CN104596955A - Cavity enhanced absorption spectrum device and method for simultaneous measurement of trace gas concentration and aerosol extinction - Google Patents
Cavity enhanced absorption spectrum device and method for simultaneous measurement of trace gas concentration and aerosol extinction Download PDFInfo
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Abstract
The invention relates to a cavity enhanced absorption spectrum device and method for simultaneous measurement of trace gas concentration and aerosol extinction. The LED temperature is controlled by a semiconductor refrigeration chip to ensure the stability of light intensity output. High reflectivity mirrors at both ends of an optical cavity have the same curvature radius and reflectivity greater than 99.9%, and compose a stable optical resonator. Usually, cavity enhanced absorption spectrum measures the light intensity in the cavity with or without gas absorption and the variation curve of the high reflectivity mirrors' lens reflectivity along with the wavelength, and finally the concentration of absorption gas in the cavity can be obtained. The device and the method provided by the invention can realize simultaneous measurement of trace gas concentration and aerosol extinction. The actual measured total absorption coefficient is divided into two parts, one part is a trace gas absorption structure changing rapidly along with the wavelength, and the other part is gas scattering and aerosol extinction coefficient changing slowly along with the wavelength. Nonlinear least-square fitting is carried out on the measured total absorption coefficient to calculate the concentration of the to-be-measured trace gas, and finally the gas absorption structure and gas scattering are deducted from the total absorption coefficient so as to obtain the aerosol extinction coefficient.
Description
Technical field
The present invention relates to trace gas and aerosol monitoring field, be specifically related to a kind of cavity reinforced absorption spectrum device and method being applied to trace gas concentration and aerosol extinction and measuring simultaneously, be applicable to monitoring trace gas concentration and Aerosol Extinction simultaneously.
Background technology
Along with the fast development of China's economy, urbanization and industrialized acceleration, problem of environmental pollution is also day by day obvious, and the regional air combined pollution problem occurred especially is in the last few years as photochemical pollution, the seriously polluted phenomenon exceeded standard of gray haze fine particle, and atmospheric pollution situation becomes increasingly conspicuous.Environmental monitoring is as the important component part of environmental protection, and the improvement of environmental monitoring technology improves promotion environmental protection and sustainable development important role and meaning.Current China Air Pollutant Discharge is O
3, SO
2, NO
xdeng trace gas and aerosol particle, these noxious pollutants drastically influence the health of people, simultaneously obtain trace gas concentration and aerosol properties significant to Pollution Study.
Research on Cavity Ring Down Spectroscopy obtains trace gas concentration or aerocolloidal extinction coefficient by ranging pulse signal change of ring-down time in optics cavity respectively.Research on Cavity Ring Down Spectroscopy basis grows up cavity reinforced absorption spectrum, adopt sequential filming light source, use the optics cavity be made up of a pair high reflective mirror, realize the effective absorption light path reaching several kilometers with the chamber of about 1m, there is high sensitivity, the advantages such as high time resolution, simplify the requirement such as light source and analytical calculation simultaneously.At present, cavity reinforced absorption spectrum technology has been used successfully to the measurement of multiple trace absorption gas concentration, and less for the research of monitoring trace gas concentration and Aerosol Extinction simultaneously.
Summary of the invention
The technical problem to be solved in the present invention is: in order to make up conventional measurement techniques cannot the survey bureau of simultaneously gas-monitoring trace gas concentration and aerosol extinction sex-limited, the present invention proposes a kind of cavity reinforced absorption spectrum device and method being applied to trace gas concentration and aerosol extinction and measuring simultaneously.
It is as follows that the present invention solves the problems of the technologies described above the technical scheme specifically taked:
Be applied to the cavity reinforced absorption spectrum device that trace gas concentration and aerosol extinction are measured simultaneously, this device comprises: wideband light source, the first lens, second lens, optical filter, diaphragm, first high reflective mirror, the second high reflective mirror, first purges protection gas circuit air intake opening, second purges protection gas circuit air intake opening, sampling gas circuit air intake opening, exhausr port, optical filter, optical fiber, spectrometer and optics cavity, the first high reflective mirror and the second high reflective mirror are installed in optics cavity two ends, the light that wideband light source sends is by after the first collimated, through diaphragm laggard enter optics cavity, light beam absorbs through multiple reflections in optics cavity, optics cavity has the first purging protection gas circuit air intake opening, second purges protection gas circuit air intake opening, sampling gas circuit air intake opening and exhausr port, first purges protection gas circuit air intake opening and second purges protection gas circuit air intake opening below optics cavity, sampling gas circuit air intake opening and exhausr port are above optics cavity, after optical filter and the second Lens Coupling enter optical fiber, spectrometer is transferred to from the optical radiation of optics cavity outgoing, carry out signal transacting.
Further, this device measures trace gas absorption simultaneously and gasoloid extinction meter calculation step is: measurement is obtained total adsorption coefficient and be divided into two parts, a part is make the trace gas absorbing structure of fast change with wavelength, and another part is make slow change gas scattering and Aerosol Extinction with wavelength.Carrying out to measuring the total adsorption coefficient obtained the concentration that nonlinear least square fitting can calculate trace gas to be measured, finally namely obtaining Aerosol Extinction from total adsorption coefficient deduction gas absorption structure and gas scattering.
Further, described wideband light source can be the thermal light sources such as xenon lamp, and light emitting diode (LED) also can be used as light source.
Further, for ensureing the stable of LED light source, LED temperature can be controlled in design temperature by semiconductor chilling plate.
Further, described high reflective mirror radius-of-curvature is identical, reflectivity is greater than 99.9% usually, is fixed on optics cavity two ends and forms stable optical resonator by three-dimensional trim holder, ensures that cavity reinforced absorption spectrum device has higher sensitivity and temporal resolution.
Further, described optical filter is positioned over optics cavity exit end usually, is mainly used in suppressing light beyond the high anti-wave band of high reflective mirror on the impact of measuring.
Further, described optics cavity two ends can increase purging gas circuit to protect high reflective mirror not by the pollution such as particle, gasoloid.
Further, described cavity reinforced absorption spectrum device is monitored while realizing other trace absorption gas concentrations and the aerocolloidal extinction coefficient of corresponding wave band by the high reflective mirror sheet of the wideband light source and the anti-region of corresponding height of replacing corresponding wave band.
The present invention provides a kind of method simultaneously measuring trace gas absorption and aerosol extinction in addition, uses above-mentioned cavity reinforced absorption spectrum device to measure trace gas simultaneously and absorbs and aerosol extinction, comprise the following steps:
Step 1), first carry out the demarcation of reflectance ratio of high reflected mirror with wavelength variations curve, be then filled with high pure nitrogen in chamber and carry out zero absorption background spectrum I
0(λ) measurement, then carries out real atmosphere spectrum I (λ) and measures.
Step 2), according to the ultimate principle of cavity reinforced absorption spectrum, total absorption coefficient (λ) can be expressed as:
Wherein, the lens reflecting rate that R (λ) is high reflective mirror, I
0(λ) represent in chamber light intensity when being filled with pure zero absorption gas and real atmosphere sampling respectively with I (λ), d is that chamber is long.Total absorption coefficient (λ) comprises makes the fast trace gas absorbing structure changed and gas scattering and the Aerosol Extinction of doing slow change with wavelength with wavelength.
Step 3), by with apparatus function convolution after high resolving power standard section and total absorption coefficient do nonlinear least square fitting and obtain trace gas concentration.
Step 4), calculate gas scattering part; Brasseur such as can be directly adopted to calculate at the algorithm that 1986 propose.
Step 5), total absorption coefficient of obtaining deducts the absorption portion structure of trace absorption gas and gas scattering can obtain Aerosol Extinction.
The present invention's advantage is compared with prior art:
(1) apparatus structure that uses of the present invention is relatively simple, can use the LED light source of novel high luminous power, cheap, energy-conserving and environment-protective and the life-span long.
(2) reflectance ratio of high reflected mirror of the present invention's use is higher, and the radius-of-curvature of two panels high reflective mirror is identical, forms stable optical resonator, has higher sensitivity and temporal resolution.
(3) device of the present invention is simple to operate, and automaticity is high, can Real-Time Monitoring trace gas concentration and Aerosol Extinction.
(4) trace gas absorption and Aerosol Extinction can distinguish by the inversion method of the cavity reinforced absorption spectrum device of the present invention's use, can avoid mutual interference, measure while realizing trace gas concentration and aerosol extinction.
(5) the present invention use the replaceable different-waveband light source of device and high reflective mirror, can measure for the Aerosol Extinction of multiple trace gas and different-waveband simultaneously.
Accompanying drawing explanation
Fig. 1 is a kind of basic structure schematic diagram simultaneously measuring the cavity reinforced absorption spectrum device of trace gas absorption and aerosol extinction of the present invention; wherein 1 is wideband light source, and 2,11 is first, second lens, and 3 is diaphragm; 4,9 is first, second high reflective mirror; 5,8 purge protection gas circuit air intake opening for first, second, 6 is sampling gas circuit air intake opening, and 7 is exhausr port; 10 is optical filter; 12 is optical fiber, and 13 is spectrometer, and 14 is optics cavity.
Fig. 2 is the cavity reinforced absorption spectrum calculation procedure schematic diagram simultaneously measuring trace gas absorption and aerosol extinction of the present invention.
Embodiment
Below in conjunction with accompanying drawing, preferred technical scheme of the present invention is described in detail, but protection domain not thereby limiting the invention.
If Fig. 1 is a kind of basic structure schematic diagram of cavity reinforced absorption spectrum device of monitoring trace gas concentration and aerosol extinction simultaneously.Wherein 1 is wideband light source, and 2,11 is first, second lens, and 3 is diaphragm, and 4,9 is first, second high reflective mirror; 5,8 purge protection gas circuit air intake opening for first, second, 6 is sampling gas circuit air intake opening, and 7 is exhausr port; 10 is optical filter, and 12 is optical fiber, and 13 is that spectrometer and 14 is for optics cavity.The light that wideband light source 1 sends enters optics cavity through diaphragm 3 after being collimated by the first lens 2, light beam absorbs through multiple reflections in optics cavity, the first high reflective mirror 4 and the second high reflective mirror 9 is installed at optics cavity 14 two ends, optics cavity 14 has the first purging protection gas circuit air intake opening 5, second purges protection gas circuit air intake opening 8, sampling gas circuit air intake opening 6 and exhausr port 7, first purges protection gas circuit air intake opening 5 and second purges protection gas circuit air intake opening 8 below optics cavity 14, sampling gas circuit air intake opening 6 and exhausr port 7 are above optics cavity 14, after optical filter 10 and the second lens 11 are coupled into optical fiber 12, spectrometer 13 is transferred to from the optical radiation of optics cavity outgoing, carry out signal transacting.Wherein, purge protection gas circuit air intake opening distance high reflective mirror comparatively near, be used for protection high reflective mirror not by the pollution such as particle, gasoloid, optical filter is positioned over optics cavity exit end usually, is mainly used in suppressing light beyond the high anti-wave band of high reflective mirror on the impact of measuring.
LED light source centre wavelength is about 365nm in the present embodiment, and spectral coverage is about 350-385nm, and LED temperature is controlled at 20 ± 0.1 DEG C by semiconductor chilling plate.High reflective mirror producer's nominal reflectivity in 360-385nm wave band is greater than 99.99%, is fixed on optics cavity two ends by adjustment rack.The cavity reinforced absorption spectrum experimental provision of this LED is used to carry out air NO
2measure with while Aerosol Extinction in the concentration of HONO and 360nm-380nm wavelength band.
The demarcation of high reflective mirror lens reflecting rate can adopt the otherness of the Rayleigh scattering of gas with various to demarcate, and the absorption gas of concentration known also can be adopted to demarcate.
When carrying out real atmosphere measurement; connect nitrogen protection gas circuit and protect high reflection mirror, first waiting system passes into the measurement that high pure nitrogen carries out zero absorption background spectrum after stablizing, and then opens aspiration pump; controlled, into chamber flow velocity, to carry out real atmosphere sampling by mass flowmeter.
Cavity reinforced absorption spectrum experimental provision regular automatic Calibration lens reflecting rate can be realized and measure zero absorbing background spectrum by writing Labview program or c language program, and absorb and the cavity reinforced absorption spectrum calculation procedure of aerosol extinction according to measuring trace gas while according to Fig. 2, realize real-time automatic monitoring trace gas concentration and Aerosol Extinction.
Concrete, use cavity reinforced absorption spectrum device of the present invention to measure trace gas simultaneously and absorb and aerosol extinction, mainly comprise following calculation procedure as shown in Figure 2:
Step 1), first carry out the demarcation of reflectance ratio of high reflected mirror with wavelength variations curve, be then filled with high pure nitrogen in chamber and carry out zero absorption background spectrum I
0(λ) measurement, then carries out real atmosphere spectrum I (λ) and measures.
Step 2), according to the ultimate principle of cavity reinforced absorption spectrum, total absorption coefficient (λ) can be expressed as:
Wherein, the lens reflecting rate that R (λ) is high reflective mirror, I
0(λ) represent in chamber light intensity when being filled with pure zero absorption gas and real atmosphere sampling respectively with I (λ), d is that chamber is long.Total absorption coefficient (λ) comprises makes the fast trace gas absorbing structure changed and gas scattering and the Aerosol Extinction of doing slow change with wavelength with wavelength.
Step 3), by with apparatus function convolution after high resolving power standard section and total absorption coefficient do nonlinear least square fitting and obtain trace gas concentration.
Step 4), gas scattering part can directly adopt Brasseur 1986 propose algorithm calculate.
Step 5), total absorption coefficient of obtaining deducts the absorption portion structure of trace absorption gas and gas scattering can obtain Aerosol Extinction.
Non-elaborated part of the present invention belongs to the known technology of those skilled in the art.
Claims (9)
1. the cavity reinforced absorption spectrum device being applied to trace gas concentration and aerosol extinction and measuring simultaneously, it is characterized in that: this device comprises: wideband light source (1), first lens (2), second lens (11), optical filter (10), diaphragm (3), first high reflective mirror (4), second high reflective mirror (9), first purges protection gas circuit air intake opening (5), second purges protection gas circuit air intake opening (8), sampling gas circuit air intake opening (6), exhausr port (7), optical filter (10), optical fiber (12), spectrometer (13) and optics cavity (14), the first high reflective mirror (4) and the second high reflective mirror (9) are installed in optics cavity (14) two ends, the light that wideband light source (1) sends is by after the first lens (2) collimation, through diaphragm (3) laggard enter optics cavity (14), light beam absorbs through multiple reflections in optics cavity (14), optics cavity (14) has the first purging protection gas circuit air intake opening (5), second purges protection gas circuit air intake opening (8), sampling gas circuit air intake opening (6) and exhausr port (7), first purges protection gas circuit air intake opening (5) and second purges protection gas circuit air intake opening (8) in optics cavity (14) below, sampling gas circuit air intake opening (6) and exhausr port (7) are in optics cavity (14) top, after optical filter (10) and the second lens (11) are coupled into optical fiber (12), spectrometer (13) is transferred to from the optical radiation of optics cavity outgoing, carry out signal transacting.
2. cavity reinforced absorption spectrum device according to claim 1, it is characterized in that: measure in this device simultaneously trace gas absorb and gasoloid extinction meter calculation step be: measurement is obtained total adsorption coefficient and is divided into two parts, a part is make the trace gas absorbing structure of fast change with wavelength, and another part is make slow change gas scattering and Aerosol Extinction with wavelength; Carrying out to measuring the total adsorption coefficient obtained the concentration that nonlinear least square fitting can calculate trace gas to be measured, finally namely obtaining Aerosol Extinction from total adsorption coefficient deduction gas absorption structure and gas scattering.
3. cavity reinforced absorption spectrum device according to claim 1, is characterized in that: described wideband light source is the thermal light sources such as xenon lamp, or is light emitting diode.
4. cavity reinforced absorption spectrum device according to claim 1, is characterized in that: for ensureing the stable of LED light source, LED temperature can be controlled at design temperature by semiconductor chilling plate.
5. cavity reinforced absorption spectrum device according to claim 1, it is characterized in that: high reflective mirror radius-of-curvature is identical, reflectivity is greater than 99.9% usually, be fixed on optics cavity two ends by three-dimensional trim holder and form stable optical resonator, ensureing that cavity reinforced absorption spectrum device has higher sensitivity and temporal resolution.
6. cavity reinforced absorption spectrum device according to claim 1, is characterized in that: described optical filter is positioned over optics cavity exit end usually, is mainly used in suppressing light beyond the high anti-wave band of high reflective mirror on the impact of measuring.
7. cavity reinforced absorption spectrum device according to claim 1, is characterized in that: described optics cavity two ends usually adopt and purge gas circuit to protect two panels high reflective mirror not by particle and Aerosol Pollution.
8. cavity reinforced absorption spectrum device according to claim 1, is characterized in that: described cavity reinforced absorption spectrum device is monitored while realizing other trace absorption gas concentrations and the aerocolloidal extinction coefficient of corresponding wave band by the high reflective mirror sheet of the wideband light source and the anti-region of corresponding height of replacing corresponding wave band.
9. measure a method for trace gas absorption and aerosol extinction simultaneously, use the cavity reinforced absorption spectrum device described in claim 1 to measure trace gas simultaneously and absorb and aerosol extinction, it is characterized in that comprising the following steps:
Step 1), first carry out the demarcation of reflectance ratio of high reflected mirror with wavelength variations curve, be then filled with the measurement that high pure nitrogen carries out zero absorption background spectrum I0 (λ) in chamber, then carry out real atmosphere spectrum I (λ) measure;
Step 2), according to the ultimate principle of cavity reinforced absorption spectrum, total absorption coefficient (λ) can be expressed as:
Wherein, the lens reflecting rate that R (λ) is high reflective mirror, I0 (λ) and I (λ) represents in chamber light intensity when being filled with pure zero absorption gas and real atmosphere sampling respectively, d is that chamber is long, total absorption coefficient (λ) comprise and make the trace gas absorbing structure of fast change with wavelength and make gas scattering and the Aerosol Extinction of slow change with wavelength;
Step 3), by with apparatus function convolution after high resolving power standard section and total absorption coefficient do nonlinear least square fitting and obtain trace gas concentration;
Step 4), calculate gas scattering part;
Step 5), total absorption coefficient of obtaining deducts the absorption portion structure of trace absorption gas and gas scattering can obtain Aerosol Extinction.
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