Background technology
Vikane, molecular formula SO
2F
2, be colourless, odorless under the 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 gas time of loosing is short, low temperature is easy to use, to germination percentage characteristics such as influence and toxicity is not 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 vikane gas has certain toxic action to human body, if vikane content surpasses 0.02g/m in air
3, after sucking, human body can cause nervous centralis impaired, cause convulsions, when serious even can cause breath stopped and death.Therefore, we want strict monitoring vikane gas concentration residual, trace, to guarantee personal safety.
Simultaneously, vikane also is a kind of potent greenhouse gases, the serious greenhouse effect that can cause environment, and people need monitor the vikane of trace, prevent the pollution of the environment.
At the detection of Determination of Trace Sulfur acyl fluorides 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 the chromatographic column analyze.The gas sample that contains vikane is carried down by inert carrier gas, slowly by arriving detecting device after the 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 be can not on-the-spot detect, analysis time is long, bulky, need to rely on to feed carrier gas continuously.
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 vikane gas is flowed through resistance wire, because vikane gas has certain thermal conductivity, can take away heat to a certain degree, cause the resistance wire temperature to change.Heat that the vikane gas of variable concentrations is taken away can be different, can cause the resistance wire temperature that different changes takes place, and by detecting the resistance wire temperature variations, thereby obtains the concentration value of vikane gas correspondence.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 vikane 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 vikane gas, the energy of light is by the vikane gas absorption, luminous flux is attenuated, measure the luminous energy that attenuates, can obtain the concentration of vikane gas.This method is used comparatively general, but when measuring because also there is the absorption spectra of other gases in 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 this method can't fine detection Determination of Trace Sulfur acyl fluorides gas.
In view of above-mentioned prior art, be necessary to be explored more preferably the detection method of vikane gas residue 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 purpose of this utility model is to provide a kind of photocaustic spectroscopy to detect the device of vikane gas residue 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.Because 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 range, and the noiseless detection in complex environment.
The purpose of this utility model is finished like this: a kind of device that utilizes photocaustic spectroscopy to detect vikane gas residue 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 the optical filter, but form the arrowband modulated spectrum, be irradiated into photoacoustic cell.
In a specific embodiment of the present utility model, described non-interference heat radiation light source works in 850 degrees centigrade, to obtain big infrared power density.
In another specific embodiment of the present utility model, described optical filter is that wave number is 860, centre wavelength is 11.6 microns narrow band pass filter, only the absorption line intensity between wave number 800 to 900 is very low owing to steam, and this narrow band pass filter can effectively shield steam and detect the undesired signal that produces for the vikane gas concentration.
In another specific embodiment of the present utility model, described microphone is the little formula microphone of silicon.
Compared with prior art, the utility model has the advantages that: provide a kind of photocaustic spectroscopy to detect the device of vikane gas residue 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.Because 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 range, and the noiseless detection in complex environment.
Embodiment:
With non-interference infrared source as light source 1, the narrow band pass filter and the mechanical chopper that cooperate 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 behind the gas molecule absorption of electromagnetic radiation in the photoacoustic cell 4, transit to the excited state of higher level.The electronic state of molecule, vibrations and rotary state all are 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 transmit energy, are referred to as radiationless relaxation phenomena.The prerequisite that this radiationless relaxation process that produces by vibration takes place 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.
The utility model light source 1 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 11.6 microns the optical filter 3, the optical source wavelength scope is filtered, forming wave number is 860, centre wavelength is on the vikane gas during monochromatic light that 11.6 microns intensity can be modulated is irradiated in the photoacoustic cell 4 of sealing, be excited behind the vikane gas molecule absorption of electromagnetic radiation, 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, by sending into data acquisition circuit behind the lock-in amplifier amplification signal in the peripheral circuit, last through type (1) formula (2) formula (3) formula calculates the quantitative test of finishing the vikane residual concentration, finishes the detection of vikane concentration with this again.
The non-interference infrared source that the utility model adopts is operated in 850 degree.The continuous spectrum that the infrared emanation light source generally has near blackbody radiation distributes, as shown in Figure 1.Be characterized in that emission spectrum is wide, 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 and form sound wave with same frequency, for the amplitude that is operated in the photoacoustic signal under the low frequency off-resonance state
Be expressed as:
Wherein be the absorption coefficient of gas, Pa is the dividing potential drop of gas,
Be the specific heat ratio of gas,
=Cp/Cv,
Be the modulating frequency of light,
For disappearing the excitation life-span, 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, modulating frequency of the amplitude of photoacoustic signal and the light intensity of exciting light and spectral characteristic,
photoacoustic cell 4 structures and light etc. is all multifactor relevant.
For optical filter 3 we to select wave number 860, centre wavelength be 11.6 microns narrow band pass filter.As the absorption spectrogram of Fig. 3 vikane absorption spectrogram and steam, the vikane absorption lines of gases has higher relatively 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 11.6 microns narrow band pass filter can effectively shield the undesired signal that steam detect to produce for the vikane gas concentration.
For photoacoustic cell 4, the utility model uses the disresonance cylindrical structure, under situation about absorbing a little less than the gas, can think that light intensity I is evenly distributed in photoacoustic cell 4, namely I (r, w)=I (w).The power that light beam is set again is W, I=Wl/V then, and wherein l is the length of photoacoustic cell 4, V is volume.Light intensity in the formula (1) is carried out can drawing after the space integral:
By formula (2) formula as can be seen, the xsect that reduces
photoacoustic cell 4 cavitys is conducive to obtain higher photoacoustic signal amplitude.But because the size of
photoacoustic cell 4 also depends on the installation site of
microphone 5, more need to consider the effect of light beam coupling and the collimation adjustment difficulty of light beam.The transverse heat transfer effect is descended and cause disappearing the excitation life-span if the volume of
photoacoustic cell 4 is too small
Increase, the result reduces photoacoustic signal.The present invention gets
photoacoustic cell 4 internal diameters 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 utility model is selected 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 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 height, and chip internal generally has pre-amplifying 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 of this silicon
Can obtain the amplitude of photoacoustic signal in the substitution formula (2)
:
As can be seen, the more low photoacoustic signal amplitude of the modulating frequency of light beam is more big in the formula (3), but for general microphone, during w<100 H z, and acousto-electric-index
Just have obvious decline, when modulating frequency was too low in addition, 1/ f noise of electronic amplification system also obviously increased.Because tested concentration C is the intrinsic standoff ratio of gas, C=Pa/P
0, this formula substitution formula (3) can be calculated final tested gas concentration.
In sum, the technical scheme that provides of the utility model 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.Because 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 range, and the noiseless detection in complex environment.