CN107764806B - Device and method for rapidly detecting total volatile organic compounds - Google Patents
Device and method for rapidly detecting total volatile organic compounds Download PDFInfo
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- 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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Abstract
The invention relates to a device for rapidly detecting total volatile organic compounds, which comprises a plasma generator, an ozone generator and a catalytic luminescence sensing device, wherein the plasma generator is provided with a sample air inlet and a sample air outlet, the ozone generator is provided with an ozone air outlet, the catalytic luminescence sensing device comprises a chemiluminescence reaction chamber and a light detector, a catalyst is arranged in the chemiluminescence reaction chamber, the sample air inlet and the ozone air outlet are respectively communicated with the chemiluminescence reaction chamber, and the light detector detects catalytic luminescence signals emitted in the chemiluminescence reaction chamber. The invention also relates to a method for rapidly detecting the total volatile organic compounds. The device for rapidly detecting the total volatile organic compounds can meet the requirements of rapid, sensitive and simple TVOC detection.
Description
Technical Field
The invention relates to the technical field of chemical detection and analysis, in particular to a device and a method for rapidly detecting total volatile organic compounds.
Background
Volatile organic pollutants (VOC) are organic compounds with a saturated vapor pressure of more than 70.9Pa or a boiling point of less than 260 ℃ at room temperature, and Total Volatile Organic Compounds (TVOC) are the sum of various volatile organic pollutants, including benzene series, alkanes, alkenes, halogenated hydrocarbons, esters, ketoaldehydes and other volatile organic compounds. The TVOC outdoor pollution source mainly comes from fuel combustion and transportation, and the indoor pollution source mainly comes from building materials such as artificial boards, plastic boards, foam heat insulation materials and the like, and decorative materials such as coatings, paints and adhesives. The volatile organic compounds have irritation, teratogenicity, carcinogenicity and mutagenicity, can directly affect the skin and mucous membranes to cause acute damage to human bodies, can also affect the functions of digestive systems to cause symptoms such as inappetence, nausea and the like, and can even affect the functions of central nervous systems to cause symptoms such as dizziness, somnolence, weakness, chest distress and the like, thereby causing serious threat to the health of the human bodies. Moreover, volatile organic compounds can cause atmospheric pollution, soil pollution, water pollution and the like, and destroy the ecological environment. Therefore, the method has important significance for enhancing the detection of the total volatile organic compounds.
The standard method for detecting TVOC in indoor air is specified by the 'control of indoor environmental pollution in civil construction engineering' (GB 50325-2001): the TVOC in the air is enriched by a Tenax-TA tube, enters a gas chromatograph after thermal analysis, is separated by a capillary chromatographic column, and is detected by an FID detector. All compounds identified from the chromatogram between n-hexane and n-hexadecane were quantified and the concentration of unidentified volatile organic compounds was calculated using the response coefficient of toluene. The method has the disadvantages of low detection limit, good precision and accuracy, long time consumption, 1h consumption for analyzing one sample, and difficult realization of real-time online monitoring. In recent years, some new TVOC detection methods such as gas chromatography-mass spectrometry, high performance liquid chromatography, ion chromatography, fluorescence spectroscopy and the like, and reflection interference spectroscopy have emerged, and although these large-scale precise instruments can perform comprehensive and accurate analysis on compounds, the instruments are expensive, the operation is complex and time-consuming, and real-time online analysis is not easy to realize, so that the application of the instruments is limited. The gas sensor has the characteristics of simple structure, small volume, relatively low manufacturing cost, convenient operation, real-time online monitoring and the like, and the application of the gas sensor in the detection of TVOC is emphasized. The TVOC detection device which is simple and convenient to develop is used for realizing the rapid determination of the TVOC of the sample to be detected, and has important significance.
The catalytic luminescence refers to the phenomenon that molecules are catalyzed and oxidized to generate chemiluminescence when passing through the surface of a catalyst, a catalytic luminescence sensor only needs to consume a sample to be detected and an oxidant (usually oxygen in air) in the determination process, an external reagent is not needed, and the catalytic luminescence sensor is simple in instrument and equipment, high in analysis speed, capable of realizing real-time online detection and widely applied to the field of rapid detection of volatile organic compounds in recent years. The prior catalytic luminescence sensor generally adopts oxygen (weak oxidant) in the air as an oxidant, adopts a catalyst with specific response to a certain compound or a certain class of compounds as a sensing element, and realizes the detection of the certain compound or the certain class of compounds, but the types of the detected compounds are limited, and the requirements of TVOC detection cannot be met.
Disclosure of Invention
In view of the defects of the prior art, the present invention aims to provide a device for rapidly detecting Total Volatile Organic Compounds (TVOC) based on catalytic luminescence, which can meet the requirements of rapid, sensitive, simple and convenient TVOC detection.
The technical scheme adopted by the invention is as follows:
the utility model provides a device of total volatile organic compounds of short-term test, includes plasma generator, ozone generator and catalytic light-emitting sensing device, plasma generator is equipped with sample air inlet and sample gas outlet, ozone generator is equipped with the ozone gas outlet, catalytic light-emitting sensing device is including inside chemiluminescence reaction chamber and the photo-detector that is provided with the catalyst, sample air inlet and ozone gas outlet communicate in with the chemiluminescence reaction chamber respectively, the photo-detector detects the catalytic light-emitting signal that sends in the chemiluminescence reaction chamber.
The plasma generator is used for activating compounds in a sample through high-voltage discharge, and crushing some compounds which are difficult to oxidize so as to facilitate the subsequent catalytic oxidation-reduction reaction; the ozone generator is used for providing ozone gas as a strong oxidant for reaction in real time on line; the chemiluminescence reaction chamber in the catalytic luminescence sensing device provides a suitable reaction environment for oxidation-reduction reaction, a catalyst arranged in the chemiluminescence reaction chamber catalyzes reaction, and the photodetector is used for detecting a catalytic luminescence signal in the chemiluminescence reaction chamber.
When the TVOC in the sample is detected, the sample gas passes through the plasma generator and then is mixed with ozone supplied by the ozone generator, then enters the chemiluminescence reaction chamber to perform oxidation-reduction reaction on the surface of the catalyst, a catalytic luminescence signal generated by the reaction is detected by the photodetector, and the concentration of a target object to be detected in the sample can be obtained by analyzing the catalytic luminescence signal.
Because the catalytic luminescence is generated by oxidation-reduction reaction, an oxidant in a reaction system has important influence on the sensitivity of catalytic luminescence detection, and most of the existing catalytic luminescence detection methods adopt oxygen in the air as the oxidant, so that the oxidation capacity of the oxygen is low, and the detectable object range of the oxygen is limited. The invention utilizes low-temperature plasma technology to activate reactants, so that some compounds which are difficult to oxidize are activated and broken into easily-oxidized compounds by plasma, and the low-temperature plasma can also provide OH and O for subsequent catalytic luminescence reaction3And. O, and the like. Meanwhile, the invention further utilizes the ozone generator to carry out real-time catalytic luminescence reactionOzone strong oxidant provided by the line. Compared with the prior art, the invention can obviously improve the sensitivity of catalytic luminescence detection, thereby realizing the rapid and sensitive detection of different volatile organic compounds, and on the other hand, the invention can be used together with a chromatographic separation device as a novel universal chromatographic detector.
The invention uses the plasma generator to activate and the ozone generator provides strong ozone oxidant, promotes the oxidation-reduction reaction, improves the sensitization effect of the organic compound catalytic luminescence detection, and combines the catalytic luminescence signal of the photodetector detection reaction, thereby realizing the rapid, sensitive and simple detection. The device for rapidly detecting the total volatile organic compounds has the advantages of simple structure, convenient operation, rapid detection, realization of online detection, high sensitivity, capability of detecting TVOC in an indoor and outdoor air environment and wide application range.
Further, the catalytic luminescence sensing device further comprises a temperature controller and an optical filter; the chemiluminescence reaction chamber is a quartz glass tube with a reaction air inlet and a reaction air outlet, a heating element is arranged in the chemiluminescence reaction chamber, the surface of the heating element is covered with a nano material serving as a catalyst, and the temperature controller is connected with the heating element; the optical filter is arranged between the light detector and the quartz glass tube, and the light detector is a photomultiplier tube and is coaxial with the optical filter.
Furthermore, the plasma generator is a dielectric barrier discharge low-temperature plasma generator and comprises a discharge electrode and a high-voltage power supply, wherein the discharge electrode consists of a quartz tube used as an insulating medium layer, a copper core arranged in the quartz tube and copper wires uniformly surrounding the outside of the quartz tube, the copper core is parallel to the quartz tube in the axial direction, and the high-voltage power supply is respectively connected with the copper core and the copper wires; one end opening of the quartz tube is the sample air inlet, and the other end opening is the sample air outlet.
Furthermore, the ozone generator takes oxygen as a gas source, is connected with the oxygen gas source through a polytetrafluoroethylene tube, and generates ozone on line in real time and leads the ozone into the chemiluminescence reaction chamber through an ozone outlet.
Furthermore, the device for rapidly detecting the total volatile organic compounds further comprises a sampling pump and a glass three-way pipe, a sampling outlet of the sampling pump is connected with a sample gas inlet of the plasma generator, a sample gas outlet of the plasma generator is connected with one port of the glass three-way pipe, an ozone gas outlet of the ozone generator is connected with the other port of the glass three-way pipe, and a reaction gas inlet of a quartz glass pipe in the catalytic light-emitting sensing device is connected with the rest port of the glass three-way pipe.
Further, the catalyst covered on the surface of the heating element is a titanium dioxide nano material.
Another object of the present invention is to provide a method for rapidly detecting total volatile organic compounds based on catalytic luminescence, which comprises the following steps: and (3) after the sample to be detected is subjected to discharge activation by a high-voltage electric field, mixing the sample to be detected with strong oxidant ozone, then carrying out redox reaction on the surface of the catalyst, and detecting and analyzing a catalytic luminescence signal generated by the reaction to obtain the concentration of the target object to be detected in the sample to be detected.
Further, the method for detecting the total volatile organic compounds by using the device for rapidly detecting the total volatile organic compounds comprises the following steps:
(1) heating the heating element with the surface sintered with the titanium dioxide nano material to 300 +/-5 ℃ through a temperature controller, preserving the temperature for 10 minutes to activate the titanium dioxide nano material, and then cooling the heating element to 205 +/-5 ℃; or preparing a suspension of the titanium dioxide nano material and deionized water, uniformly coating the suspension on the surface of a clean heating element, installing the heating element in a quartz glass tube, heating the surface of the heating element to 300 +/-5 ℃ through a temperature controller, preserving the temperature for 10 minutes, sintering a layer of the titanium dioxide nano material as a catalyst, and cooling the surface of the heating element to 205 +/-5 ℃;
(2) preparing standard samples with different concentrations in a sampling bag for later use;
(3) starting an ozone generator to provide ozone on line in real time, and starting a high-voltage power supply of a plasma generator;
(4) introducing a sample in a sampling bag into a plasma generator by using a sampling pump for activation, mixing the activated sample with ozone, introducing the mixture into a chemiluminescence reaction chamber, performing an oxidation-reduction reaction on the surface of a titanium dioxide nano material, detecting a generated catalytic luminescence signal by using a light detector after the generated catalytic luminescence signal is subjected to light splitting by using an optical filter, recording the luminescence intensity, and then processing data to obtain a linear equation of the concentration and the luminescence intensity of a target object to be detected;
(5) and (4) detecting a sample to be detected according to the step (4), and then substituting the luminous intensity detected by the light detector into the linear equation obtained in the step (4) to calculate the concentration of the target object to be detected in the sample to be detected.
The titanium dioxide nano material sintered on the surface of the heating element is used as a catalyst, and can not be consumed in the detection process, so that the titanium dioxide nano material can be repeatedly used. If the activity of the catalyst is found to be reduced, impurities adsorbed on the surface of the catalyst can be removed by calcining the catalyst at a high temperature to activate the catalyst, ensure the catalytic activity of the catalyst, or re-sinter a layer of the catalyst on the surface of the heating element.
Further, in the step (4), the flow rate of the sample introduced by the sampling pump is controlled to be 0.9L/min, the flow rate of the ozone supplied by the ozone generator is controlled to be 0.3L/min, the reaction temperature in the chemiluminescence reaction chamber is controlled to be 205-210 ℃, and the optical filter plate is used for detecting the catalytic luminescence signal after the catalytic luminescence signal is dispersed to the wavelength of 425nm by the optical detector.
Furthermore, the device for rapidly detecting the total volatile organic compounds is combined with a chromatographic separation device, and a sample to be detected is separated by the chromatographic separation device and then directly enters the device for rapidly detecting the total volatile organic compounds for detection.
The device for rapidly detecting the total volatile organic compounds can be independently used to realize the detection of the total characteristic signals of different compounds in a sample, and can also be used together with a chromatographic separation device as a novel chromatographic detector to realize the one-by-one detection of each target component in the sample.
For a better understanding and practice, the invention is described in detail below with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic diagram of an apparatus for rapid detection of total volatile organic compounds according to the present invention, in which the solid line arrows indicate the gas flow direction and the dotted line arrows indicate the catalytic luminescence signal transmission direction;
wherein, 1, a sampling pump; 2. a plasma generator; 3. an ozone generator; 4. a catalytic luminescence sensing device; 5. a glass three-way pipe; 20. a discharge electrode; 21. a high voltage power supply; 40. a chemiluminescent reaction chamber; 41. a temperature controller; 42. an optical filter; 43. a photodetector; 44. a heating element; 45. a nanomaterial; a. a sample gas inlet; b. a sample gas outlet; c. an ozone outlet.
FIG. 2 is a graph showing the comparison of the chemiluminescence signals of benzene compounds, alkane compounds, halogenated hydrocarbon compounds, and olefin compounds under different reaction conditions, wherein a in the graph1、a2、a3、a4、a5、b1、b2、b3、b4、c1、c2、c3、c4、d1、d2、d3、d4Respectively, the measured luminescence intensities of toluene, o-xylene, p-xylene, m-xylene, styrene, propane, n-hexane, n-heptane, n-octane, monochloromethane, dichloromethane, dichloroethane, bromobutane, isobutene, dipentene, myrcene, and 1-octen-3-ol under the iv reaction conditions of example 1 are shown in columns.
FIG. 3 is a comparison graph of chemiluminescence signals of alcohol compounds, aldehyde compounds, ketone compounds, and ester compounds under different reaction conditions, wherein e is1、e2、e3、e4、f1、f2、f3、f4、g1、g2、g3、g4、h1、h2、h3、h4Respectively correspond to the column of luminescence intensity of methanol, n-propanol, n-hexanol, sec-butanol, formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, acetone, 2-pentanone, 3-octanone, cyclopentanone, ethyl acetate, butyl acetate, ethyl hexanoate and ethyl butyrate detected under the iv reaction condition of the example 1。
FIG. 4 is a graph of signal-to-noise ratio versus luminescence intensity for toluene at different temperatures.
FIG. 5 is a graph of signal-to-noise ratio versus luminescence intensity for toluene at different wavelengths.
FIG. 6(A) is a graph showing the relationship between the emission intensity of toluene and the flow rate of ozone, and FIG. 6(B) is a graph showing the relationship between the emission intensity of toluene and the flow rate of a sampling pump.
FIG. 7 is a graph of toluene concentration versus chemiluminescence intensity.
FIG. 8 shows the results of using the apparatus of the present invention as a chromatographic detector for obtaining methanol, ethanol, n-propanol, and ethyl acetate; chromatogram of a mixture of n-butanol, ethyl butyrate, butyl acetate and ethyl hexanoate.
Detailed Description
Please refer to fig. 1, which is a block diagram of an apparatus for rapidly detecting total volatile organic compounds according to the present invention.
The device for rapidly detecting the total volatile organic compounds comprises a sampling pump 1, a plasma generator 2, an ozone generator 3, a catalytic light-emitting sensing device 4 and a glass three-way pipe 5. The sampling pump 1 is connected with a plasma generator 2, and the plasma generator 2 and the ozone generator 3 are respectively connected with a catalytic light-emitting sensing device 4 through a glass three-way pipe 5.
In particular, the sampling pump 1 is used to introduce a sample into a plasma generator 2, which is provided with a sampling outlet.
The plasma generator 2 is a dielectric barrier discharge low-temperature plasma generator, and comprises a discharge electrode 20 and a high-voltage power supply 21. The discharge electrode 20 is composed of a quartz tube (8.0 cm in length and 1.5cm in diameter) as an insulating medium layer, a copper core arranged in the quartz tube and copper wires uniformly surrounding the quartz tube, the copper core is parallel to the quartz tube in the axial direction, and the high-voltage power supply 21 is respectively connected with the copper core and the copper wires. One end opening of the quartz tube is a sample air inlet a, and the other end opening of the quartz tube is a sample air outlet b.
The ozone generator 3 is provided with an air source inlet and an ozone outlet c, oxygen is used as an air source, and the air source inlet is connected with an oxygen air source through a polytetrafluoroethylene tube. The ozone generated by the ozone generator 3 on line in real time is supplied to the catalytic luminescence sensing device 4 through the ozone outlet c.
The catalytic luminescence sensing device 4 comprises a chemiluminescence reaction chamber 40, a temperature controller 41, an optical filter 42 and a photodetector 43.
The chemiluminescent reaction chamber 40 is a quartz glass tube with a reaction gas inlet and a reaction gas outlet, and has a heating element 44 disposed therein. The surface of the heating element 44 is covered with a nano material 45 as a catalyst, further, the heating element 44 may be a ceramic heating rod, a ceramic heating core, a stainless steel heating rod, or other electric heating elements, and the catalyst covered on the surface is a sintered titanium dioxide nano material 45.
The temperature controller 41 is connected to the heating element 44 for regulating the temperature of the heating element 44.
The photodetector 43 is located outside the quartz glass tube and is used for detecting a catalytic luminescence signal generated by an oxidation-reduction reaction in the chemiluminescent reaction chamber 40. The optical filter 42 is disposed between the photodetector 43 and the quartz glass tube. The light detector 43 is embodied as a photomultiplier tube, which is arranged coaxially with the optical filter 42.
The specific connection relation of the sampling pump 1, the plasma generator 2, the ozone generator 3, the catalytic light-emitting sensing device 4 and the glass three-way pipe 5 is as follows: the sampling outlet of the sampling pump 1 is connected with the sample air inlet a of the plasma generator 2, the sample air outlet b of the plasma generator 2 is connected with one port of the glass three-way pipe 5, the ozone air outlet c of the ozone generator 3 is connected with the other port of the glass three-way pipe 5, and the reaction air inlet of the quartz glass pipe in the catalytic light-emitting sensing device 4 is connected with the rest port of the glass three-way pipe 5.
When the device for rapidly detecting the total volatile organic compounds works, a gas sample is introduced into a quartz tube of a plasma generator 2 through a sampling outlet and a sample inlet a by a sampling pump 1, enters a glass three-way tube 5 through a sample outlet b after being discharged and activated in a high-voltage electric field, is mixed with ozone discharged from an ozone outlet c, enters the quartz glass tube serving as a chemiluminescence reaction chamber 40 through a reaction inlet of a catalytic luminescence sensing device 4, then undergoes an oxidation-reduction reaction on the surface of a titanium dioxide nano material 45 on a heating element 44, and finally is discharged from a reaction outlet of the quartz glass tube. The catalytic luminescence signal generated by the reaction is dispersed by the optical filter 42 and then detected and recorded by the photodetector 43.
The device for rapidly detecting the total volatile organic compounds is used for detection, and comprises the following steps:
(1) adding deionized water into 0.2g of titanium dioxide nano material, stirring uniformly to prepare a suspension, uniformly coating the suspension on the surface of a clean heating element 44, then installing the heating element 44 in a quartz glass tube, sealing completely, starting a temperature controller 41, adjusting the heating voltage of the temperature controller, raising the surface temperature of the heating element 44 to 300 +/-5 ℃, keeping the temperature for 10 minutes, sintering a layer of titanium dioxide nano material 45 as a catalyst, and then lowering the surface temperature of the heating element 44 to 205 +/-5 ℃.
(2) Preparing standard samples with different concentrations in a polytetrafluoroethylene sampling bag for later use.
(3) The ozone generator 3 is started to provide ozone on line in real time, and the high-voltage power supply 21 of the plasma generator 2 is started.
(4) A sample in a polytetrafluoroethylene sampling bag is introduced into a plasma generator 2 by a sampling pump 1 for activation, the activated sample and ozone are mixed and enter a chemiluminescence reaction chamber 40, an oxidation-reduction reaction occurs on the surface of a titanium dioxide nano material 45, a generated catalytic luminescence signal is subjected to light splitting by an optical filter 42, a light detector 43 detects and records the luminescence intensity, and a linear equation of the concentration and the luminescence intensity of a target object to be detected is obtained through data processing.
(5) And (4) detecting the sample to be detected according to the step (4), and then substituting the luminous intensity detected by the photodetector 43 into the linear equation obtained in the step (4) to calculate the concentration of the target object to be detected in the sample to be detected.
Further, when toluene is used as a detection reference substance, the optical filter 42 with a wavelength of 425nm is selected, the flow rate of the sample introduced by the sampling pump 1 is set to 0.9L/min, the flow rate of the ozone supplied by the ozone generator 3 is set to 0.3L/min, and the reaction temperature in the chemiluminescence reaction chamber 40 is controlled to 205-.
After the titanium dioxide nano material 45 is sintered on the surface of the heating element 44, the titanium dioxide nano material 45 as a catalyst is not consumed in the detection process and can be repeatedly used. Therefore, the step (1) can be replaced by: starting a temperature controller 41 to adjust the heating element 44 with the titanium dioxide nano material 45 sintered on the surface to be heated to 205 +/-5 ℃; or, the temperature controller 41 is started to adjust the heating element with the surface sintered with the titanium dioxide nano material to be heated to 300 +/-5 ℃, the temperature is kept for 10 minutes to activate the titanium dioxide nano material, and then the heating element is cooled to 205 +/-5 ℃.
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
In the embodiment, different types of organic compounds are selected, and the sensitization effect of the device on the catalytic luminescence detection of the organic compounds is verified.
A total of 8 major classes, 33 organic compounds were investigated as subjects, including: benzene series, alcohol compounds, alkane compounds, aldehyde compounds, ketone compounds, olefin compounds, ester compounds and halogenated hydrocarbon compounds under 4 reaction conditions. The method comprises the following steps: taking about 0.2g of titanium dioxide nano material, adding deionized water, stirring uniformly to form a suspension, and uniformly coating the suspension on a heating element. And (3) placing the heating element in a quartz glass tube, sealing completely, starting a temperature controller, adjusting the heating voltage of the temperature controller, and adjusting the surface temperature of the heating element to 205 +/-5 ℃. Then, the catalytic luminescence signal was detected under the following 4 reaction conditions:
i. and (3) switching off the power supplies of the ozone generator and the plasma generator, namely detecting a catalytic luminescence signal under the condition that oxygen is used as an oxidant and the organic compound is not subjected to plasma activity. Respectively prepared to have a concentration of 250mg/m3Toluene, o-xylene, p-xylene, m-xylene, styrene, methanol, n-propanol, n-hexanol, sec-butanol, propane,Normal hexane, normal heptane, normal octane, formaldehyde, acetaldehyde, propionaldehyde, normal butyraldehyde, acetone, 2-pentanone, 3-octanone, cyclopentanone, isobutene, dipentene, myrcene, 1-octene-3 alcohol, ethyl acetate, butyl acetate, ethyl hexanoate, ethyl butyrate, methyl chloride, dichloromethane, dichloroethane and butyl bromide gas are taken as samples to be detected, the samples to be detected are respectively introduced into a chemiluminescence reaction chamber by a sampling pump at the flow rate of 0.9L/min, when a compound in the samples to be detected passes through a titanium dioxide nano material on the surface of a heating element, the compound is oxidized by oxygen to generate a catalytic luminescence reaction, and a generated catalytic luminescence signal is detected by a light detector after being subjected to light splitting by an optical filter.
And ii, turning off the power supply of the ozone generator, and turning on the power supply of the plasma generator, namely detecting a catalytic luminescence signal of the organic compound under the condition that oxygen is taken as an oxidant and the plasma activity is carried out. Respectively prepared to have a concentration of 250mg/m3The 33 compound gases are used as samples to be detected, the sampling pump respectively introduces the samples to be detected into the plasma generator at the flow rate of 0.9L/min for activation, the activated samples to be detected enter the chemiluminescence reaction chamber, when the compounds in the samples to be detected pass through the titanium dioxide nano material on the surface of the heating element, the compounds are oxidized by oxygen to generate catalytic luminescence reaction, and the generated catalytic luminescence signals are detected by the light detector after being subjected to light splitting by the optical filter.
And iii, turning on the power supply of the ozone generator, and turning off the power supply of the plasma generator, namely detecting a catalytic luminescence signal under the condition that ozone is used as an oxidant and organic compounds are not subjected to plasma activity. Respectively prepared to have a concentration of 250mg/m3The 33 compound gases are used as samples to be detected, the sampling pump respectively introduces the samples to be detected into the chemiluminescence reaction chamber at the flow rate of 0.9L/min, when the compounds in the samples to be detected pass through the titanium dioxide nano material on the surface of the heating element, the compounds are oxidized by ozone to generate catalytic luminescence reaction, and the generated catalytic luminescence signals are detected by a light detector after being subjected to light splitting by the optical filter.
iv, simultaneously turning on the power supply of the ozone generator and the plasma generator, namely detecting the catalytic luminescence of the organic compound under the condition of taking ozone as an oxidant and plasma activityA signal. Respectively prepared to have a concentration of 250mg/m3The 33 compound gases are used as samples to be detected, the sampling pump respectively introduces the samples to be detected into the plasma generator at the flow rate of 0.9L/min for activation, the activated samples to be detected enter the chemiluminescence reaction chamber, when the compounds in the samples to be detected pass through the titanium dioxide nano material on the surface of the heating element, the compounds are oxidized by ozone to generate catalytic luminescence reaction, and the generated catalytic luminescence signals are detected by the light detector after being subjected to light splitting by the optical filter.
The catalytic luminescence signals detected under the above 4 reaction conditions are shown in fig. 2 and 3. As can be seen from FIGS. 2 and 3, under the reaction condition of i, only very weak catalytic luminescence signals can be detected, even no luminescence signals can be detected; under the condition of ii reaction, the catalytic luminescence is enhanced by a lower multiple; under the reaction condition of iii, a stronger catalytic luminescence signal can be detected, and under the reaction condition of iv, the catalytic luminescence signals of different compounds are obviously enhanced, namely, different compounds generate catalytic luminescence responses and can be sensitively detected. The results show that the device can detect catalytic luminescence signals of different organic compounds, and compared with the technology of using oxygen as an oxidant, the device provided by the invention has the advantage that the catalytic luminescence detection sensitivity of the organic compounds is obviously improved.
Example 2
The coverage range of volatile organic compounds is extremely wide, the types are complex, and it is difficult to identify all compounds one by one, so the concentration of unidentified compounds is calculated by using the response coefficient of toluene. Therefore, establishing a toluene detection method is crucial to TVOC detection, and in this embodiment, toluene is used as a target object, and a method for rapidly detecting toluene is established based on the apparatus of the present invention, and condition optimization is performed.
i. Reaction temperature optimization
Adding deionized water into 0.2g of titanium dioxide nano material, stirring uniformly to obtain turbid liquid, uniformly coating the turbid liquid on a heating element of a heat supply element, placing the heating element in a quartz glass tube, sealing completely, and adjusting the surface temperature of the quartz glass tube by a temperature controller. The prepared concentration is 250mg/m3Toluene gas of (2) and turning on the ozone generatorThe flow rate of the generated ozone is controlled to be 0.3L/min, the sampling pump introduces toluene and strong oxidant ozone into a quartz glass tube serving as a chemiluminescence reaction chamber at the flow rate of 0.9L/min, a luminescent signal generated after catalytic reaction is subjected to light splitting by an optical filter and then is detected by a photodetector, and the luminescent intensity and the signal-to-noise ratio at different reaction temperatures are respectively measured. As shown in FIG. 4, since the maximum signal-to-noise ratio was obtained at a reaction temperature of 205 ℃, 210 ℃ was selected as the reaction temperature for measuring toluene.
Optimization of detection wavelength
Different catalytic luminescence reaction systems have characteristic emission spectra, and optical filters with wavelengths of 350nm, 380nm, 425nm, 440nm, 460nm, 490nm, 535nm, 575nm and 620nm are respectively selected to optimize the detection wavelength in order to obtain the characteristic spectra of the toluene catalytic luminescence reaction. Adding deionized water into 0.2g of titanium dioxide nano material, stirring uniformly to obtain a suspension, uniformly coating the suspension on a heating element, placing the heating element in a quartz glass tube, sealing completely, and adjusting the heating voltage through a temperature controller to fix the temperature of the heating element at 210 ℃. The prepared concentration is 250mg/m3The ozone generator is started, the flow rate of ozone is controlled to be 0.3L/min, the sampling pump introduces toluene and strong oxidant ozone into a quartz glass tube serving as a chemiluminescence reaction chamber at the flow rate of 0.9L/min, luminescent signals generated after catalytic reaction are subjected to light splitting through optical filters with different wavelengths and then are detected by a light detector, and a luminescent intensity curve and a signal-to-noise ratio curve with the detection wavelength of 350-620 nm are obtained. As shown in FIG. 5, since there is a maximum signal-to-noise ratio at the detection wavelength of 425nm, 425nm is selected as the detection wavelength for detecting toluene.
Flow rate optimization
Adding deionized water into 0.2g of titanium dioxide nano material, stirring uniformly to obtain a suspension, uniformly coating the suspension on a heating element of a heating element, placing the heating element in a quartz glass tube, sealing completely, adjusting the heating voltage of the quartz glass tube by a temperature controller, and adjusting the surface temperature of the heating element to 205 +/-5 ℃. The prepared concentration is 250mg/m3The flow rate of the fixed sampling pump is 0.9L/min, and the opening odor is generatedThe oxygen generator changes the flow rate of ozone within the range of 0.1L/min-0.7L/min, toluene and strong oxidant ozone are introduced into a quartz glass tube of the chemiluminescence reaction chamber, a luminescence signal generated after catalytic reaction is subjected to light splitting through an optical filter and then is detected by a light detector, and the luminescence intensity under different ozone flow rates is obtained, and the result is shown in figure 6(A), and the maximum luminescence intensity is obtained when the flow rate of ozone is 0.3L/min. Meanwhile, the fixed ozone flow rate is 0.3L/min, and the luminous intensity at different sample flow rates can be measured by changing the sampling pump flow rate within the range of 0.4L/min to 1.5L/min, and as a result, as shown in FIG. 6(B), the sampling pump flow rate of 0.9L/min has the maximum luminous intensity.
Method build
In order to verify the application value of the method in TVOC detection, a toluene working curve is drawn according to the following process: taking about 0.2g of titanium dioxide nano material, adding deionized water, stirring uniformly to form turbid liquid, and uniformly coating the turbid liquid on a heating element of a heating element. And (3) placing the heating element in a quartz glass tube, sealing completely, starting a temperature controller, adjusting the heating voltage of the temperature controller, and adjusting the surface temperature of the heating element to 205 +/-5 ℃. Starting the ozone generator, controlling the flow rate of ozone to be 0.3L/min, and starting the plasma generating device. Respectively configuring the concentration range to be 0.08-537mg/m3The sample to be detected is introduced into a plasma generator for activation by a sampling pump at the flow rate of 0.9L/min, then enters a glass three-way pipe, is uniformly mixed with strong oxidant ozone at the position and then enters a quartz glass pipe serving as a chemiluminescence reaction chamber, when the mixture passes through a titanium dioxide nano material on the surface of a heating element, the mixture is oxidized by ozone to generate a catalytic luminescence reaction, and a generated catalytic luminescence signal is detected by a light detector after being subjected to light splitting by an optical filter. The concentration of toluene was plotted on the abscissa and the intensity of luminescence on the ordinate to obtain a standard curve, and the result is shown in FIG. 7, in which the concentration of toluene was 0.08-537mg/m3The range is in linear relation with the luminous intensity, the linear regression equation is that I is 102.6C +1096.6(I is luminous intensity, C is toluene concentration), and the correlation coefficient R20.9934, detection limit of 0.02mg/m3The method can be used for detecting the toluene, and can further calculate samples by using the response coefficient of the tolueneThe product contains TVOC.
Example 3
The device can obviously enhance the catalytic luminescence signals of different organic compounds, namely can generate signal response to different organic compounds, so that the device can be used together with a chromatographic separation device to serve as a novel chromatographic photodetector for detecting TVOC. Connecting the device with a 1.5 m polar gas chromatography packed column, adopting nitrogen as carrier gas, and using the nitrogen as the carrier gas under the condition that the pressure of the carrier gas is 0.2mPa for methanol, ethanol, n-propanol and ethyl acetate; the analysis and separation of the mixture of n-butanol, ethyl butyrate, butyl acetate and ethyl hexanoate are performed to verify the application value of the device of the invention as a novel chromatographic photodetector, and the result is shown in fig. 8. FIG. 8 shows that the 8 organic compounds can be detected one by the device of the present invention after being effectively separated by the chromatographic column, and the peak sequences are methanol, ethanol, n-propanol and ethyl acetate; n-butanol, ethyl butyrate, butyl acetate, ethyl hexanoate. The novel chromatographic light detector formed by combining the device and the chromatographic separation device has the advantages of high sensitivity, high measurement speed, universality, strong universality and the like, and can provide an effective new technical means for the rapid separation and analysis of volatile organic compounds.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (9)
1. An apparatus for rapidly detecting total volatile organic compounds, comprising: the device comprises a plasma generator, an ozone generator and a catalytic luminescence sensing device, wherein the plasma generator is provided with a sample air inlet and a sample air outlet, the ozone generator is provided with an ozone air outlet, the catalytic luminescence sensing device comprises a chemiluminescence reaction chamber and a light detector, a catalyst is arranged in the chemiluminescence reaction chamber, the sample air inlet and the ozone air outlet are respectively communicated with the chemiluminescence reaction chamber, and the light detector detects a catalytic luminescence signal sent out in the chemiluminescence reaction chamber; the chemiluminescence reaction chamber is a quartz glass tube with a reaction air inlet and a reaction air outlet, a heating element is arranged in the chemiluminescence reaction chamber, and the surface of the heating element is covered with a nano material serving as a catalyst; the catalyst covered on the surface of the heating element is a titanium dioxide nano material.
2. The device for rapidly detecting total volatile organic compounds according to claim 1, wherein: the catalytic luminescence sensing device also comprises a temperature controller and an optical filter; the temperature controller is connected with the heating element; the optical filter is arranged between the light detector and the quartz glass tube, and the light detector is a photomultiplier tube and is coaxial with the optical filter.
3. The device for rapidly detecting total volatile organic compounds according to claim 2, wherein: the plasma generator is a dielectric barrier discharge low-temperature plasma generator and comprises a discharge electrode and a high-voltage power supply, wherein the discharge electrode consists of a quartz tube used as an insulating medium layer, a copper core arranged in the quartz tube and copper wires uniformly surrounding the outside of the quartz tube, the copper core is parallel to the quartz tube in the axial direction, and the high-voltage power supply is respectively connected with the copper core and the copper wires; one end opening of the quartz tube is the sample air inlet, and the other end opening is the sample air outlet.
4. The device for rapidly detecting total volatile organic compounds according to claim 3, wherein: the ozone generator takes oxygen as a gas source, is connected with the oxygen gas source through a polytetrafluoroethylene tube, generates ozone on line in real time, and leads the ozone into the chemiluminescence reaction chamber through an ozone outlet.
5. The device for rapidly detecting total volatile organic compounds according to claim 4, wherein: the device is characterized by further comprising a sampling pump and a glass three-way pipe, wherein a sampling outlet of the sampling pump is connected with a sample air inlet of the plasma generator, a sample air outlet of the plasma generator is connected with one port of the glass three-way pipe, an ozone air outlet of the ozone generator is connected with the other port of the glass three-way pipe, and a reaction air inlet of a quartz glass pipe in the catalytic luminescence sensing device is connected with the rest port of the glass three-way pipe.
6. A method for rapidly detecting total volatile organic compounds, which is characterized by comprising the following steps: the method comprises the following steps: after a sample to be detected is subjected to high-voltage electric field discharge activation in a quartz tube of a plasma generator, the sample to be detected is mixed with strong oxidant ozone, then an oxidation-reduction reaction is carried out on the surface of a catalyst, and a catalytic luminescence signal generated by the reaction is detected and analyzed to obtain the concentration of a target object to be detected in the sample to be detected; the catalyst is a titanium dioxide nano material on a heating element arranged in a quartz tube.
7. The method for the rapid detection of total volatile organic compounds according to claim 6, characterized in that: the device for rapidly detecting total volatile organic compounds according to any one of claims 2 to 5, comprising the following steps:
(1) heating the heating element with the surface sintered with the titanium dioxide nano material to 300 +/-5 ℃ through a temperature controller, preserving the temperature for 10 minutes to activate the titanium dioxide nano material, and then cooling the heating element to 205 +/-5 ℃; or preparing a suspension of the titanium dioxide nano material and deionized water, uniformly coating the suspension on the surface of a clean heating element, installing the heating element in a quartz glass tube, heating the surface of the heating element to 300 +/-5 ℃ through a temperature controller, preserving the temperature for 10 minutes, sintering a layer of the titanium dioxide nano material as a catalyst, and cooling the surface of the heating element to 205 +/-5 ℃;
(2) preparing standard samples with different concentrations in a sampling bag for later use;
(3) starting an ozone generator to provide ozone on line in real time, and starting a high-voltage power supply of a plasma generator;
(4) introducing a sample in a sampling bag into a plasma generator by using a sampling pump for activation, mixing the activated sample with ozone, introducing the mixture into a chemiluminescence reaction chamber, performing an oxidation-reduction reaction on the surface of a titanium dioxide nano material, detecting a generated catalytic luminescence signal by using a light detector after the generated catalytic luminescence signal is subjected to light splitting by using an optical filter, recording the luminescence intensity, and then processing data to obtain a linear equation of the concentration and the luminescence intensity of a target object to be detected;
(5) and (4) detecting a sample to be detected according to the step (4), and then substituting the luminous intensity detected by the light detector into the linear equation obtained in the step (4) to calculate the concentration of the target object to be detected in the sample to be detected.
8. The method for the rapid detection of total volatile organic compounds according to claim 7, characterized in that: in the step (4), the flow rate of the sample introduced by the sampling pump is controlled to be 0.9L/min, the flow rate of the ozone supplied by the ozone generator is controlled to be 0.3L/min, the reaction temperature in the chemiluminescence reaction chamber is controlled to be 205-210 ℃, and the optical filter plate is used for detecting the catalytic luminescence signal after the catalytic luminescence signal is split into 425nm wavelength by the optical detector.
9. The method for the rapid detection of total volatile organic compounds according to claim 7, characterized in that: the device for rapidly detecting the total volatile organic compounds is combined with a chromatographic separation device, and a sample to be detected is separated by the chromatographic separation device and then directly enters the device for rapidly detecting the total volatile organic compounds for detection.
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| CN110031454A (en) * | 2019-05-06 | 2019-07-19 | 中山大学 | A kind of the cyclic chemical luminescence detection apparatus and method of quick identification complex sample |
| CN111912839B (en) * | 2020-08-13 | 2022-10-28 | 广东药科大学 | Catalytic light-emitting reactor, and butanone peroxide detection device and detection method |
| TWI791179B (en) * | 2020-12-14 | 2023-02-01 | 嘉藥學校財團法人嘉南藥理大學 | Test device of oxidtion catalyst having low catalytic temperature for volatile organic compound and odor gas |
| CN112964806B (en) * | 2021-03-22 | 2023-06-20 | 北京高斯匹克技术有限公司 | System for be applied to on-line analysis, automatic calibration, quality control and evaluation of silicon, nitrogen, phosphorus, sulphur and halogen element organic gas |
| 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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