Utilize photocaustic spectroscopy to detect the method for sulfuryl fluoride gas residual concentration
Technical field
The invention belongs to the trace gas detection technical field, be specifically related to a kind of method of utilizing photocaustic spectroscopy to detect Determination of Trace Sulfur acyl fluorides gas concentration, be applicable to such as the residual detection of inspection and quarantine fumigating gas.
Background technology
Vikane, molecular formula SO
2F
2, be colourless, odorless under normal temperature and pressure.Vikane has that diffusion permeability is strong, broad spectrum disinfestation, dosage are economized, residual quantity is low, desinsection speed fast, the loose gas time is short, low temperature is easy to use, on germination percentage not impact and the characteristics such as toxicity is lower, therefore be widely used in the survive the winter control of insect, the tree moth dryness insect that lives of warehouse, freighter, container and buildings, reservoir dam, termite control and gardens, for example, in customs inspection quarantine field, vikane is as fumigant, is used for stifling etc. to control, crops and the secondary product of harmful organism.
But residual sulfuryl fluoride gas has certain toxic action to human body, if vikane content surpasses 0.02g/m in air
3, human body can cause nervous centralis impaired after sucking, and causes convulsions, even can cause breath stopped and death when serious.Therefore, we will strictly monitor sulfuryl fluoride gas concentration residual, trace, to ensure personal safety.
Simultaneously, vikane is also a kind of potent greenhouse gases, the serious greenhouse effect that can cause environment, and people need to monitor the vikane of trace, prevent the pollution of the environment.
For the detection of micro-sulfuryl fluoride gas, China's standard has mainly defined three kinds of detection methods: vapor-phase chromatography, thermal conductivity method and infrared detection method.
Aforesaid chromatographic ultimate principle is sample gas to be injected in chromatographic column analyze.The gas sample that contains vikane is carried down by inert carrier gas, slowly by arriving detecting device after chromatographic column, need control the temperature of chromatographic column therebetween so that the gas sample during by chromatographic column classes of compounds separate out asynchronism(-nization) and reach purpose to its separation.Subsequently, obtain its concentration value after will separating out the parameter such as time, area of collection of illustrative plates and the contrast of this compound concentration known collection of illustrative plates by the compound that detecting device obtains.This method is domestic experimental determination vikane method commonly used, its advantage be highly sensitive, antijamming capability good.Shortcoming is can not Site Detection, analysis time is long, bulky, need to rely on and pass into continuously carrier gas.
Aforesaid thermal conductivity method is based on the characteristic that gas with various has different thermal conductivities, detects gas concentration according to the variation of thermal conductivity.The thermal conductivity method core is thermal conductivity sensor, at the inner integrated resistive heater of thermal conductivity sensor.When sulfuryl fluoride gas is flowed through resistance wire, because sulfuryl fluoride gas has certain thermal conductivity, can take away heat to a certain degree, cause the resistance wire temperature to change.The heat that the sulfuryl fluoride gas of variable concentrations is taken away can be different, can cause the resistance wire temperature that different changes occurs, and by detection resistance wire temperature variations, thereby obtains concentration value corresponding to sulfuryl fluoride gas.The advantage of this detection method is highly sensitive; Shortcoming is poor anti jamming capability, and sensor is short serviceable life, needs frequent calibrating instrument.
Aforesaid Infrared Detection Method is to utilize sulfuryl fluoride gas to carry out measurement of concetration in the light absorption of mid infrared region (6.82 ~ 9 μ m), when the infrared light of a branch of constant 6.82~9 μ m when containing the medium of sulfuryl fluoride gas, the energy of light is absorbed by sulfuryl fluoride gas, luminous flux is attenuated, measure the luminous energy that attenuates, can obtain the concentration of sulfuryl fluoride gas.This method is used comparatively general, but also there is the absorption spectra of other gases when measuring due to mid infrared region, moisture for example, carbon dioxide etc., cause accuracy of detection and the lower limit of vikane to be interfered, so the concentration that the method can't the micro-sulfuryl fluoride gas of fine detection.
In view of above-mentioned prior art, be necessary to be explored more preferably the detection method of sulfuryl fluoride gas residual concentration, for this reason, the present invention has done a large amount of and useful research, and technical scheme described below produces under this background.
Summary of the invention
The object of the present invention is to provide a kind of photocaustic spectroscopy to detect the method for sulfuryl fluoride gas residual concentration.Photocaustic spectroscopy is based on the novel spectral technique of optoacoustic effect, is different from traditional infrared spectrum technology, and it is effectively converted into acoustical signal with light signal, and by accurate microphone, the detection computations of voice signal is obtained final gas concentration.Due to the special optical structure of optoacoustic spectroscopy and the specific calculations process in signals collecting, signal processing, make the method energy highly effective gathering faint light acoustical signal, and effectively reject the interference of background signal, be highly suitable for trace gas concentration detection field, and the noiseless detection in complex environment.
The objective of the invention is to complete like this: a kind of device that utilizes photocaustic spectroscopy to detect the sulfuryl fluoride gas residual concentration comprises light source, chopper, optical filter, photoacoustic cell, microphone and infrared humidity sensor; Wherein light source connects chopper, is arranged on photoacoustic cell one side with optical filter; Infrared humidity sensor is arranged on the opposite side of photoacoustic cell; Microphone is arranged on the bottom of photoacoustic cell, and light source sends light source and is transmitted into chopper, cuts light by chopper, forms light modulated; After light modulated shines on optical filter, but form the arrowband modulated spectrum, be irradiated into photoacoustic cell.
A kind of method of utilizing photocaustic spectroscopy to detect the sulfuryl fluoride gas residual concentration said method comprising the steps of:
Step 1, light source adopt non-interference infrared source, cut light and optical filter optical filtering by chopper, obtain the monochromatic light that intensity can be modulated;
Step 2, can modulate spectral illumination the sealing photoacoustic cell in micro-sulfuryl fluoride gas on, be excited after the electromagnetic radiation of sulfuryl fluoride gas molecule absorption, transit to the excited state of higher level, and get back to ground state by stretching vibration and deformation vibration;
Step 3, vibrations cause the rising of gas temperature, and discharge heat energy, and the heat energy of release makes the vikane molecule produce periodically heating by the modulating frequency of light, thereby produces the periodic pressure fluctuation;
Step 4, pressure surge adopt the vibration sensing degree to survey less than the little microphone of silicon of<1dB, and obtain photoacoustic signal by the change-over circuit amplifying signal, photoacoustic signal converts electric signal to by peripheral circuit, by sending into data acquisition circuit after the lock-in amplifier amplification signal in peripheral circuit, calculate at last and complete the vikane residual concentration again.
In a specific embodiment of the present invention, described non-interference heat radiation light source works in 850 degrees centigrade, to obtain larger infrared power density.
In another specific embodiment of the present invention, described optical filter 3 is 860 for wave number, centre wavelength is the narrow band pass filter of 11.6 microns, only the absorption line intensity between wave number 800 to 900 is very low due to steam, and this narrow band pass filter can effectively shield steam and detect the undesired signal that produces for sulfuryl fluoride gas concentration.
In another specific embodiment of the present invention, described microphone is the little formula microphone of silicon.
Compared with prior art, advantage of the present invention is: provide a kind of photocaustic spectroscopy to detect the method for sulfuryl fluoride gas residual concentration.Photocaustic spectroscopy is that light signal is effectively converted into acoustical signal, and by accurate microphone, the detection computations of voice signal is obtained final gas concentration.Due to the special optical structure of optoacoustic spectroscopy and the specific calculations process in signals collecting, signal processing, make the method energy highly effective gathering faint light acoustical signal, and effectively reject the interference of background signal, be highly suitable for trace gas concentration detection field, and the noiseless detection in complex environment.
Description of drawings
Fig. 1 is the present invention's blackbody radiation light source used spectral radiance under different temperatures.
Fig. 2 is the structural representation of equipment therefor of the present invention.
Fig. 3 is steam and the absorption spectrogram of sulfuryl fluoride gas in 400 to 1700 wave-number ranges.
Embodiment:
With non-interference infrared source as light source 1, the narrow band pass filter and the mechanical chopper that coordinate 11.6 microns of centre wavelengths, 860 wave numbers, obtaining the monochromatic light that intensity can modulate is irradiated in the photoacoustic cell 4 of sealing, be excited after the interior gas molecule absorption of electromagnetic radiation of photoacoustic cell 4, transit to the excited state of higher level.The electronic state of molecule, vibrations and rotary state are all quantized.Usually, gas molecule can be got back to ground state by emitting fluorescence or vibrations, and vibrations cause the rising of gas temperature, and transferring energy, are referred to as radiationless relaxation phenomena.The prerequisite that this Non-radiative relaxation processes by generation of vibration occurs is, the relaxation time is than fast many of lifetime of excited state.Attenuation is 10 in the common time of visible light
-7S is 10 at the 10um place
-2s。Be to produce radiationless decay, the relation of relaxation time and pressure is close (die-away time, t and pressure were inversely proportional to) and can under atmospheric pressure produce great changes (10 very
-3– 10
-8S).
Radiation source is modulated to the acoustic frequency that makes the temperature cycle variation, causes the cyclical variation of pressure, this variation can produce voice signal, and in gas detected, this voice signal was detected by highly sensitive microphone.
Utilize the optoacoustic spectroscopy sensor to detect the vikane residual concentration and just be based on this optoacoustic effect, this optoacoustic spectroscopy sensor as shown in Figure 2, comprise: light source 1, chopper 2, optical filter 3, photoacoustic cell 4, microphone 5, infrared humidity sensor 6 and peripheral circuit, wherein light source 1 connects chopper 2; Be embedded in photoacoustic cell 4 one sides with optical filter 3; Infrared humidity sensor 6 is embedded in the opposite side of photoacoustic cell 4; Microphone 5 is embedded in the bottom of photoacoustic cell 4.
light source 1 of the present invention uses non-interference infrared source, and non-interference infrared source sends broad spectrum light source, after broad spectrum light source is transmitted into chopper 2, cuts light by chopper 2, forms light modulated, after this light modulated shines on the optical filter 3 of 11.6 microns, the optical source wavelength scope is filtered, forming wave number is 860, centre wavelength is that monochromatic light that the intensity of 11.6 microns can be modulated is irradiated on the photoacoustic cell 4 of the sealing sulfuryl fluoride gas in interior, be excited after the electromagnetic radiation of sulfuryl fluoride gas molecule absorption, transit to the excited state of higher level, and get back to ground state by vibrations, vibrations cause the rising of gas temperature, and release heat energy, the heat energy that discharges makes the vikane molecule produce periodically heating by the modulating frequency of light, thereby produce the periodic pressure fluctuation, this pressure surge can be surveyed with sensitive microphone 5, and obtain photoacoustic signal by the change-over circuit amplifying signal, photoacoustic signal converts electric signal to by peripheral circuit, again by sending into data acquisition circuit after the lock-in amplifier amplification signal in peripheral circuit, last through type (1) formula (2) formula (3) formula calculates the quantitative test of completing the vikane residual concentration, complete the detection of vikane concentration with this.
The non-interference infrared source that the present invention adopts is operated in 850 degree.The continuous spectrum that IR thermal emitter generally has near blackbody radiation distributes, as shown in Figure 1.Be characterized in the utilizing emitted light spectrum width, easy to use in conjunction with narrow band pass filter, working stability is reliable.When light beam during with audio frequency (tens hertz to several KHz) modulation, air pressure is just modulated with same frequency and form sound wave, for the amplitude A that is operated in the photoacoustic signal under low frequency off-resonance state
0(w)
Be expressed as:
Be wherein the absorption coefficient of gas, Pa is the dividing potential drop of gas, and v is ratio of the molar heat capacities of gas, and v=Cp/Cv, w are the modulating frequency of light, and T is for disappearing the excitation life-span, and I is beam intensity, and wherein r is the radial distance of photon; W is spot radius, and V is the volume of photoacoustic cell 4, and i is imaginary unit.For specific gas, the amplitude of photoacoustic signal is relevant with the factors such as modulating frequency of the light intensity of exciting light and spectral characteristic, photoacoustic cell 4 structures and light.
For optical filter 3 we to select wave number 860, centre wavelength be the narrow band pass filter of 11.6 microns.Absorb the absorption spectrogram of spectrogram and steam as Fig. 3 vikane, the Absorption Line of sulfuryl fluoride gas has relatively high intensity and density in wave number 500 to 550,800 to 900,1250 to 1300,1450 to 1550 base band.And steam only the absorption line intensity between wave number 800 to 900 is very low, be 860 so we select wave number, centre wavelength is that the narrow band pass filter of 11.6 microns can effectively shield the undesired signal that steam detect to produce for sulfuryl fluoride gas concentration.
For photoacoustic cell 4, the present invention uses the disresonance cylindrical structure, in the situation that absorb a little less than gas, can think that light intensity I is evenly distributed in photoacoustic cell 4, i.e. I (r, w)=I (w).The power that light beam is set again is W, I=Wl/V, and wherein l is the length of photoacoustic cell 4, V is volume.Light intensity in formula (1) is carried out can drawing after space integral:
Can be found out by formula (2) formula, the xsect that reduces photoacoustic cell 4 cavitys is conducive to obtain higher photoacoustic signal amplitude.But the installation site of also depending on microphone 5 due to the size of photoacoustic cell 4 more needs to consider the effect of light beam coupling and the collimation adjustment difficulty of light beam.If the too small transverse heat transfer effect that also can make of the volume of photoacoustic cell 4 descends and the excitation life-span T increase that causes disappearing, result reduces photoacoustic signal.The present invention gets photoacoustic cell 4 internal diameter 15 mm in native system, and length is 50 mm, to reduce the coherent noise that is produced because of the window absorption.
For microphone 5, the present invention selects the little microphone of silicon.Because traditional capacitor microphone suppresses ability without any power supply, very little mains fluctuations just will cause intermittent noise.And aspect Machine Design, the conventional condenser microphone not only can detect voice signal, can also detect mechanical vibration, and finally vibration is converted to the low-frequency sound signal, like this, when this type of microphone is placed in vibration environment, vibration will become the main noise source of audio system.The little microphone of the silicon that the present invention uses is to utilize silicon thin film to detect acoustic pressure, it can be on chip an integrated analog to digital converter, form the microphone with numeral output.Compare with traditional capacitor microphone, the little microphone sound pressure level of silicon is high, and chip internal generally has the pre-amplification circuit, so sensitivity is very high; Its Hz-KHz is wide, generally at 100~10KHZ; And distortion is little, total harmonic distortion<1% (at 1KHZ, 500mV p-p); The vibration sensing degree is less than<1dB.In addition, the little microphone of silicon also has excellent anti-emi characteristics, and humidity environment and temperature shock.We are with the little microphonic acoustic-electric conversion coefficient S of this silicon
m(w) can obtain the amplitude A of photoacoustic signal in substitution formula (2)
m(w):
Formula can find out in (3), and the lower photoacoustic signal amplitude of the modulating frequency of light beam is larger, but for general microphone, during w<100 H z, and acousto-electric-index S
m(w) just have obvious decline, when modulating frequency was too low in addition, 1/ f noise of electronic amplification system also obviously increased.Be the intrinsic standoff ratio of gas due to tested concentration C, C=Pa/P
0, this formula substitution formula (3) can be calculated final tested gas concentration.
In sum, technical scheme provided by the invention has high sensitivity, wide dynamic range, high stability, the shielding interference is good and device volume is little strong point.The principle that photocaustic spectroscopy is surveyed vikane need not to add any chemical substance, and this inventive method once dispatch from the factory demarcate calibration after, optical texture is stable, need not to do secondary or repeatedly calibration, has also avoided the shortcoming of electrical conductivity method.Compare with the non-dispersion infrared analytic approach, it is effectively converted into acoustical signal with light signal, and by accurate microphone, the detection computations of voice signal is obtained final gas concentration.Due to the special optical structure of optoacoustic spectroscopy and the specific calculations process in signals collecting, signal processing, make the method energy highly effective gathering faint light acoustical signal, and effectively reject the interference of background signal, be highly suitable for trace gas concentration detection field, and the noiseless detection in complex environment.