CN108333120A - A kind of synchronous photodissociation H2O and O2Device and correlation technique - Google Patents
A kind of synchronous photodissociation H2O and O2Device and correlation technique Download PDFInfo
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- CN108333120A CN108333120A CN201810023738.8A CN201810023738A CN108333120A CN 108333120 A CN108333120 A CN 108333120A CN 201810023738 A CN201810023738 A CN 201810023738A CN 108333120 A CN108333120 A CN 108333120A
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- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—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
- G01N21/27—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using photo-electric detection ; circuits for computing concentration
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Abstract
The invention discloses a kind of synchronous photodissociation H2O and O2Device, including flow duct, light path and light intensity detection unit, photodissociation unstrpped gas feed unit and absorb gas feed unit；The photodissociation unstrpped gas feed unit is connected to the flow duct；The light path and light intensity detection unit include light source, photo-electric conversion element and light intensity absorption pond, the light source is located at the radial direction opposite sides of the flow duct with the photo-electric conversion element, the light intensity absorption pond is between the light source and the flow duct, the light that the light source is sent out passes through the light intensity absorption pond and the flow duct to be radiated on the photo-electric conversion element, and the absorption gas feed unit is connected to the light intensity absorption pond.The present invention is passed through the absorption gas of various concentration into light intensity absorption pond to adjust the intensity size of incident ray by absorption gas feed unit, and the actinic absorption emitted light source may be implemented without being brought greater impact to oxygen absorption section.
Description
Technical field
The present invention relates to atmospheric monitoring fields, relate in particular to a kind of synchronous photodissociation H2O and O2Device and related side
Method.
Background technology
In troposphere photochemistry, OH and HO2Free radical plays crucial role, is the oxidability for weighing air
One index exists with Brownish haze problem and closely contacts.OH free radicals have higher activity, can in other air
Trace gas react such as CO, VOCs, SO2, NOx etc..Since the short concentration of OH radical lifes is low, (OH free radicals are dense in air
Degree 106cm-3), the accurate concentration for measuring OH free radicals is always the challenging work in one, Atmospheric Chemistry field.Currently,
Mainly there are gas flaring laser Induced Fluorescence Technology (FAGE), CIMS, difference absorption spectrum technology using probing survey technology
(DOAS) etc..FAGE technologies become application by feat of detection limit is low, background interference is small, can establish the advantages that mobile actuating device
Extensive OH free radicals outfield measuring technique.
Currently, FAGE detection systems need to improve the accuracy of detection by scaling experiment, calibrating method has following three kinds:
1) direct method of measurement directly measures photodissociation H2The luminous flux and photolysis period of O calculates the concentration of OH free radicals, and calibration is not known
Degree is ± 32% or so；2) alkene and ozone reaction generate OH free radicals, and the concentration of OH free radicals, OH are calculated by steady-state model
The concentration uncertainty of free radical is about ± 43%；3) box reaction method (continuously stirred are persistently stirred
Tank reactor, CSTR), the lasting stirring being made by Teflon FEP materials at one Jing Guo ultraviolet radioactive is box
In reactor, the concentration of OH free radicals is disappeared by synchro measure hydro carbons (Hydrocarbon, abbreviation HC) and OH radical reactions
Rate is consumed to calculate (Hard et al.1986；Chan et al.1990), the calibration uncertainty of this method is ± 36%
Left and right.
Wherein, the synchronizable optical solution of steam because its uncertainty it is low, the uncertainty of calibration is easy to outer ± 23% or so
Calibration the features such as current FAGE detection systems primary calibration method.
Meanwhile going deep into air HOx free-radical chemistry researchs, observation condition turns to high dirt from clean atmosphere area
Air or Urban Areas (Report of the International HOx Workshop 2015) are contaminated, to ensure complexity
The accuracy of HOx free radicals measurement data under atmospheric conditions, needs higher calibration accuracy and more frequent calibration number.From
From the point of view of the result of synchronizable optical solution calibration, ozone concentration measurement, oxygen absorption section, water vapor absorption section and steam rely on
The factor constitutes the main source of systematic uncertainty.
Invention content
Technical problem to be solved by the invention is to provide one kind can be used for the calibration of FAGE detection systems, and accuracy is higher
Synchronous photodissociation H2O and O2Device and its correlation technique.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that：A kind of synchronous photodissociation H2O and O2Device,
Including flow duct, light path and light intensity detection unit, photodissociation unstrpped gas feed unit and absorb gas feed unit；The light
Solution unstrpped gas feed unit is connected to the flow duct；
The light path and light intensity detection unit include light source, photo-electric conversion element and light intensity absorption pond, the light source with
The photo-electric conversion element is located at the radial direction opposite sides of the flow duct, and the light intensity absorption pond is located at the light
Between source and the flow duct, the absorption gas feed unit is connected to the light intensity absorption pond, the light that the light source is sent out
Line passes through the light intensity absorption pond and the flow duct to be radiated on the photo-electric conversion element.
Further, device further includes covering on the flow duct and the light path and the shading shell outside light intensity detection unit
Body.
Further, device further includes purge gass feed unit, and the purge gass feed unit connects with the shading shell
It is logical.
Further, light intensity absorption pond upper edge is respectively equipped with air inlet and outlet perpendicular to the both sides of optical path direction
Mouthful, the absorption gas feed unit is connected to through the air inlet with the light intensity absorption pond.
Further, the light path and light intensity detection unit further include setting the light intensity absorption pond and the light source it
Between the first condenser lens, the optical filter that is arranged between the light intensity absorption pond and first condenser lens and setting exist
Diaphragm between the lamp source and first condenser lens.
Further, the light path further includes being arranged in the photo-electric conversion element and the flowing with light intensity detection unit
The second condenser lens between pipe.
Further, the photodissociation unstrpped gas feed unit includes zero air reservoir and steam generating mechanism, described
Zero air reservoir is connected to by pipeline with the flow duct, has one section of trouble to be divided into two branch pipes parallel with one another on the pipeline
Road, on the steam generating mechanism bye-pass installed therein.
One of correlation technique provided by the invention is to use above-mentioned synchronous photodissociation H2O and O2Device carry out ozone concentration survey
The method of amount, includes the following steps：
(1) it opens lamp source and photodissociation unstrpped gas is passed through into flow duct by photodissociation unstrpped gas feed unit, then
The absorption gas of various concentration is passed through into light intensity absorption pond by absorption gas feed unit to adjust the intensity of incident ray
Size obtains the concentration data of multigroup ozone generated in flow duct under different incident ray intensity, it is strong to establish incident ray
The functional relation of degree and ozone concentration；
(2) via the functional relation established ozone concentration is finally inversed by by measuring incident ray intensity.
Correlation technique provided by the invention second is that using above-mentioned synchronous photodissociation H2O and O2Device carry out FAGE detection system
System determines calibration method, includes the following steps：
(1) lamp source is opened, is passed through the photodissociation of different vapour concentrations into flow duct by photodissociation unstrpped gas feed unit
Unstrpped gas obtains the concentration numbers of multigroup OH free radicals generated in flow duct under the photodissociation unstrpped gas of different vapour concentrations
According to establishing the concentration of OH free radicals and the functional relation of vapour concentration, obtain FAGE detection systems calibration curve one；
(2) lamp source is opened, photodissociation unstrpped gas is passed through into flow duct by photodissociation unstrpped gas feed unit, is then led to
Cross absorb gas feed unit be passed through into light intensity absorption pond various concentration absorption gas it is big come the intensity for adjusting incident ray
It is small, the concentration data of multigroup OH free radicals generated in flow duct under different incident ray intensity is obtained, OH free radicals are established
Concentration and incident ray intensity functional relation, obtain FAGE detection systems calibration curve two；
In the above process, the concentration calculation formula of OH free radicals is as shown in following formula 1：
Wherein,For H2The absorption cross-section of O,For O2Absorption cross-section,For incident ray intensity, [H2O] be
H2The concentration of O, [O2] it is O2Concentration.
Further,Obtaining means it is as follows：Lamp source is opened, is passed through into flow duct containing oxygen, without steam
Admixture of gas, wherein oxygen concentration is identical as atmospheric oxygen concentration, is calculated according to formula shown in formula 2 Obtaining means it is as follows：Lamp source is opened, is passed through into flow duct containing steam, not oxygenous admixture of gas, according to
Formula is calculated shown in formula 2
Wherein, [m] represents H2O or O2Concentration, m=H2O or O2；I0Indicate that incident intensity, I indicate to penetrate admixture of gas
Light intensity later, l represent optical thickness.
Beneficial effects of the present invention are embodied in：
In apparatus of the present invention, flow duct is used to provide flowing and the photolysis place of photodissociation unstrpped gas, for
It when FAGE detection systems are calibrated, can be connected with FAGE detection systems, photodissociation unstrpped gas feed unit will be for that will include H2O and O2
Photodissociation unstrpped gas be passed through in flow duct, the present invention is not to change incident ray by being directly changed the emissive porwer of light source
Intensity, but incident ray intensity is changed by the cooperation of light intensity absorption pond and absorption gas feed unit, particular by
It absorbs gas feed unit and is passed through the absorption gas of various concentration into light intensity absorption pond to adjust the intensity size of incident ray,
This regulative mode, the actinic absorption that may be implemented to emit light source is without bringing oxygen absorption section larger shadow
It rings, to more accurate.
The method that ozone concentration of the present invention measures goes out the concentration of ozone by measuring the inversion method of light intensity, for outfield reality
Standard inspection has great convenience surely, can meet nA grades of photoelectricity flow measurement needs, can accurately measure dim light light intensity, and pass through
Ozone and the functional relation of light intensity are accurately finally inversed by low ozone concentration value, solve existing ozone analyzer since detection limits
In 0.5ppb, the defect that ozone can not be measured accurately under conditions of strong compared with dim light.
FAGE detection systems of the present invention determine calibration method due to the provision of two calibration curves, therefore by calibrating two
Curve be mutually authenticated can, promoted calibration accuracy.For calibration curve one, OH is adjusted by changing vapour concentration in calibration process
Number of free radical, but the fluorescent quenching that high vapour concentration can increase OH free radicals influences the sensitivity of FAGE systems, and curve
Second is that keeping the vapour concentration inflexible OH free radicals for overregulating light intensity and obtaining various concentration under the conditions of low vapour concentration, will determine
Mark song line one is compared to each other with curve two can correct the shadow that high vapour concentration observes FAGE system calibratings and OH free radicals
It rings.
Description of the drawings
Fig. 1 is the structural schematic diagram of one embodiment of the invention.
In attached drawing the label of each component be：1 light source, 2 first condenser lenses, 3 optical filters, 4 light intensity absorption ponds, 5 second are gathered
Focus lens, 6 photo-electric conversion elements, 7 flow ducts, 8 ozone analyzers, 9 shading shells, 10FAGE detection systems, zero air of 11-1
Storage tank, 11-2 absorb gas reservoir, 11-3 purgings gas storage tank, 12 flowmeters, 13 Hygrothermographs, 14 steam generating mechanisms.
Specific implementation mode
The present invention will be described in detail below with reference to the accompanying drawings and embodiments.It should be noted that in the feelings not conflicted
Under condition, the features in the embodiments and the embodiments of the present application can be combined with each other.
Referring to Fig. 1.
The present invention synchronizes photodissociation H2O and O2Device, including flow duct 7, light path and light intensity detection unit, photodissociation unstripped gas
Object supply unit and absorption gas feed unit；The photodissociation unstrpped gas feed unit is connected to the flow duct 7；
The light path and light intensity detection unit include light source 1, photo-electric conversion element 6 and light intensity absorption pond 4, the light source
1 is located at the radial direction opposite sides of the flow duct 7 with the photo-electric conversion element 6, and the light intensity absorption pond 4 is located at
Between the light source 1 and the flow duct 7, the absorption gas feed unit is connected to the light intensity absorption pond 4, the light source
1 light sent out passes through the light intensity absorption pond 4 and the flow duct 7 to be radiated on the photo-electric conversion element 6.
In the present invention, flow duct 7 provides flowing and the photolysis place of photodissociation unstrpped gas, is being detected for FAGE
It when 10 calibration of system, can be connected with FAGE detection systems 10, photodissociation unstrpped gas feed unit will be for that will include H2O and O2Photodissociation
Unstrpped gas is passed through in flow duct 7, in order to improve precision, generally can be used the mixed gas of zero air and steam, light path with
Light intensity detection unit is used to provide the intensity of light and detection light, and most important one thes improvement is that the present invention does not pass through
The emissive porwer of light source 1 is directly changed to change incident ray intensity, but list is supplied with gas is absorbed by light intensity absorption pond 4
The cooperation of member changes incident ray intensity, and into light intensity absorption pond 4 difference is passed through particular by gas feed unit is absorbed
The absorption gas of concentration adjusts the intensity size of incident ray, and photo-electric conversion element 6 can receive and measure incident ray intensity.
Although the emissive porwer by adjusting light source 1 can change the power of incident ray, lamp source transmitting is also resulted in
Some changes occur for lamp source spectral composition, lead to the oxygen absorption alternation of cross-section, and use this regulative mode of the present invention, then can be with
Actinic absorption emit to light source is realized without being brought greater impact to oxygen absorption section, to more accurately.
In the present invention, photodissociation unstrpped gas feed unit and absorption gas feed unit are for supply gas, now
There is supply gas in technology there is no technology barrier, there are very more ripe realization methods, the present invention not to repeat, the example only in figure
Show that a kind of structure is as follows：Photodissociation unstrpped gas feed unit include zero air reservoir 11-1 and steam generating mechanism 14, zero
Air reservoir 11-1 is connected to by pipeline with flow duct 7, has one section of trouble to be divided into two bye-passes parallel with one another, steam on pipeline
On 14 installed therein bye-passes of generating mechanism, the photodissociation unstrpped gas of this structure is simply easily implemented, and can be square
Just the concentration of steam is adjusted, is installed for convenience of monitoring, on two bye-passes and is separately installed with flowmeter 12, zero air reservoir
Hygrothermograph 13 is installed on the pipeline between 11-1 and flow duct 7；It includes absorbing gas reservoir 11- to absorb gas feed unit
2, it absorbs gas reservoir 11-2 and is connected to light intensity absorption pond 4 also by pipeline, similarly, for convenience of controlling, absorb gas reservoir
Flowmeter is also installed on the pipeline between 11-2 and light intensity absorption pond 4, in specific implementation, gas is absorbed and selects N2O, effect is more
It is good.
Steam generating mechanism 14 is existing equipment, can directly commercially available acquisition.Zero air is led in steam generating mechanism 14
The generation of bubbling method is crossed, water was controlled respectively by two mass flowmenters and only water gas flow velocity adjusts vapour concentration, and
Entering the full and uniform mixing in flow duct front end.It is needed zero air when use device measures the absorption cross-section of steam
It changes and makees high-purity N2, need to close steam generating mechanism when measuring oxygen absorption section.
In one embodiment, device further includes covering on the flow duct 7 and the light path and the screening outside light intensity detection unit
Bare hull body 9.Shading shell 9 is interfered for eliminating ambient, and the part is made to be operated under conditions of darkroom, improves precision,
In specific implementation, shading shell 9 uses aluminum material, effect reliable and light；In addition, to shading shell 9 carry out anodization and
Blackening process is done what cavity progress blackening process can effectively absorb in light path that mixed and disorderly scattering light reduces that ambient light brings
It disturbs；Anodization is carried out, the anticorrosive and wear-resisting property of aluminum cavity is increased.
In one embodiment, device further includes purge gass feed unit, the purge gass feed unit and the shading shell
Body 9 is connected to.It designs in this way, purge gass can be passed through into shading shell 9 by purge gass feed unit, to drive away in light path
O2、H2O and other interference gas, while to blow away the surrounding air heated by mercury lamp, keeping stabilized intensity and extending the mercury lamp longevity
Life；Similarly, purge gass feed unit also has very more ripe realization methods, and it is as follows that a kind of structure is only exemplified in figure：It blows
Scavenging feed unit includes purging gas storage tank 11-3, and purging gas storage tank 11-3 is connected to by pipeline with shading shell 9, similarly,
For convenience of control, purges and flowmeter is installed on the pipeline between gas storage tank 11-3 and shading shell 9, in specific implementation, purging
Gas selects high-purity N2So that entire light path is in N (except photodissociation region and light intensity absorption pond)2Environment in, effect is more preferable.
In one embodiment, 4 upper edge of light intensity absorption pond perpendicular to the both sides of optical path direction be respectively equipped with air inlet and
Gas outlet, the absorption gas feed unit are connected to through the air inlet with the light intensity absorption pond 4.This design in this way can be with
Accurately control absorbs the size of light path, while air-flow can eliminate surface local turbulence with respect to stabilization and be disturbed to what light was brought
It is dynamic.
In specific implementation, light inlet and light-emitting window is respectively set in the both ends of 4 upper edge light path of light intensity absorption pond, in light inlet and
Light-emitting window is sealed entire light intensity absorption pond 4 using window, and light beam transversal passes through light intensity absorption pond 4.
In one embodiment, the present invention selects mercury lamp as light source 1, sends out the light of 185nm.H2O can be in 185nm light
Irradiation under effectively decompose and generate OH free radicals and H2O free radicals, in specific implementation, low pressure pen type mercury lamp of the present invention, low pressure
Pen type mercury lamp is considered as cylinder light source 1, and pen type mercury lamp is easily installed and replaces, and the 185nm light for including in radiation spectrum simultaneously can be with
Meet and generates the required stabilized intensity degree of low concentration OH free radicals.
In one embodiment, the light path and light intensity detection unit further include setting the light intensity absorption pond 4 with it is described
The first condenser lens 2 between light source 1, the optical filter being arranged between the light intensity absorption pond 4 and first condenser lens 2
3 and the diaphragm that is arranged between the lamp source and first condenser lens 2.Diaphragm is for limiting lighting area and diverging
Angle, the first condenser lens 2 are used to light being organized into approximately parallel light beam, and optical filter 3 is for filtering out the radiation of its all band
The interference of light.
In specific implementation, keep the light that light source 1 is sent out incident perpendicular to gas flow duct 7, light path is handed over gas flow duct 7
Equitant part is photodissociation region, and is completed to H in photodissociation region2O and O2Photodissociation generate certain density HOx (OH,
HO2) free radical and O3。
In one embodiment, the light path further includes being arranged in the photo-electric conversion element 6 and institute with light intensity detection unit
State the second condenser lens 5 between flow duct 7.Second condenser lens 5, which is used to that photoelectricity will to be converged to by the light in photodissociation region, to be turned
It changes on the photosurface of element 6.Photo-electric conversion element 6 can select photoelectric tube.
In one embodiment, device further includes light intensity detection circuit and low-pass filter circuit.Light intensity detection circuit and low
Bandpass filter circuit is existing common circuit, connects and using being techniques known, this will not be repeated here.Light
The light intensity signal of strong detection circuit output is transferred data to using a high-precision analog-digital converter at computer
Reason.The luminous flux measurement of high s/n ratio may be implemented in light intensity detection circuit, accurately reflects the variation of incident ray intensity.
The error of stabilization and the light intensity quantization of light intensity is all the key factor for influencing absorption cross-section measurement accuracy, to mercury lamp
Surrounding purging " purge gass " drives the gas heated by mercury lamp away, and ensures that the enough small generation turbulent flows that is unlikely to of purge gass show
As；Low-pass filter circuit is added in the circuit of design, filters out the power supply of mercury lamp to giving off electromagnetic interference in the air；It is protecting
It demonstrate,proves nA grades of photoelectric current amplifications 3 × 10 in the case of higher signal-to-noise ratio8Times, using the high-precision analog of 12 low zero noises
Digital quantizer converts photoelectric current to the manageable digital signal of computer.
The present invention calculates the gas reaction for being specially designed internal diameter 20cm, length 60cm according to modeling and relevant parameter
Flow duct 7 is passed through N into flow duct 72、O2And H2The gaseous mixture of O.In photodissociation region to 10 gas sampling mouth of FAGE detection systems
In section, the flow velocity of gas reaches 20L/min and so that air-flow is laminar flow in flow duct 7；And transmission time it is enough it is few without
It can be influenced by chemical loss and free radical mixing.In specific implementation, to ensure the light maximum transmission of deep ultraviolet band, entirely
Lens, window and flow duct are all made of the material making of JGS1 in light path.
In specific implementation, the present invention is based on Labview software programming environment to write synchronous photodissociation calibration software, and software includes
Two bottom modules of control and intensity collection of mass flowmenter, ozone concentration measurement, oxygen absorption section gauge, H2O absorbs
Section gauge and FAGE detection systems 10 demarcate four function modules.
One of correlation technique provided by the invention is to use above-mentioned synchronous photodissociation H2O and O2Device carry out ozone concentration survey
The method of amount, includes the following steps：
(1) it opens lamp source and photodissociation unstrpped gas is passed through into flow duct 7 by photodissociation unstrpped gas feed unit, then
The absorption gas of various concentration is passed through into light intensity absorption pond 4 by absorption gas feed unit to adjust photo-electric conversion element 6
The intensity size of the incident ray measured is received, acquisition is multigroup (according to specific required precision determination group number, in general, to organize number
Much, more accurate) concentration data of ozone that is generated in flow duct 7 under different incident ray intensity, establish incident ray intensity
With the functional relation of ozone concentration；
Ozone concentration can be measured by ozone analyzer 8, and incident ray intensity can be received by photoelectric conversion element 6
Further measured by light intensity detection circuit；
(2) via the functional relation established ozone concentration is finally inversed by by measuring incident ray intensity.
It is verified repeatedly by experiment, what the ozone concentration that ozone analyzer measurement obtains was obtained with light intensity detection circuit measurement
Light intensity numerical value has certain functional relation, also means that the concentration that can go out ozone by measuring the inversion method of light intensity,
There is great convenience for outfield experiments calibration.Due to the Flow Field Distribution in flow duct 7 present center flow velocity it is fast, close to pipe
The slow feature of wall flow velocity, ozone concentration is uneven along 7 radial distribution of flow duct, and air-flow (about total gas of only middle section
The 5% of stream) it is calibrated, while commercial ozone analyzer is since detection limit is in 0.5ppb, ozone under conditions of strong compared with dim light
It can not accurately measure, and can then meet nA grades by photo-electric conversion element, light intensity detection circuit and low-pass filter circuit
Photoelectricity flow measurement needs, and can accurately measure dim light light intensity, and is accurately finally inversed by by ozone and the functional relation of light intensity low
Ozone concentration value.
Correlation technique provided by the invention second is that using above-mentioned synchronous photodissociation H2O and O2Device carry out FAGE detection system
System determines calibration method, includes the following steps：
(1) lamp source is opened, is passed through the photodissociation of different vapour concentrations into flow duct 7 by photodissociation unstrpped gas feed unit
Unstrpped gas obtains the concentration of multigroup OH free radicals generated in flow duct 7 under the photodissociation unstrpped gas of different vapour concentrations
Data establish the concentration of OH free radicals and the functional relation of vapour concentration, obtain FAGE detection systems calibration curve one；
(2) lamp source is opened, photodissociation unstrpped gas is passed through into flow duct 7 by photodissociation unstrpped gas feed unit, then
The absorption gas of various concentration is passed through into light intensity absorption pond 4 by absorption gas feed unit to adjust photo-electric conversion element 6
The intensity size of the incident ray measured is received, obtains multigroup OH generated in flow duct 7 under different incident ray intensity certainly
By the concentration data of base, the functional relation of the concentration and incident ray intensity of OH free radicals is established, it is fixed to obtain FAGE detection systems
Mark song line two；
In the above process, the concentration calculation formula of OH free radicals is as shown in following formula 1：
Wherein,For H2The absorption cross-section of O,For O2Absorption cross-section,For incident ray intensity, [H2O] be
H2The concentration of O, [O2] it is O2Concentration.
WithIt is widely measured, the prior art is not repeated herein in the prior art.
The present invention due to the provision of two calibration curves, therefore by by two calibration curves be mutually authenticated can, it is fixed to be promoted
Mark accuracy.For calibration curve one, OH number of free radical is adjusted by changing vapour concentration in calibration process, but high steam
Concentration can increase the sensitivity of the fluorescent quenching influence FAGE systems of OH free radicals, and curve is second is that under the conditions of low vapour concentration
The inflexible OH free radicals for overregulating light intensity and obtaining various concentration of vapour concentration are kept, calibration curve one and curve two are mutually compared
Compared with the influence that can be corrected high vapour concentration and observe FAGE system calibratings and OH free radicals.
But synchronous photodissociation H2O and O2Scaling method in important error source be exactlyWithIndeterminacy, in order to
Precision is improved, in one embodiment, using the synchronous photodissociation H of the present invention2O and O2Device voluntarily obtainWith's
Obtaining means are as follows：Lamp source is opened, the admixture of gas containing oxygen, without steam is passed through into flow duct, wherein oxygen is dense
Degree is identical as atmospheric oxygen concentration, is calculated according to formula shown in formula 2Obtaining means it is as follows：It opens
Lamp source is passed through containing steam, not oxygenous admixture of gas into flow duct, is calculated according to formula shown in formula 2
WithIt is calculated based on Beear-Lambert laws, the ratio and incident light that light is absorbed by transparent medium
Intensity it is unrelated；Per the light of blanket layer Absorption of Medium same ratio value on light path, specifically it is represented by shown in following formula 2：
Wherein, [m] represents H2O or O2Concentration, m=H2O or O2；I0Indicate that incident intensity, I indicate to penetrate admixture of gas
Light intensity later, l represent optical thickness；Specifically, it will be passed through and eliminate O2And H2When the photodissociation unstrpped gas of O, photoelectric conversion element
Part receives the incident ray intensity measured as I0, will be passed through admixture of gas containing oxygen, without steam or containing steam,
Photo-electric conversion element receives the incident ray intensity light intensity measured as I, according to formula meter after not oxygenous admixture of gas
It obtains.
Since the different mercury lamp measurements section that is absorbed has a certain difference, oxygen Schumann-Runge bands are very
Close to 185nm, the spectral composition at mercury lamp 185nm, which varies slightly, all causes absorption cross-section to change, even identical pen shape mercury
Lamp supply current it is different also can pair cross-section measurement be also not quite similar, and pen type mercury lamp has certain service life, and it is fixed to need
Phase is replaced, therefore the present invention is the error for reducing absorption cross-section and bringing, and increases the step of absorption cross-section measures in a device.Make
The absorption cross-section that corresponding mercury lamp can be easily and effectively measured with the device, is further reduced the error of calibration experiment.
It should be understood that example as described herein and embodiment are not intended to restrict the invention, this field only for explanation
Technical staff can make various modifications or variation according to it, all within the spirits and principles of the present invention, made by it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of synchronous photodissociation H2O and O2Device, it is characterised in that：Including flow duct, light path and light intensity detection unit, photodissociation
Unstrpped gas feed unit and absorption gas feed unit；The photodissociation unstrpped gas feed unit connects with the flow duct
It is logical；
The light path and light intensity detection unit include light source, photo-electric conversion element and light intensity absorption pond, the light source with it is described
Photo-electric conversion element is located at the radial direction opposite sides of the flow duct, the light intensity absorption pond be located at the light source with
Between the flow duct, the absorption gas feed unit is connected to the light intensity absorption pond, and the light that the light source is sent out is worn
It crosses the light intensity absorption pond and the flow duct is radiated on the photo-electric conversion element.
2. synchronous photodissociation H as described in claim 12O and O2Device, it is characterised in that：Device further includes covering on the flowing
Pipe and the light path and the shading shell outside light intensity detection unit.
3. synchronous photodissociation H as claimed in claim 22O and O2Device, it is characterised in that：Device further includes that purge gass supply is single
Member, the purge gass feed unit are connected to the shading shell.
4. the synchronization photodissociation H as described in claims 1 or 2 or 32O and O2Device, it is characterised in that：On the light intensity absorption pond
Along air inlet and gas outlet is respectively equipped with perpendicular to the both sides of optical path direction, the absorption gas feed unit is through the air inlet
It is connected to the light intensity absorption pond.
5. the synchronization photodissociation H as described in claims 1 or 2 or 32O and O2Device, it is characterised in that：The light path is visited with light intensity
Unit is surveyed to further include the first condenser lens being arranged between the light intensity absorption pond and the light source, be arranged and inhale in the light intensity
Optical filter between receives pond and first condenser lens and it is arranged between the lamp source and first condenser lens
Diaphragm.
6. the synchronization photodissociation H as described in claims 1 or 2 or 32O and O2Device, it is characterised in that：The light path is visited with light intensity
It further includes the second condenser lens being arranged between the photo-electric conversion element and the flow duct to survey unit.
7. the synchronization photodissociation H as described in claims 1 or 2 or 32O and O2Device, it is characterised in that：The photodissociation unstrpped gas
Feed unit includes zero air reservoir and steam generating mechanism, and zero air reservoir is connected by pipeline and the flow duct
It is logical, there is one section of trouble to be divided into two bye-passes parallel with one another, one installed therein of the steam generating mechanism on the pipeline
On the bye-pass.
8. using such as synchronous photodissociation H described in any item of the claim 1 to 82O and O2Device carry out ozone concentration measurement
Method, it is characterised in that：Include the following steps：
(1) it opens lamp source and photodissociation unstrpped gas is passed through into flow duct by photodissociation unstrpped gas feed unit, then pass through
It absorbs gas feed unit and is passed through the absorption gas of various concentration into light intensity absorption pond to adjust the intensity size of incident ray,
The concentration data for obtaining multigroup ozone generated in flow duct under different incident ray intensity, establish incident ray intensity with it is smelly
The functional relation of oxygen concentration；
(2) via the functional relation established ozone concentration is finally inversed by by measuring incident ray intensity.
9. using such as synchronous photodissociation H described in any item of the claim 1 to 82O and O2Device to carry out FAGE detection systems fixed
Calibration method, it is characterised in that：Include the following steps：
(1) lamp source is opened, is passed through the photodissociation raw material of different vapour concentrations into flow duct by photodissociation unstrpped gas feed unit
Gas obtains the concentration data of multigroup OH free radicals generated in flow duct under the photodissociation unstrpped gas of different vapour concentrations,
The concentration of OH free radicals and the functional relation of vapour concentration are established, FAGE detection systems calibration curve one is obtained；
(2) lamp source is opened, photodissociation unstrpped gas is passed through into flow duct by photodissociation unstrpped gas feed unit, then passes through suction
Getter object supply unit is passed through the absorption gas of various concentration into light intensity absorption pond to adjust the intensity size of incident ray, obtains
The concentration data for taking multigroup OH free radicals generated in flow duct under different incident ray intensity, establishes the concentration of OH free radicals
With the functional relation of incident ray intensity, FAGE detection systems calibration curve two is obtained；
In the above process, the concentration calculation formula of OH free radicals is as shown in following formula 1：
Wherein,For H2The absorption cross-section of O,For O2Absorption cross-section,For incident ray intensity, [H2O] it is H2O's
Concentration, [O2] it is O2Concentration.
10. synchronous photodissociation H as claimed in claim 92O and O2Device carry out FAGE detection systems determine calibration method, feature
It is：Obtaining means it is as follows：Lamp source is opened, the admixture of gas containing oxygen, without steam is passed through into flow duct,
Wherein, oxygen concentration is identical as atmospheric oxygen concentration, is calculated according to formula shown in formula 2 Obtaining means
It is as follows：Lamp source is opened, is passed through into flow duct containing steam, not oxygenous admixture of gas, according to formula meter shown in formula 2
It obtains
Wherein, [m] represents H2O or O2Concentration, m=H2O or O2；I0Indicate that incident intensity, I are indicated through after admixture of gas
Light intensity, l represents optical thickness.
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