CN115236012A - Detection device and method for benzene series volatile organic compounds - Google Patents
Detection device and method for benzene series volatile organic compounds Download PDFInfo
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- CN115236012A CN115236012A CN202210792362.3A CN202210792362A CN115236012A CN 115236012 A CN115236012 A CN 115236012A CN 202210792362 A CN202210792362 A CN 202210792362A CN 115236012 A CN115236012 A CN 115236012A
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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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
- G01N21/3151—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths using two sources of radiation of different wavelengths
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/47—Scattering, i.e. diffuse reflection
- G01N21/49—Scattering, i.e. diffuse reflection within a body or fluid
- G01N21/51—Scattering, i.e. diffuse reflection within a body or fluid inside a container, e.g. in an ampoule
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- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
- G01N2021/3155—Measuring in two spectral ranges, e.g. UV and visible
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Abstract
The invention discloses a detection device of benzene series volatile organic compounds, which comprises a gas collection and supply unit, a gas rapid oxidation unit and a scattering and extinction characteristic measurement unit, wherein an ozone generator, a gas sampling pump and a nitrogen oxide generator in the gas collection and supply unit are respectively connected with an oxidation flow reactor through pipelines arranged in the gas collection and supply unit, the gas rapid oxidation unit comprises an oxidation flow reactor internally provided with an ultraviolet lamp tube, the scattering and extinction characteristic measurement unit comprises a smoke box and an optical characteristic measurement platform, the smoke box is positioned at the other side of the oxidation flow reactor, and the bottom of the smoke box is connected with the oxidation flow reactor through a pipeline arranged in the smoke box.
Description
Technical Field
The invention relates to the technical field of detection of atmospheric volatile organic compounds, in particular to a device and a method for detecting benzene series volatile organic compounds.
Background
Volatile organic compounds, commonly represented by VOCs, are compounds commonly existing in the atmosphere, are mostly in a gaseous state at normal temperature and normal pressure, and play a special role in the atmospheric oxidation process. The composition of the atmospheric VOCs is complex and can be divided into compounds such as benzene series, alkane, alkene, alkyne, halogenated hydrocarbon, aldehyde, ester, ketone and the like according to chemical components. The benzene series volatile organic compounds are one of important components of VOCs, mainly come from petrochemical industry, motor vehicle tail gas, organic solvent and other artificial source emissions, are important atmospheric pollutants commonly existing in indoor and outdoor air, and have important influence in the formation process of atmospheric pollution. Many benzene series volatile organic compounds have toxicity to organisms in different degrees and can directly harm human health. Therefore, the detection of the benzene series volatile organic compounds has important significance.
As the benzene series volatile organic compound has the characteristics of low concentration, high activity, easy volatilization, complex components and the like, the detection and analysis process is required to be simple, quick, efficient and pollution-free. The currently used measuring methods of the benzene series volatile organic compounds mainly comprise gas chromatography, gas chromatography-mass spectrometry combined method, high performance liquid chromatography and the like, and although the measuring methods have high detection precision, the measuring methods are expensive, complex in operation, time-consuming, difficult to realize online detection and inconvenient for real-time monitoring of air quality. However, in patent nos. CN 107764806A and CN113340882A, total volatile organic compounds are detected by a catalytic luminescence method, ozone is activated by a plasma or microwave method to promote the oxidation-reduction reaction, so as to improve the sensitivity of the catalytic luminescence detection and realize the rapid and sensitive detection of volatile organic compounds. Benzene series volatile organic compounds are important precursors of secondary organic aerosol, and the secondary organic aerosol is usually expressed by SOA and can be oxidized to generate brown carbon with spectrum dependence of absorption characteristics in ultraviolet and visible light regions under the condition of atmosphere, particularly in the presence of oxynitride and ozone. Therefore, the benzene series volatile organic compound is rapidly oxidized in the presence of the oxynitride and the ozone to form the secondary organic aerosol, and the multi-wavelength scattering and extinction characteristics of the secondary organic aerosol are detected, so that the online detection of the benzene series volatile organic compound can be realized.
Disclosure of Invention
The invention aims to provide a device and a method for quickly oxidizing benzene volatile organic compounds to form secondary organic aerosol in the presence of nitrogen oxides and ozone and detecting multi-wavelength scattering and extinction characteristics of the secondary organic aerosol, so as to realize online detection of the benzene volatile organic compounds.
In order to achieve the purpose, the invention provides the following technical scheme: a detection device for benzene series volatile organic compounds comprises a gas acquisition and supply unit, a gas rapid oxidation unit and a scattering and extinction characteristic measurement unit;
the gas collecting and supplying unit comprises an ozone generator, a gas sampling pump and a nitrogen oxide generator, and the gas rapid oxidation unit comprises an oxidation flow reactor internally provided with an ultraviolet lamp tube; the scattering and extinction characteristic measurement unit comprises a smoke box and an optical characteristic measurement platform;
ozone generator, gas sampling pump and nitrogen oxide generator respectively through the pipeline that is equipped with oxidation flow reactor links to each other, the smoke box is located oxidation flow reactor opposite side, just smoke box bottom through the pipeline that is equipped with oxidation flow reactor links to each other, optical property measuring platform is located inside the smoke box is placed at middle position.
Preferably, optical property measuring platform includes laser instrument, diaphragm, photo detector, light filter, annular guide rail and nozzle, the nozzle is located optical property measuring platform central point puts, just the nozzle links to each other with the pipeline of lower extreme, annular guide rail encircles and is located optical property measuring platform is all around, laser instrument, diaphragm, photo detector and light filter are located a straight line, just the laser instrument with the diaphragm is located nozzle one side, the photo detector with the light filter is located the nozzle opposite side, laser instrument, diaphragm, light detection and light filter all center on the annular guide rail removes.
Preferably, the laser comprises a first laser source emitting light with wavelength in ultraviolet region and wavelength λ 1 and a second laser source emitting light with wavelength in visible region and wavelength λ 2, the filter is a dual-band-pass filter with wavelength λ 1 and wavelength λ 2, and the photodetector is a photodiode or a photomultiplier.
Preferably, the aperture includes a first aperture and a second aperture, the photodetector includes a first photodetector and a second photodetector, and the filter includes a first filter and a second filter.
Preferably, the upper end of the smoke box is provided with an exhaust pipeline, and the reactant is sprayed out from the pipeline at the lower end of the smoke box through the nozzle and is exhausted from the exhaust pipeline.
A detection method of a detection device for benzene series volatile organic compounds comprises the following steps:
s1, collecting a gas sample containing benzene volatile organic compounds in real time by using a gas sampling pump, and respectively providing nitrogen oxides and ozone for the rapid oxidation reaction of the benzene volatile organic compounds in real time by using a nitrogen oxide generator and an ozone generator;
s2, carrying out rapid oxidation reaction on the sampled gas and the mixed gas of the nitrogen oxide and the ozone under the irradiation of ultraviolet rays emitted by an ultraviolet lamp tube in an oxidation flow reactor to form secondary organic aerosol;
s3, the reacted secondary organic aerosol and gas mixture enters the smoke box from the bottom through a pipeline, is sprayed out from a nozzle, enters an optical characteristic measuring platform arranged in the middle of the interior of the smoke box, and is discharged out of the smoke box from an exhaust pipeline at the upper part;
s4, on the optical characteristic measuring platform, a group of light source-light detection devices are formed by a laser light source and a light detector which is positioned on the same straight line, and the laser light source-light detection devices move on the annular guide rail simultaneously through the group of light source-light detection devices, so that the extinction characteristic of the aerosol is measured; the relative positions of the two groups of light sources and the light detection devices are adjusted within the range of 10-170 degrees, so that the scattering characteristics of the aerosol under different angles are measured;
and S5, finally, realizing the detection of the benzene series volatile organic compound according to the relation between the scattering and extinction characteristics under the laser light sources with the two wavelengths and the wavelengths.
Preferably, one set of the light source-light detecting devices includes a first light source emitting light with wavelength λ 1, a second light source emitting light with wavelength λ 2, a second light source emitting light with wavelength λ 1, a second light source emitting light with wavelength λ 2, and a second light source emitting light with wavelength λ 1.
Preferably, another set of the light source-light detection device includes that the transmitted light of the light source laser with the wavelength of λ 2 emitted by the second laser light source after passing through the nozzle is detected by the second light detector which is positioned on the same straight line through the two-band-pass second filters with the wavelengths of λ 1 and λ 2, and the scattered light is detected by the first light detector through the two-band-pass first filters with the wavelengths of λ 1 and λ 2.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, benzene volatile organic compounds can be oxidized to generate brown carbon with spectrum dependence on absorption characteristics in ultraviolet and visible light regions in the presence of nitrogen oxides and ozone in the atmosphere, dual-wavelength laser is adopted to simultaneously detect aerosol scattering and extinction characteristics under two wavelengths, and benzene volatile organic compounds capable of being oxidized to generate aerosols with different scattering and extinction characteristics are distinguished according to the relationship between the scattering and extinction characteristics and the wavelengths.
2. In the invention, the filter used in the light source-light detection device is a dual-band-pass filter with the wavelength in the ultraviolet and visible light regions, and the simultaneous detection of the scattering and extinction characteristics under the two wavelengths of the ultraviolet and visible light regions is realized.
3. The invention can continuously and simultaneously measure the scattering and extinction characteristics of the benzene series volatile organic compounds, the nitrogen oxide compounds and the mixture of ozone which are rapidly oxidized under the irradiation of ultraviolet rays at different angles and the relationship between the aerosol and ultraviolet and visible light wavelengths, and is used for distinguishing different kinds of benzene series volatile organic compounds.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
In the drawings:
FIG. 1 is a schematic view of an apparatus for detecting benzene-based volatile organic compounds according to the present invention;
FIG. 2 is a schematic view of an optical characteristic measuring platform in the detecting apparatus for benzene-based VOC according to the present invention;
reference numbers in the figures: 1. an ozone generator; 2. a gas sampling pump; 3. a nitrogen oxide generator; 4. an oxidation flow reactor; 41. an ultraviolet lamp tube; 5. a smoke box; 6. an optical property measurement platform; 60. an annular guide rail; 61. a nozzle; 62. a first laser light source; 63. a first diaphragm; 64. a second laser light source; 65. a second diaphragm; 66. a first light detector; 67. a first optical filter; 68. a second photodetector; 69. a second filter.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it should be understood that they are presented herein only to illustrate and explain the present invention and not to limit the present invention.
The embodiment is as follows: as shown in fig. 1 and 2, a detection device for benzene series volatile organic compounds comprises a gas collecting and supplying unit, a gas rapid oxidation unit and a scattering and extinction characteristic measuring unit;
the gas collecting and supplying unit comprises an ozone generator 1, a gas sampling pump 2 and a nitrogen oxide generator 3, and the gas rapid oxidation unit comprises an oxidation flow reactor 4 with an ultraviolet lamp tube 41 arranged inside; the scattering and extinction characteristic measurement unit comprises a smoke box 5 and an optical characteristic measurement platform 6, the ozone generator 1, the gas sampling pump 2 and the nitrogen oxide generator 3 are respectively connected with the oxidation flow reactor 4 through pipelines, the smoke box 5 is positioned at the other side of the oxidation flow reactor 4, the bottom of the smoke box 5 is connected with the oxidation flow reactor 4 through a pipeline, the optical characteristic measurement platform 6 is positioned in the smoke box 5 at the central position, the optical characteristic measurement platform 6 comprises a laser, a diaphragm, a light detector, a light filter, an annular guide rail 60 and a nozzle 61, the laser comprises a first laser source 62 with the emission wavelength of lambda 1 in an ultraviolet region and a second laser source 64 with the emission wavelength of lambda 2 in a visible light region, and the light filter is a dual-band pass filter with the wavelengths of lambda 1 and lambda 2, the light detector is a photodiode or a photomultiplier, the diaphragm comprises a first diaphragm 63 and a second diaphragm 65, the light detector comprises a first light detector 66 and a second light detector 68, the light filters comprise a first light filter 67 and a second light filter 69, the nozzle 61 is positioned at the center of the optical property measuring platform 6, the nozzle 61 is connected with a lower end pipeline, an exhaust pipeline is arranged at the upper end of the smoke box 5, reactants are sprayed out from the lower end pipeline of the smoke box 5 through the nozzle 61 and are discharged through the exhaust pipeline, the annular guide rail 60 is positioned around the optical property measuring platform 6, the laser, the diaphragm, the light detectors and the light filters are positioned on a straight line, the laser and the diaphragm are positioned at one side of the nozzle 61, and the light detector and the light filters are positioned at the other side of the nozzle 61, the laser, diaphragm, photo detector and filter all move around the ring guide 60.
A detection method of a detection device for benzene series volatile organic compounds specifically comprises the following steps:
s1, collecting a gas sample containing benzene volatile organic compounds in real time by using a gas sampling pump 2, and respectively providing nitrogen oxides and ozone for the rapid oxidation reaction of the benzene volatile organic compounds in real time by using a nitrogen oxide generator 3 and an ozone generator 1;
s2, carrying out rapid oxidation reaction on the sampling gas, the mixed gas of the nitrogen oxide and the ozone under the irradiation of ultraviolet rays emitted by an ultraviolet lamp tube 41 in the oxidation flow reactor 4 to form secondary organic aerosol;
s3, the reacted secondary organic aerosol and gas mixture enters the smoke box 5 from the bottom through a pipeline, is sprayed out from the nozzle 61, enters the optical characteristic measuring platform 6 arranged in the middle inside the smoke box 5, and is discharged out of the smoke box 5 from an exhaust pipeline at the upper part;
s4, on the optical characteristic measuring platform 6, one set of the light source-light detecting devices includes that the transmitted light of the light source laser with the wavelength λ 1 emitted by the first laser source passes through the nozzle 61 and then passes through the two-band-pass first filter 67 with the wavelengths λ 1 and λ 2, and is detected by the first light detector 66 located on the same straight line, and the scattered light thereof passes through the two-band-pass second filter 69 with the wavelengths λ 1 and λ 2 and is detected by the other second light detector 68, wherein the other set of the light source-light detecting devices includes that the transmitted light of the light source laser with the wavelength λ 2 emitted by the second laser source 64 passes through the nozzle 61 and then passes through the two-band-pass second filter 69 with the wavelengths λ 1 and λ 2 and is detected by the second light detector 68 located on the same straight line, and the scattered light thereof passes through the two-band-pass first filter 67 with the wavelengths λ 1 and λ 2 and is detected by the first light detector 66, and the laser source and the light detector form a set of light source-light detecting devices located on the same straight line, and the light source-light detecting devices are moved on the annular guide rail 60 at the same time to measure the extinction characteristic of the aerosol; the relative position of the two groups of light sources and the light detection device is adjusted within the range of 10-170 degrees, so that the scattering characteristics of the aerosol under different angles are measured;
and S5, finally, realizing the detection of the benzene series volatile organic compound according to the relation between the scattering and extinction characteristics under the laser light sources with the two wavelengths and the wavelengths.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A detection device for benzene series volatile organic compounds is characterized in that: the device comprises a gas collecting and supplying unit, a gas rapid oxidation unit and a scattering and extinction characteristic measuring unit;
the gas collecting and supplying unit comprises an ozone generator, a gas sampling pump and a nitrogen oxide generator, and the gas rapid oxidation unit comprises an oxidation flow reactor internally provided with an ultraviolet lamp tube; the scattering and extinction characteristic measuring unit comprises a smoke box and an optical characteristic measuring platform;
ozone generator, gas sampling pump and nitrogen oxide generator respectively through the pipeline that is equipped with oxidation flow reactor links to each other, the smoke box is located oxidation flow reactor opposite side, just smoke box bottom through the pipeline that is equipped with oxidation flow reactor links to each other, optical property measuring platform is located inside the smoke box is placed at middle position.
2. The detection apparatus for benzene series volatile organic compound according to claim 1, characterized in that: optical property measurement platform includes laser instrument, diaphragm, photo detector, light filter, annular guide rail and nozzle, the nozzle is located optical property measurement platform central point puts, just the nozzle links to each other with the pipeline of lower extreme, annular guide rail encircles and is located optical property measurement platform is all around, laser instrument, diaphragm, photo detector and light filter are located a straight line, just the laser instrument with the diaphragm is located nozzle one side, the photo detector with the light filter is located the nozzle opposite side, laser instrument, diaphragm, light detection and light filter all center on the annular guide rail removes.
3. The device for detecting a benzene-based volatile organic compound according to claim 2, wherein: the laser comprises a first laser light source with the emission wavelength in an ultraviolet region and the wavelength of lambda 1 and a second laser light source with the emission wavelength in a visible light region and the wavelength of lambda 2, the optical filter is a dual-band-pass optical filter with the wavelengths of lambda 1 and lambda 2, and the light detector is a photodiode or a photomultiplier.
4. The apparatus for detecting benzene-based volatile organic compound according to claim 3, wherein: the diaphragm comprises a first diaphragm and a second diaphragm, the light detector comprises a first light detector and a second light detector, and the light filter comprises a first light filter and a second light filter.
5. The apparatus for detecting benzene-based volatile organic compound according to claim 4, wherein: an exhaust pipeline is arranged at the upper end of the smoke box, and reactants are sprayed out from the pipeline at the lower end of the smoke box through the nozzle and are discharged from the exhaust pipeline.
6. A detection method based on the detection device for benzene-based volatile organic compounds according to any one of claims 1 to 5, comprising the steps of:
s1, collecting a gas sample containing benzene volatile organic compounds in real time by using a gas sampling pump, and respectively providing nitrogen oxides and ozone for the rapid oxidation reaction of the benzene volatile organic compounds in real time by using a nitrogen oxide generator and an ozone generator;
s2, carrying out rapid oxidation reaction on the sampled gas and the mixed gas of the nitrogen oxide and the ozone under the irradiation of ultraviolet rays emitted by an ultraviolet lamp tube in an oxidation flow reactor to form secondary organic aerosol;
s3, the reacted secondary organic aerosol and gas mixture enters the smoke box from the bottom through a pipeline, is sprayed out of a nozzle, enters an optical characteristic measuring platform arranged in the middle of the interior of the smoke box, and is discharged out of the smoke box from an exhaust pipeline at the upper part;
s4, on the optical characteristic measuring platform, a group of light source-light detection devices are formed by a laser light source and a light detector which is positioned on the same straight line, and the laser light source-light detection devices move on the annular guide rail simultaneously through the group of light source-light detection devices, so that the extinction characteristic of the aerosol is measured; the relative positions of the two groups of light sources and the light detection devices are adjusted within the range of 10-170 degrees, so that the scattering characteristics of the aerosol under different angles are measured;
and S5, finally, realizing the detection of the benzene series volatile organic compound according to the relation between the scattering and extinction characteristics under the laser light sources with the two wavelengths and the wavelengths.
7. The detection method of the detection apparatus for benzene-based volatile organic compounds according to claim 6, wherein: one set of the light source-light detection device comprises a first light source, a second light source and a third light source, wherein the first light source emits light source laser with the wavelength of lambda 1, the transmitted light of the light source laser with the wavelength of lambda 1 passes through a nozzle and then passes through a dual-band-pass first optical filter with the wavelengths of lambda 1 and lambda 2, the transmitted light is detected by a first light detector which is positioned on the same straight line, and the scattered light of the first light source passes through a dual-band-pass second optical filter with the wavelengths of lambda 1 and lambda 2 and is detected by another second light detector.
8. The detection method for a detection apparatus for a benzene-based volatile organic compound according to claim 6, characterized in that: the other group of the light source-light detection device comprises a second laser source, wherein the light source laser with the wavelength of lambda 2 emitted by the second laser source passes through a nozzle, the transmitted light passes through a double-band-pass second optical filter with the wavelengths of lambda 1 and lambda 2 and is detected by a second optical detector which is positioned on the same straight line, and the scattered light passes through a double-band-pass first optical filter with the wavelengths of lambda 1 and lambda 2 and is detected by a first optical detector.
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