CN104655601A - OH free radical measurement calibration system by adopting fluorescence assay by gas expansion - Google Patents
OH free radical measurement calibration system by adopting fluorescence assay by gas expansion Download PDFInfo
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- CN104655601A CN104655601A CN201510056379.2A CN201510056379A CN104655601A CN 104655601 A CN104655601 A CN 104655601A CN 201510056379 A CN201510056379 A CN 201510056379A CN 104655601 A CN104655601 A CN 104655601A
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- free radical
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Abstract
The invention discloses an OH free radical measurement calibration system by adopting fluorescence assay by gas expansion. The OH free radical measurement calibration system comprises a wideband light source, a water vapor generation part, an OH free radical generation part and a signal collection part, wherein the OH free radical generation part comprises an aluminum cavity, a U-shaped air inlet pipe, a multiple-reflection cell, a quartz sleeve and a high power ultraviolet lamp. The OH free radical calibration system disclosed by the invention can integrate generation and measurement of OH free radicals, and the concentration of the generated OH free radicals is measured by adopting a differential optical absorption spectroscopy (DOAS), so that the accuracy of the measured concentration of the OH free radicals is improved; the concentration of the OH free radicals is measured by adopting an optical method, the collection system is simple, and convenient and easy to operate; the wideband light source is adopted by the OH free radical calibration system disclosed by the invention, and visible light in the light source is used as an indication and adjustment light source of 308nm to solve the problem that the optical distance of the multiple-reflection cell is hard to measure due to the invisibility of 308nm.
Description
Technical field
The present invention relates to environmental monitoring technology field, particularly relate to a kind of for gas flaring OH Radical Measurement Using Laser Induced Fluorescence Technique scaling system.
Background technology
OH free radical is most important oxygenant in air, and it is not only the important indicator of atmospheric oxidn ability, is also a tolerance of trace gas automatically cleaning ability in air.It can with most atmospheric trace gas component generation chemical reaction, affect the life-span of many trace gas in troposphere.The course of reaction of OH free radical can the change of range of influence and global climate, the great environmental problem such as atmospheric oxidn level and acid deposition.
At present, the common method measuring troposphere OH free radical has three kinds: gas flaring laser Induced Fluorescence Technology (fluorescence assay by gas expansion, referred to as FAGE), long-range differential optical absorption spectroscopy (long path-differential optical absorption spectroscopy, referred to as LP-DOAS) and chemical ionization mass spectrometry technology.In three kinds of methods, except DOAS method, other two kinds of methods all need calibration, and the accuracy of scaling system directly has influence on the accuracy of OH radical measuring system.At present, FAGE technology is low by feat of detection limit, background interference is little, can set up the advantages such as mobile actuating device, becomes widely used OH free radical outfield measuring technique.
The air calibrating method of current FAGE technology is conventional following two kinds: the synchronizable optical solution of (1) steam; (2) alkene and ozone reaction method. (1) kind method adopts the synchronous photodissociation H of ultraviolet of 185nm
2o and O
2, produce OH free radical and O
3.By H
2o concentration value, O
3concentration value, O
2concentration value and H
2o and O
2absorption cross section value substitute into formula, calculate OH number of free radical.The O that system is used
2absorption cross section value need be determined by actual measurement, the size of value is relevant with the characteristic of optical path length in measuring process and lamp, so O
2the uncertainty of absorption cross section larger, reach 10%; The uncertainty that the absorption cross section of adding steam is measured and steam and O
3the factors such as the error of the measurement of concentration, the uncertainty of a whole set of calibrating method is greatly about ± 25%.
(2) plants mode O
3produce OH free radical with olefine reaction, calculated the concentration of the OH free radical obtained by steady-state model.The concentration uncertainty of OH free radical is made up of the following aspects: O
3with olefine reaction speed (± 35%), O
3reaction constant (± 20%) and the O of the productive rate (± 15%) of OH free radical, OH free radical and alkene is generated with olefine reaction
3the error (3%) of measurement of concetration.Comprehensive above factor, the uncertainty of a whole set of robot scaling equipment is greatly about ± 43%.
Above two kinds of methods are all the concentration values by calculating OH free radical, and resultant error is larger.
Summary of the invention
The object of the invention is exactly the defect in order to make up prior art, provides a kind of for gas flaring OH Radical Measurement Using Laser Induced Fluorescence Technique scaling system.
The present invention is achieved by the following technical solutions:
A kind of for gas flaring OH Radical Measurement Using Laser Induced Fluorescence Technique scaling system, include wideband light source, steam generating portion, OH free radical generating portion and signals collecting part, described OH free radical generating portion includes aluminum cavity, U-shaped draft tube, multiple reflecting pool, quartz socket tube and high power uviol lamp, gas outlet is had in the bottom of described aluminum cavity, anodization is all done in the inside of aluminum cavity, the right side of aluminum cavity has light inlet and light-emitting window, light inlet and light-emitting window seal by quartz window sheet respectively, the length of described quartz socket tube equals the length of aluminum cavity, the middle part being fixed on aluminum cavity of quartz socket tube level, described U-shaped draft tube is laterally fixed on the inside of aluminum cavity and is looped around around quartz socket tube, described high power uviol lamp is arranged on the inside of quartz socket tube, multiple bleeder vent is had uniformly in the inner side of U-shaped draft tube, described multiple reflecting pool is fixed on the base plate of aluminum cavity, described wideband light source includes xenon lamp, diaphragm and turning mirror group, the light source of xenon lamp is successively through diaphragm, the quartz window sheet of the light inlet of turning mirror group and aluminum cavity enters multiple reflecting pool, roundtrip between multiple reflecting pool, described steam generating portion includes High Purity Nitrogen gas cylinder, mass flowmeter one, mass flowmeter two, mass flowmeter three and water tank, the escape pipe of High Purity Nitrogen gas cylinder divides two-way, the import of one road quality of connection flowmeter three, the inlet end of the quartz socket tube described in outlet connection of mass flowmeter three, nitrogen enters in quartz socket tube the temperature and power stability that keep high power uviol lamp, another road is connected with the import of mass flowmeter one and mass flowmeter two respectively, the outlet of mass flowmeter one connects the air intake opening of water tank, the outlet of mass flowmeter two is connected with the gas outlet of water tank and is connected with the inlet end of U-shaped draft tube, steam is obtained from mass flowmeter two and water tank gas and vapor permeation out, steam enters U-shaped draft tube and is diffused into whole aluminum cavity uniformly from the bleeder vent inside U-shaped draft tube, the photodissociation being subject to high power uviol lamp 185nm line produces OH free radical, xenon lamp light intensity 308nm line in the OH radical pair multiple reflecting pool produced absorbs, xenon lamp light intensity with OH free radical is overflowed from multiple reflecting pool, quartz window sheet through light-emitting window returns al-made chamber external body, described signal acquisition part divides and includes light path turning mirror group, bandpass filter, high resolution spectrometer and computing machine, described light path turning mirror group, bandpass filter and high resolution spectrometer incidence hole are in the same horizontal line, from aluminum cavity effusion xenon lamp light intensity through light path turning mirror group, through bandpass filter, high resolution spectrometer is entered after elimination interference wave, the wavelength of spectrum and intensity signal are recorded by high resolution spectrometer, and be uploaded to computing machine preservation.
The catoptron adopted in described multiple reflecting pool is greater than 99% to 308nm ultraviolet light reflectance.
Described high resolution spectrometer has the resolution of the highest 3.3pm.
The diameter of described bleeder vent is 1mm.
In the present invention, need accordingly to measure spectral intensity when once not having OH free radical, compose as lamp; Spectrum when absorbing there being OH free radical is as measurement spectrum.Carry out least square fitting finally by DOAS method, obtain the concentration of OH free radical.
Advantage of the present invention is: 1, the present invention can integrate the generation of OH free radical and measure, and is measured the OH number of free radical produced, improve the OH number of free radical accuracy of measurement by differential absorption method (DOAS);
2, the present invention adopts optical method for measuring number of free radical, and acquisition system is simple, it is easy to operate to facilitate;
3, the present invention adopts wideband light source, utilize the visible ray in light source as 308nm instruction, adjustment light source, solve multiple reflecting pool light path due to 308nm invisible and be difficult to measure a difficult problem.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention.
Embodiment
As shown in Figure 1, a kind of for gas flaring OH Radical Measurement Using Laser Induced Fluorescence Technique scaling system, include wideband light source, steam generating portion, OH free radical generating portion and signals collecting part, described OH free radical generating portion includes aluminum cavity 8, U-shaped draft tube 9, multiple reflecting pool 11, quartz socket tube 10 and high power uviol lamp, gas outlet is had in the bottom of described aluminum cavity 8, anodization is all done in the inside of aluminum cavity 8, the right side of aluminum cavity 8 has light inlet and light-emitting window, light inlet and light-emitting window seal by quartz window sheet 3 respectively, the length of described quartz socket tube 10 equals the length of aluminum cavity 8, the middle part being fixed on aluminum cavity 8 of quartz socket tube 10 level, described U-shaped draft tube 9 is laterally fixed on the inside of aluminum cavity 8 and is looped around quartz socket tube 10 around, described high power uviol lamp is arranged on the inside of quartz socket tube 10, multiple bleeder vent is had uniformly in the inner side of U-shaped draft tube 9, described multiple reflecting pool 11 is fixed on the base plate of aluminum cavity 8, described wideband light source includes xenon lamp 5, diaphragm 6 and turning mirror group 7, the light source of xenon lamp 5 is successively through diaphragm 6, the quartz window sheet 3 of the light inlet of turning mirror group 7 and aluminum cavity 8 enters multiple reflecting pool 11, at multiple reflecting pool 11 roundtrip, described steam generating portion includes High Purity Nitrogen gas cylinder 1, mass flowmeter one 2-1, mass flowmeter two 2-2, mass flowmeter three 2-3 and water tank 4, the escape pipe of High Purity Nitrogen gas cylinder 1 divides two-way, the import of one road quality of connection flowmeter three 2-3, the inlet end of the quartz socket tube 10 described in outlet connection of mass flowmeter three 2-3, nitrogen enters the temperature and power stability that keep high power uviol lamp in quartz socket tube 10, another road is connected with the import of mass flowmeter one 2-1 and mass flowmeter two 2-2 respectively, the outlet of mass flowmeter one 2-1 connects the air intake opening of water tank 4, the outlet of mass flowmeter two 2-2 is connected with the gas outlet of water tank 4 and is connected with the inlet end of U-shaped draft tube 9, steam is obtained from mass flowmeter two 2-2 and water tank 4 gas and vapor permeation out, steam enters U-shaped draft tube 9 and is diffused into whole aluminum cavity 8 uniformly from the bleeder vent inside U-shaped draft tube 9, the photodissociation being subject to high power uviol lamp 185nm line produces OH free radical, xenon lamp light intensity 308nm line in the OH radical pair multiple reflecting pool 11 produced absorbs, xenon lamp light intensity with OH free radical is overflowed from multiple reflecting pool 11, quartz window sheet 3 through light-emitting window returns to aluminum cavity 8 outside, described signal acquisition part divides and includes light path turning mirror group 12, bandpass filter 13, high resolution spectrometer 14 and computing machine 15, described light path turning mirror group 12, bandpass filter 13 and high resolution spectrometer 14 incidence hole are in the same horizontal line, from aluminum cavity 8 overflow xenon lamp light intensity through light path turning mirror group 12, through bandpass filter 13, high resolution spectrometer 14 is entered after elimination interference wave, the wavelength of spectrum and intensity signal are recorded by high resolution spectrometer 14, and be uploaded to computing machine 15 and preserve.
The catoptron adopted in described multiple reflecting pool 11 is greater than 99% to 308nm ultraviolet light reflectance.
Described high resolution spectrometer 14 has the resolution of the highest 3.3pm.
The diameter of described bleeder vent is 1mm.
In the present invention, need accordingly to measure spectral intensity when once not having OH free radical, compose as lamp; Spectrum when absorbing there being OH free radical is as measurement spectrum.Carry out least square fitting finally by DOAS method, obtain the concentration of OH free radical.
Claims (4)
1. one kind for gas flaring OH Radical Measurement Using Laser Induced Fluorescence Technique scaling system, it is characterized in that: include wideband light source, steam generating portion, OH free radical generating portion and signals collecting part, described OH free radical generating portion includes aluminum cavity, U-shaped draft tube, multiple reflecting pool, quartz socket tube and high power uviol lamp, gas outlet is had in the bottom of described aluminum cavity, anodization is all done in the inside of aluminum cavity, the right side of aluminum cavity has light inlet and light-emitting window, light inlet and light-emitting window seal by quartz window sheet respectively, the length of described quartz socket tube equals the length of aluminum cavity, the middle part being fixed on aluminum cavity of quartz socket tube level, described U-shaped draft tube is laterally fixed on the inside of aluminum cavity and is looped around around quartz socket tube, described high power uviol lamp is arranged on the inside of quartz socket tube, multiple bleeder vent is had uniformly in the inner side of U-shaped draft tube, described multiple reflecting pool is fixed on the base plate of aluminum cavity, described wideband light source includes xenon lamp, diaphragm and turning mirror group, the light source of xenon lamp is successively through diaphragm, the quartz window sheet of the light inlet of turning mirror group and aluminum cavity enters multiple reflecting pool, roundtrip between multiple reflecting pool, described steam generating portion includes High Purity Nitrogen gas cylinder, mass flowmeter one, mass flowmeter two, mass flowmeter three and water tank, the escape pipe of High Purity Nitrogen gas cylinder divides two-way, the import of one road quality of connection flowmeter three, the inlet end of the quartz socket tube described in outlet connection of mass flowmeter three, another road is connected with the import of mass flowmeter one and mass flowmeter two respectively, the outlet of mass flowmeter one connects the air intake opening of water tank, the outlet of mass flowmeter two is connected with the gas outlet of water tank and is connected with the inlet end of U-shaped draft tube, steam is obtained from mass flowmeter two and water tank gas and vapor permeation out, steam enters U-shaped draft tube and is diffused into whole aluminum cavity uniformly from the bleeder vent inside U-shaped draft tube, the photodissociation being subject to high power uviol lamp 185nm line produces OH free radical, xenon lamp light intensity 308nm line in the OH radical pair multiple reflecting pool produced absorbs, xenon lamp light intensity with OH free radical is overflowed from multiple reflecting pool, quartz window sheet through light-emitting window returns al-made chamber external body, described signal acquisition part divides and includes light path turning mirror group, bandpass filter, high resolution spectrometer and computing machine, described light path turning mirror group, bandpass filter and high resolution spectrometer incidence hole are in the same horizontal line, from aluminum cavity effusion xenon lamp light intensity through light path turning mirror group, through bandpass filter, high resolution spectrometer is entered after elimination interference wave, the wavelength of spectrum and intensity signal are recorded by high resolution spectrometer, and be uploaded to computing machine preservation.
2. according to claim 1 for gas flaring OH Radical Measurement Using Laser Induced Fluorescence Technique scaling system, it is characterized in that: the catoptron adopted in described multiple reflecting pool is greater than 99% to 308nm ultraviolet light reflectance.
3. according to claim 1 for gas flaring OH Radical Measurement Using Laser Induced Fluorescence Technique scaling system, it is characterized in that: described high resolution spectrometer has the resolution of the highest 3.3pm.
4. according to claim 1 for gas flaring OH Radical Measurement Using Laser Induced Fluorescence Technique scaling system, it is characterized in that: the diameter of described bleeder vent is 1mm.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104931471A (en) * | 2015-06-08 | 2015-09-23 | 北京大学 | Laser induced fluorescence detection system for active free radicals in air |
| CN105158183A (en) * | 2015-09-08 | 2015-12-16 | 安徽理工大学 | Method for improving sensitivity for detecting NO3 in atmosphere by deducting vapor interference |
| CN105300952A (en) * | 2015-12-02 | 2016-02-03 | 南京先进激光技术研究院 | Atmosphere OH free radical measurement system and method |
| CN106018363A (en) * | 2016-05-17 | 2016-10-12 | 中国科学院合肥物质科学研究院 | Wavelength correction control system for dye laser |
| CN108120681A (en) * | 2017-12-20 | 2018-06-05 | 中国科学院合肥物质科学研究院 | A kind of measurement HO2Transfer efficiency and RO2The apparatus and method for disturbing size |
| CN108169218A (en) * | 2017-12-15 | 2018-06-15 | 中国科学院合肥物质科学研究院 | A kind of hydroxy radical in-situ measurement system |
| CN108333120A (en) * | 2018-01-10 | 2018-07-27 | 中国科学院合肥物质科学研究院 | A kind of synchronous photodissociation H2O and O2Device and correlation technique |
| CN110455735A (en) * | 2019-08-28 | 2019-11-15 | 燕山大学 | A kind of carbon monosulfide absorption cross-section measuring device and method |
| CN110954794A (en) * | 2019-12-11 | 2020-04-03 | 中国科学院力学研究所 | Liquid propellant constant-pressure discharge characteristic parameter measuring device |
| CN111948187A (en) * | 2020-09-18 | 2020-11-17 | 南开大学 | Device and method for detecting free radicals |
| CN113959995A (en) * | 2020-07-20 | 2022-01-21 | 中国科学院化学研究所 | Measuring device and measuring method for hydroxyl free radicals and application thereof |
| CN114216507A (en) * | 2021-12-14 | 2022-03-22 | 苏州科技大学 | OH free radical double-generation system for concentration calibration |
| CN114216507B (en) * | 2021-12-14 | 2024-04-19 | 苏州科技大学 | OH free radical double-generation system for concentration calibration |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104931471A (en) * | 2015-06-08 | 2015-09-23 | 北京大学 | Laser induced fluorescence detection system for active free radicals in air |
| CN105158183A (en) * | 2015-09-08 | 2015-12-16 | 安徽理工大学 | Method for improving sensitivity for detecting NO3 in atmosphere by deducting vapor interference |
| CN105300952B (en) * | 2015-12-02 | 2018-05-25 | 南京先进激光技术研究院 | Atmosphere OH radical measuring system and method |
| CN105300952A (en) * | 2015-12-02 | 2016-02-03 | 南京先进激光技术研究院 | Atmosphere OH free radical measurement system and method |
| CN106018363B (en) * | 2016-05-17 | 2018-10-16 | 中国科学院合肥物质科学研究院 | A kind of wavelength Correction and Control system for dye laser |
| CN106018363A (en) * | 2016-05-17 | 2016-10-12 | 中国科学院合肥物质科学研究院 | Wavelength correction control system for dye laser |
| CN108169218A (en) * | 2017-12-15 | 2018-06-15 | 中国科学院合肥物质科学研究院 | A kind of hydroxy radical in-situ measurement system |
| CN108120681B (en) * | 2017-12-20 | 2020-05-01 | 中国科学院合肥物质科学研究院 | Measurement HO2Conversion efficiency and RO2Apparatus and method for interference magnitude |
| CN108120681A (en) * | 2017-12-20 | 2018-06-05 | 中国科学院合肥物质科学研究院 | A kind of measurement HO2Transfer efficiency and RO2The apparatus and method for disturbing size |
| CN108333120A (en) * | 2018-01-10 | 2018-07-27 | 中国科学院合肥物质科学研究院 | A kind of synchronous photodissociation H2O and O2Device and correlation technique |
| CN110455735A (en) * | 2019-08-28 | 2019-11-15 | 燕山大学 | A kind of carbon monosulfide absorption cross-section measuring device and method |
| CN110455735B (en) * | 2019-08-28 | 2020-09-04 | 燕山大学 | Device and method for measuring absorption cross section of carbon sulfide |
| CN110954794A (en) * | 2019-12-11 | 2020-04-03 | 中国科学院力学研究所 | Liquid propellant constant-pressure discharge characteristic parameter measuring device |
| CN110954794B (en) * | 2019-12-11 | 2022-04-12 | 中国科学院力学研究所 | Liquid propellant constant-pressure discharge characteristic parameter measuring device |
| CN113959995A (en) * | 2020-07-20 | 2022-01-21 | 中国科学院化学研究所 | Measuring device and measuring method for hydroxyl free radicals and application thereof |
| CN113959995B (en) * | 2020-07-20 | 2023-12-26 | 中国科学院化学研究所 | Measuring device, measuring method and application of hydroxyl radical |
| CN111948187A (en) * | 2020-09-18 | 2020-11-17 | 南开大学 | Device and method for detecting free radicals |
| CN114216507A (en) * | 2021-12-14 | 2022-03-22 | 苏州科技大学 | OH free radical double-generation system for concentration calibration |
| CN114216507B (en) * | 2021-12-14 | 2024-04-19 | 苏州科技大学 | OH free radical double-generation system for concentration calibration |
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