can detect different organic compounds using apparatus of the present invention
The catalytic luminescence signal of thing, with doing the contrast of oxidant technology using oxygen, invention significantly improves the catalysis of organic compound
The sensitivity of luminous detection.
Embodiment 2
Volatile organic matter covering scope is extremely wide, and species is complicated, to identify that all compounds are more difficult one by one, therefore conventional
The response coefficient of toluene calculates the concentration of non-authenticating compound.Therefore the detection method for establishing toluene is detected to TVOC to pass weight
Will, the present embodiment establishes the method for quick detection toluene based on apparatus of the present invention and to carry out condition excellent using toluene as destination object
Change.
I. reaction temperature optimizes
About 0.2g titanium dioxide nano material is taken, deionized water is added, stirs in suspension, be uniformly applied to confession
On thermal element heating element heater, then heating element heater is placed in quartz glass tube, after sealing is complete, it is adjusted by temperature controller
Surface temperature.Configuration concentration is 250mg/m3Toluene gas, open ozone generator, caused ozone flow control is
0.3L/min, sampling pump introduce toluene and strong oxidizer ozone using 0.9L/min flow velocity in the stone as chemiluminescence reactor
In English glass tube, caused luminous signal is detected after the light splitting of optically filtering piece by photodetector after catalytic reaction occurs, point
Not Ce Ding differential responses temperature when luminous intensity and signal to noise ratio.As shown in figure 4, there is maximum when reaction temperature is 205 DEG C
Signal to noise ratio, therefore 210 DEG C are selected to determine the reaction temperature of toluene.
Ii. Detection wavelength optimizes
Different catalytic luminescence reaction systems have its characteristic emission spectrum, in order to obtain the feature of toluene catalytically luminescence-producing reaction
Spectrum, the light that wavelength is 350nm, 380nm, 425nm, 440nm, 460nm, 490nm, 535nm, 575nm, 620nm is chosen respectively
Filter plate is learned with optimizing detection wavelength.About 0.2g titanium dioxide nano material is taken, deionized water is added, stirs in suspended
Liquid, uniformly it is applied on heating element heater, then heating element heater is placed in quartz glass tube, after sealing is complete, passes through temperature control
Device adjusts its heating voltage, the temperature of heating element heater is fixed on 210 DEG C.Configuration concentration is 250mg/m3Toluene gas, beat
Ozone generator is driven, and it is 0.3L/min to control ozone flow velocity, sampling pump is with 0.9L/min flow velocity by toluene and strong oxidizer
Ozone is introduced as caused luminous signal after catalytic reaction in the quartz glass tube of chemiluminescence reactor, occurs by different
Detected after the light splitting of wavelength optical filter plate by photodetector, it is bent to obtain luminous intensity of the Detection wavelength between 350nm-620nm
Line and signal to noise ratio curve.As shown in figure 5, having maximum signal to noise ratio under the conditions of 425nm Detection wavelengths, therefore 425nm is selected as inspection
Survey the Detection wavelength of toluene.
Iii. flowing rate
About 0.2g titanium dioxide nano material is taken, deionized water is added, stirs in suspension, be uniformly applied to confession
On thermal element heating element heater, then heating element heater is placed in quartz glass tube, after sealing is complete, it is adjusted by temperature controller
Heating voltage, the surface temperature of heating element heater is adjusted to 205 ± 5 DEG C.Configuration concentration is 250mg/m3Toluene gas, fixation adopt
Sample flow rate pump is 0.9L/min, opens ozone generator, changes ozone flow velocity in the range of 0.1L/min-0.7L/min, by first
Benzene is introduced with strong oxidizer ozone in the quartz glass tube of chemiluminescence reactor, and caused luminous signal after catalytic reaction occurs
Detected after the light splitting of optically filtering piece by photodetector, obtain the luminous intensity under different ozone flow velocitys, as a result such as Fig. 6 (A)
Shown, ozone flow velocity has maximum emission intensity when being 0.3L/min.At the same time, fixed ozone flow velocity is 0.3L/min,
Change sampling flow rate pump can measure the luminous intensity under different sample flow rates in the range of 0.4L/min-1.5L/min, as a result such as Fig. 6
(B) shown in, sampling flow rate pump is that 0.9L/min has maximum emission intensity.
Iv. method is established
In order to verify application value of the inventive method in TVOC detections, the work song of toluene is drawn according to the following procedure
Line：About 0.2g titanium dioxide nano material is taken, deionized water is added, stirs in suspension, it is uniformly applied to confession
On thermal element heating element heater.Heating element heater is placed in quartz glass tube, after sealing is complete, opening temperature controller, adjusts it
Heating voltage, the surface temperature of heating element heater is adjusted to 205 ± 5 DEG C.Ozone generator is opened, it is 0.3L/ to control ozone flow velocity
Min, open plasma producing apparatus.It is 0.08-537mg/m that concentration range, which is respectively configured,3Toluene, sampling pump is with 0.9L/
Testing sample is introduced into plasma generator by min flow velocity to be activated, and subsequently enters glass three-way pipe, with strong oxidizer
Ozone enters as in the quartz glass tube of chemiluminescence reactor after being well mixed here, by the two of heater element surface
During titanium dioxide nano material, catalytic luminescence reaction is occurred by ozone oxidation, caused catalytic luminescence signal passes through optically filtering piece
Detected after light splitting by photodetector.Using toluene concentration as abscissa, luminous intensity is that ordinate draws standard curve, as a result as schemed
Shown in 7, toluene concentration is in 0.08-537mg/m3In the range of, equation of linear regression I=linear with luminous intensity
(102.6C+1096.6 I is luminous intensity, and C is toluene concentration), coefficient R2For 0.9934, detection is limited to 0.02mg/m3, table
Bright the inventive method can be used for the detection of toluene, and then the response coefficient of toluene can be used to calculate the content of TVOC in sample.
Embodiment 3
Because apparatus of the present invention can significantly increase the catalytic luminescence signal of variety classes organic compound, i.e., to variety classes
Organic compound can produce signal response, therefore itself and chromatographic separation device can be combined, as a detection TVOC's
New chromatographic photodetector.Apparatus of the present invention are connected with 1.5 meters of polarity gas-chromatography packed columns, employ nitrogen as carrier gas,
Under the conditions of nebulizer gas pressure is 0.2mPa, for methanol, ethanol, normal propyl alcohol, ethyl acetate；N-butanol, ethyl butyrate, acetic acid fourth
Ester, the Analyze ＆ separate of ethyl hexanoate mixture, using verify apparatus of the present invention can as the application value of new chromatographic photodetector,
As a result it is as shown in Figure 8.Fig. 8 shows that this 8 kinds of organic compounds, can be by apparatus of the present invention one by one after chromatographic column efficiently separates
Detection, its peak sequence are methanol, ethanol, normal propyl alcohol, ethyl acetate；N-butanol, ethyl butyrate, butyl acetate, ethyl hexanoate.
Apparatus of the present invention have that high sensitivity, finding speed are fast with the new chromatographic photodetector that chromatographic separation device is combined into, general
Adaptive and it is versatile the advantages that, can for volatile organic matter quick separating analysis effective new technical meanses are provided.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that come for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.
Claims (10)
- A kind of 1. device of quick detection TOVC, it is characterised in that：Including plasma generator, ozone Generator and catalytic luminescence sensing device, the plasma generator is provided with sample air inlet and sample gas outlet, described smelly Oxygen Generator is provided with ozone outlet, and the catalytic luminescence sensing device includes being internally provided with the chemiluminescence reaction of catalyst Room and photodetector, the sample air inlet and ozone outlet in chemiluminescence reactor respectively with connecting, the light detection The catalytic luminescence signal sent in device detection chemiluminescence reactor.
- 2. the device of quick detection TOVC according to claim 1, it is characterised in that：The catalysis Luminous sensing device also includes temperature controller and optically filtering piece；The chemiluminescence reactor be with reaction air inlet and The quartz glass tube of gas outlet is reacted, it is built-in with heating element heater, and the heater element surface is covered with receiving as catalyst Rice material, the temperature controller are connected with heating element heater；The optically filtering piece is arranged on photodetector and quartz glass tube Between, the photodetector is photomultiplier, is coaxially disposed with optically filtering piece.
- 3. the device of quick detection TOVC according to claim 2, it is characterised in that：The grade from Daughter generator is dielectric barrier discharge low-temperature plasma generator, including sparking electrode and high voltage power supply, the electric discharge electricity Pole is by the quartz ampoule as insulating medium layer, the copper core being placed in inside the quartz ampoule and the copper being uniformly looped around outside the quartz ampoule Silk composition, the copper core and quartz ampoule it is axially in parallel, the high voltage power supply is connected with copper core and copper wire respectively；The quartz ampoule One end open be the sample air inlet, another end opening is the sample gas outlet.
- 4. the device of quick detection TOVC according to claim 3, it is characterised in that：The ozone Using oxygen as source of the gas, it is connected generator by polyfluortetraethylene pipe with oxygen source, and real-time online produces ozone via smelly Oxygen gas outlet is passed through in chemiluminescence reactor.
- 5. the device of quick detection TOVC according to claim 4, it is characterised in that：Also include adopting Sample pump and glass three-way pipe, the sample outlet of the sampling pump and the sample air inlet of plasma generator connect, described etc. The sample gas outlet of plasma generator is connected with the Single port of glass three-way pipe, the ozone outlet of the ozone generator with The another port of glass three-way pipe connects, the reaction air inlet of quartz glass tube and glass three in the catalytic luminescence sensing device The remaining port connection of siphunculus.
- 6. the device of quick detection TOVC according to claim 2, it is characterised in that：The heating The catalyst of element surface covering is titanium dioxide nano material.
- A kind of 7. method of quick detection TOVC, it is characterised in that：Comprise the following steps：By testing sample After high voltage electric field discharge activation, mixed with strong oxidizer ozone, redox reaction then occurs in catalyst surface, then By being detected and analyzed to catalytic luminescence signal caused by reaction, the concentration of object to be measured in testing sample is drawn.
- 8. the method for quick detection TOVC according to claim 7, it is characterised in that：Usage right It is required that the device of the quick detection TOVC described in any one of 2-6 is detected, following steps are specifically included：(1) heating element heater that surface sintering has titanium dioxide nano material is warming up to 300 ± 5 DEG C by temperature controller, protected Temperature is cooled to 205 ± 5 DEG C in 10 minutes to activate titanium dioxide nano material, then by heating element heater；Or by nano titania Material is configured to suspension with deionized water, is uniformly applied to clean heater element surface, then heating element heater is installed on into quartz In glass tube, heater element surface is then warming up to 300 ± 5 DEG C by temperature controller and is incubated 10 minutes, sinters one layer Heater element surface is then cooled to 205 ± 5 DEG C by titanium dioxide nano material as catalyst；(2) standard sample that various concentrations are prepared in sampler bag is standby；(3) open ozone generator real-time online and ozone is provided, open the high voltage power supply of plasma generator；(4) sample in sampler bag is introduced in plasma generator with sampling pump and activated, the sample after activation with it is smelly Oxygen is mixed into chemiluminescence reactor, and redox reaction, caused catalysis occurs on titanium dioxide nano material surface Luminous signal is detected by photodetector after the light splitting of optically filtering piece and records luminous intensity, then is obtained through data processing to be measured The linear equation of target concentration and luminous intensity；(5) by step (4) detection testing sample, the luminous intensity for then detecting photodetector substitutes into line obtained by step (4) In property equation, the concentration of object to be measured in testing sample is obtained.
- 9. the method for quick detection TOVC according to claim 8, it is characterised in that：Step (4) In, the flow velocity for controlling sampling pump introducing sample is 0.9L/min, and the flow velocity for controlling ozone generator ozone supply is 0.3L/min, It is 205-210 DEG C to control the reaction temperature in chemiluminescence reactor, and the light splitting of catalytic luminescence signal is 425nm by optically filtering piece Detected after wavelength by photodetector.
- 10. the method for quick detection TOVC according to claim 8, it is characterised in that：By described in The device of quick detection TOVC is combined with chromatographic separation device, and testing sample is by chromatographic separation device point From rear, it is directly entered in the device of the quick detection TOVC and is detected.
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| CN113340882A (en) * | 2021-06-08 | 2021-09-03 | 白伟东 | Device and method for rapidly detecting total volatile organic compounds |
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