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CN109765185A - A laser photoacoustic spectroscopy detection device using a single photoacoustic cell to measure multi-component gases - Google Patents

A laser photoacoustic spectroscopy detection device using a single photoacoustic cell to measure multi-component gases Download PDF

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CN109765185A
CN109765185A CN201910060515.3A CN201910060515A CN109765185A CN 109765185 A CN109765185 A CN 109765185A CN 201910060515 A CN201910060515 A CN 201910060515A CN 109765185 A CN109765185 A CN 109765185A
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gas
photoacoustic
wavelength
quantum cascade
detection device
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CN109765185B (en
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陈伟根
万福
王有元
杨天荷
王品一
杜林�
谭亚雄
李剑
黄正勇
王飞鹏
周湶
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Beijing Baif Maihak Analytical Instrument Co ltd
Chongqing University
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Chongqing University
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Abstract

A kind of optoacoustic spectroscopy detection device using single photoacoustic cell measurement multicomponent gas, the device includes shut-off valve (1), particulate matter filter device (2), gas drier (3), electromagnetic switch valve one (4), pressure sensor (5), electromagnetic switch valve two (6), sonic nozzle (7), vacuum pump (8), quantum cascade laser array module (9), spectroscope module (10), reference gas chamber (11) to be measured, difference resonates photoacoustic cell (12), acoustic-electric conversion module (13), insulating box (14), optical power detector (15), delustring pond (16), locking phase amplifying circuit (17) and industrial personal computer (18);Multiple laser is coupled in a branch of optical path by the quantum cascade laser array module (9).The arrangement achieves single photoacoustic cells to measure various faults gas composition simultaneously.With strong antijamming capability, equipment long-time stability are good, and precision is high, later period non-maintaining advantage, it can be achieved that measurement trace gas to 100% concentration gases.

Description

A kind of Laser Photoacoustic Spectroscopy detection device using single photoacoustic cell measurement multicomponent gas
Technical field
The invention belongs to optoacoustic spectroscopy gas detection technology fields, more particularly in a kind of electric power, nuclear energy, petrochemical industry The on-line monitoring or off-line detection device of characteristic gas component.
Background technique
It can be decomposed inside the equipment such as power transformer, GIS in electric power/nuclear energy industry and generate the various nature of trouble and absolutely of capable of reacting The gas of edge ageing properties;Accurate detection failure and aging character gas are to realize that important transformer equipment operating status diagnoses It is crucial;The raw material of the basic chemical industries such as ethyl alcohol material and fine chemical product is mainly natural gas, accurate real-time monitoring raw material and production Gas component and content in the process are the cores for guaranteeing above-mentioned quality of chemical products.Accurate detection CO, CO in real time2、CH4(first Alkane), C2H4(ethylene), C2H6(ethane), C2H2(acetylene), H2、SO2F2(bifluoride sulfonyl), CF4(carbon tetrafluoride), SO2、H2S and The gases such as COS (hydroxyl sulphur) are to ensuring that it is important that the industry devices such as electric power, nuclear energy, petrochemical industry operational safety or product quality have Meaning.Traditional detection method has chromatography, electrochemical sensor method, nano-sensor method, absorption spectrometry etc..Wherein chromatography Method needs timing replacement chromatographic column, increases testing cost and manpower loss, cannot achieve the long-term on-line monitoring of equipment;Electrochemistry The gaseous species of sensor method detection and sensitivity are all limited;Nano-sensor method poor repeatability is never effectively solved Certainly.Spectroscopic methodology detection gas is novel detection method popular in recent years, wherein shadow of the absorption spectrometry vulnerable to light scattering, refraction It rings, needs the absorption cell of long light path, and higher cost;Structure is complicated for FTIR spectrum method, and quantitative analysis accuracy needs It improves;Raman spectroscopy detection sensitivity is lower, can not detect trace gas.Optoacoustic spectroscopy detection is a kind of no background measurement side Method, the not influence of light scattering have wide application market in field of gas detection.Its core component is mainly by light source, light The module compositions such as sound conversion pool, acoustical-electrical transducer, ambient noise deduction.But traditional photocaustic spectroscopy shakes vulnerable to ambient enviroment Dynamic, noise, temperature change interference, and the resonant frequency for the photoacoustic cell that resonates can generate drift because of the variation of photoacoustic cell internal gas component It moves.When long-term measurement, impurity and corrosive gas under test gas can pollute corrosion microphone, influence its acoustic characteristic.
The interference that difference type photoacoustic cell can effectively weaken ambient enviroment vibration, noise, temperature change are brought, and under test gas is not It is contacted with acoustical-electrical transducer, it is possible to prevente effectively from the corrosion to acoustical-electrical transducer.Resonance photoacoustic cell can be formed pair in photoacoustic cell The standing wave of photoacoustic signal amplifies, and further increases the detection sensitivity of system, and cylinder resonance photoacoustic cell presses standing wave distribution mode Difference can be divided into longitudinal, angular, radial three kinds of resonance modes, wherein working in the resonance photoacoustic cell pond of longitudinal resonance mode Constant highest is most obvious to the standing wave enlarge-effect of photoacoustic signal.But traditional difference type photoacoustic cell is mostly using single photoacoustic cell Cooperate the mode of single laser, difference type photoacoustic cell is only filled with a kind of calibrating gas of component to be detected, is only able to satisfy single gas The detection of body, system structure can become extremely complex when detection gas type is more.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of on-line monitoring or offline inspection electric power, nuclear energy, petrochemical industries The device of middle characteristic gas component can carry out real-time online prison to electric power, nuclear energy, petrochemical industry characteristic gas component content Survey or offline inspection have while monitoring Multicomponent, do not consume carrier gas, is pollution-free, strong antijamming capability, apparatus simplified, inspection Survey high sensitivity, it is non-maintaining the features such as.The present invention is the mode using quantum cascade laser array, and multiple laser is coupled to In a branch of optical path, and it is real by way of the ratio preliminary filling certain concentration multicomponent gas being absorbed in photoacoustic cell according to gas The function of single difference resonance type photoacoustic cell measurement multicomponent gas is showed.
The technical scheme is that electric power, nuclear energy, petrochemical industry characteristic gas component on-line monitoring or offline inspection system System, it is connected on equipment characteristic gas air hatch to be monitored or extracts the process gas in process of producing product when detection, Particulate matter filter device, gas drier, electromagnetic switch valve one, pressure sensor, reference to be measured are sequentially connected on shut-off valve Gas chamber, electromagnetic switch valve two, sonic nozzle, vacuum pump, characteristic gas to be detected pass sequentially through above-mentioned module and eventually by true Sky pump discharge;Detection device includes quantum cascade laser array module, spectroscope module, reference gas chamber to be measured, difference resonance Photoacoustic cell, acoustic-electric conversion module, insulating box, optical power detector, delustring pond, locking phase amplifying circuit and industrial personal computer.
Above-mentioned quantum cascade laser array module include laser driving and temperature control module, quantum cascade laser array, Light path calibration laser, all-wave length total reflective mirror, specific wavelength total reflective mirror, each quantum cascade laser can be inspired for single Or the super-narrow line width laser of various features gas component absorption peak, and after being focused by condenser lens by specific wavelength total reflective mirror with All-wave length total reflective mirror is injected in spectroscope module after converging to same optical path, the optoacoustic generated by the laser to different wave length Signal carries out the concentration that detection can be finally inversed by each component gas.Light path calibration laser is the laser of naked eyes visible wavelength, same Sample is by injecting spectroscope module after specific wavelength total reflective mirror and the convergence of all-wave length total reflective mirror, for calibrating quantum cascade laser The optical path of array module is not used in excitation under test gas and generates photoacoustic signal, and light path calibration laser is 0.38 μm -0.78 μm of wavelength Visible light.Laser driving and temperature control module can freely adjust the size of electric current, output voltage range according to the actual situation 0-20V exports electric current 0-1A, and current stability is better than 0.1mA, kHz modulation output can be realized as needed, in conjunction with semiconductor system Cooler (TEC) realizes chip temperature control, precisely adjusts chip wavelength.Laser driving and temperature control module in each laser it Between switched over using analog switch mode, to realize different wavelength output.
Above-mentioned quantum cascade laser array can realize that single laser detects the function of more gas compositions, in which:
1) for when detecting electric power, nuclear energy transformer:
The tunable wave length range of the quantum cascade laser one of configuration is 7.10 μm -7.38 μm, and wavelength covers C2H4、CH4、 C2H2The characteristic absorption peak of three kinds of gas, selected C2H4、CH4、C2H2Gas characteristic absorption peak wavelength is located at 7.10 μm, 7.38 μm,7.37μm;
The tunable wave length range of the quantum cascade laser two of configuration is 4.34 μm -4.54 μm, and wavelength covers CO, CO2Two kinds The characteristic absorption peak of gas, selected CO, CO2Gas characteristic absorption peak wavelength is located at 4.54 μm, 4.34 μm;
The wavelength of the quantum cascade laser three of configuration is 3.35 μm, covers C2H6The characteristic absorption peak of gas, selected C2H6Gas Characteristic absorption peak wavelength is located at 3.35 μm.
2) for detecting electric power GIS equipment SF6When decomposing gas:
The wavelength of the quantum cascade laser one of configuration is 7.07 μm, and wavelength covers H2The characteristic absorption peak of S gas, selected H2S Gas characteristic absorption peak wavelength is located at 7.07 μm;
The tunable wave length range of the quantum cascade laser two of configuration is 4.34 μm -4.54 μm, and wavelength covers CO, CO2Two kinds The characteristic absorption peak of gas, selected CO, CO2Gas characteristic absorption peak wavelength is located at 4.54 μm, 4.34 μm;
The tunable wave length range of the quantum cascade laser three of configuration is 7.43 μm -7.87 μm, and wavelength covers SO2、CF4、 SO2F2The characteristic absorption peak of three kinds of gas, selected SO2、CF4、SO2F2Gas characteristic absorption peak wavelength be located at 7.43 μm, 7.79μm、7.87μm。
3) when for detecting gas in the control of petrochemical industry quality of natural gas:
The wavelength of the quantum cascade laser one of configuration is 7.07 μm -7.43 μm, and wavelength covers H2S、SO2The feature of two kinds of gas Absorption peak, selected H2S、SO2Gas characteristic absorption peak wavelength is located at 7.07 μm, 7.43 μm;
The wavelength of the quantum cascade laser two of configuration is 4.34 μm, and wavelength covers CO2The characteristic absorption peak of gas, selected CO2 Gas characteristic absorption peak wavelength is located at 4.34 μm;
The tunable wave length range of the quantum cascade laser three of configuration is 4.83 μm, and wavelength covers the characteristic absorption of COS gas Peak, selected COS gas characteristic absorption peak wavelength are located at 4.83 μm.
4) for detecting petrochemical industry methanol production equipment conversion combined coefficient monitoring gas:
The wavelength of the quantum cascade laser one of configuration is 7.54 μm, and wavelength covers CH4The characteristic absorption peak of gas, selected CH4 Gas characteristic absorption peak wavelength is located at 7.54 μm;
The tunable wave length range of the quantum cascade laser two of configuration is 4.34 μm -4.54 μm, and wavelength covers CO, CO2Two kinds The characteristic absorption peak of gas, selected CO, CO2Gas characteristic absorption peak wavelength is located at 4.54 μm, 4.34 μm;
Quantum cascade laser three can not be configured when detection petrochemical industry methanol production equipment conversion combined coefficient monitoring gas.
The upper spectroscope module includes one piece of semi-transparent semi-reflecting lens and one piece of total reflective mirror, by quantum cascade laser array mould The laser induced breakdown that block is injected is the identical laser of two beam energies.Semi-transparent semi-reflecting lens in spectroscope module are that broadband is semi-transparent semi-reflecting Mirror, or be made of the narrowband semi-transparent semi-reflecting lens turntable that driving motor controls, turntable converts certain wave according to the optical maser wavelength of transmitting The semi-transparent semi-reflecting lens of section.The angle of semi-transparent semi-reflecting lens and total reflective mirror can be manually adjusted by pedestal.
Above-mentioned reference gas chamber to be measured is the chamber of the two identical sizes hollowed out in a square piece, wherein gas chamber to be measured It is the container that under test gas enters detection device.And gas chamber to be measured and reference gas chamber interior walls are coated with gold or nickel, gas chamber to be measured and ginseng It is more identical than air cell size, diameter 5mm-50mm, length 0.1mm-200mm.The reference gas chamber N pure by one preliminary filling of capillary2、 He, Ar or air, in detection SF6It can the pure SF of preliminary filling when decomposing gas and natural gas component6, standard natural gas to be to offset background Interference of the gas absorption spectrum line to gas absorption spectrum line to be measured.
Above-mentioned difference resonance photoacoustic cell is single order longitudinal resonance photoacoustic cell, is the container that photoacoustic signal generates, material is brass Or stainless steel, it is assembled single piece after the chamber for digging out identical size respectively in two square pieces, and two sides The junction of shape part hollows out out the horn-like cavity that can place acoustic-electric conversion module, and the junction diameter of cavity and photoacoustic cell is 1mm-2mm is 10mm-20mm with acoustic-electric conversion module connected component diameter.Its material is brass or stainless steel, and in photoacoustic cell Wall is coated with gold or nickel, and photoacoustic cell diameter is in 5mm-10mm, and for length in 50mm-200mm, draw ratio is greater than or equal to 12:1, and light Sound pond works in first order resonant mode.Difference of the ratio of filled calibrating gas according to absorption peak absorption intensity selected by gas with various It matches, is respectively positioned in the flat response curve of acoustic-electric conversion module, is obtained with the photoacoustce signal intensity for guaranteeing that gas with various generates Obtain wide detection dynamic range.The photoacoustic spectrum signals that system generates may be expressed as:
Wherein S is the photoacoustic spectrum signals intensity generated, and P is excitation light power, and M is the sensitivity of acoustic-electric conversion module, CcellFor photoacoustic cell pond constant, ηiTo absorb the efficiency that luminous energy is converted into thermal energy, αiFor absorbent components rubbing under incentive optical wavelength That absorption coefficient of light, ciFor the concentration for absorbing component, AbFor the generation efficiency of background signal.When modulating frequency is lower than 10kHz, ηiIt can be approximately constant 1.In a determining system: sensitivity M, the photoacoustic cell of excitation light power P, acoustic-electric conversion module Pond constant CcellIt is definite value, therefore is in acoustic-electric conversion module to meet the photoacoustce signal intensity that each gas generates in photoacoustic cell In flat response curve, ciWith αiProduct should be definite value.Difference resonance photoacoustic cell combination above-mentioned theory basis and actual test Afterwards, by two preliminary filling electric power of inflating port, nuclear energy, petrochemical industry individual features gas composition calibrating gas, ratio system Number are as follows:
1) for when detecting electric power, nuclear energy transformer: difference resonance photoacoustic cell passes through two preliminary filling C of inflating port2H4、CH4、C2H2、 CO、CO2、C2H6And N2Seven kinds of gases.Wherein C2H4、CH4、C2H2、CO、CO2、C2H6Ratio it is directly proportional to its absorption coefficient, This six kinds of void fraction proportionality coefficients of preliminary filling are 700:70:50:5:5:1.
2) for detecting electric power GIS equipment SF6When decomposing gas: difference resonance photoacoustic cell passes through two preliminary filling H of inflating port2S、CO、 CO2、SO2、CF4、SO2F2And N2Seven kinds of gases.Wherein H2S、CO、CO2、SO2、CF4、SO2F2Ratio and its absorption coefficient at Direct ratio, this six kinds of void fraction proportionality coefficients of preliminary filling are 60000:80:80:120:1:10.
3) when for detecting gas in the control of petrochemical industry quality of natural gas: difference resonance photoacoustic cell passes through two preliminary filling H of inflating port2S、 SO2、CO2, COS and N2Five kinds of gases.Wherein H2S、SO2、CO2, the ratio of COS it is directly proportional to its absorption coefficient, preliminary filling this Four kinds of void fraction proportionality coefficients are 4000:10:5:1.
4) when for detecting petrochemical industry methanol production equipment conversion combined coefficient monitoring gas: difference resonance photoacoustic cell passes through inflating port Two preliminary filling CH4, CO, CO and N2Four kinds of gases.Wherein CH4、CO、CO2Ratio it is directly proportional to its absorption coefficient, preliminary filling this Three kinds of void fraction proportionality coefficients are 10:1:1.
Above-mentioned acoustic-electric conversion module is the capacitive microphone for detecting difference photoacoustic signal, sensitivity 30mV/Pa.
Above-mentioned insulating box is Resistant heating insulating box, for maintaining temperature in reference gas chamber to be measured and difference resonance photoacoustic cell At 50 DEG C.
Above-mentioned optical power detector is used to detect the power excursion of laser, and laser drift signal Real-time Feedback is driven to laser And temperature control module, by realizing laser driving and the adjustment of temperature control module parameter to quantum cascade laser array output wave Long and energy is modified.
Above-mentioned delustring pond is used to absorb the laser energy for being not used for excitation photoacoustic signal, be full of high concentration in delustring pond with light The congener gas composition in sound pond, and proportionality coefficient is identical with photoacoustic cell.
Above-mentioned locking phase amplifying circuit and industrial personal computer may filter that other than 1kHz-4kHz for extracting specific wavelength frequency signal Noise signal, the noise of conversion to input terminal is 50nV, temperature drift≤10ppm/ DEG C, the amplification factor of amplifier is adjustable model It encloses not less than 104
Detailed description of the invention
Some specific embodiments of the present invention is described in detail by way of example and not limitation below in reference to attached drawing.Attached drawing In identical appended drawing reference denote same or similar part or part.It should be appreciated by those skilled in the art that these attached drawings It is not necessarily drawn to scale.
Fig. 1 is optoacoustic spectroscopy detection device overall structure diagram of the invention.
Fig. 2 is that laser one detects C2H4、CH4、C2H2Wavelength schematic diagram selected by three kinds of gases.
Fig. 3 is that laser two detects CO, CO2Wavelength schematic diagram selected by two kinds of gases.
Fig. 4 is that laser three detects C2H6Wavelength schematic diagram selected by gas.
Appended drawing reference meaning is as follows in figure:
1- shut-off valve, 2- particulate matter filter device, 3- gas drier, 4- electromagnetic switch valve one, 5- pressure sensor, 6- electricity Magnetic switch valve two, 7- sonic nozzle, 8- vacuum pump, 9- quantum cascade laser array module, the driving of 91- laser and temperature control mould Block, 92- quantum cascade laser array, 921- laser one, 922- laser two, 923- laser three, 924- condenser lens One, 925- condenser lens two, 926- condenser lens three, 93- light path calibration laser, 94- all-wave length total reflective mirror, 95- specific wavelength Total reflective mirror one, 96- specific wavelength total reflective mirror two, 97- specific wavelength total reflective mirror three, 98- specific wavelength total reflective mirror four, 10- light splitting Mirror module, 101- semi-transparent semi-reflecting lens, 102- total reflective mirror, 11- reference gas chamber to be measured, 111- air inlet, 112- exhaust outlet, 113- window Mouth piece one, 114- diaphragm two, 115- diaphragm three, 116- diaphragm four, 117- gas chamber to be measured, 118- reference gas chamber, 119- Inflating port one, 12- difference resonance photoacoustic cell, 121- diaphragm five, 122- diaphragm six, 123- diaphragm seven, 124- diaphragm Eight, 125- photoacoustic cell one, 126- photoacoustic cell two, 127- inflating port two, 13- acoustic-electric conversion module, 131- acoustic-electric modulus of conversion block film Piece, 14- insulating box, 15- optical power detector, 16- delustring pond, 17- locking phase amplifying circuit, 18- industrial personal computer.
Specific embodiment
With reference to the accompanying drawings of the specification and specific embodiment, technical solution of the present invention is described in further detail.
Fig. 1 shows one embodiment that the present invention measures the optoacoustic spectroscopy detection device of multicomponent gas using single photoacoustic cell, The embodiment is for detecting Power Transformer Faults characteristic gas component.As shown in Figure 1, the detection device includes shut-off valve 1, Grain object filter device 2, gas drier 3, electromagnetic switch valve 1, pressure sensor 5, electromagnetic switch valve 26, sonic nozzle 7, vacuum pump 8, quantum cascade laser array module 9, spectroscope module 10, reference gas chamber 11 to be measured, difference resonance photoacoustic cell 12, acoustic-electric conversion module 13, insulating box 14, optical power detector 15, delustring pond 16, locking phase amplifying circuit 17, industrial personal computer 18.
In one embodiment, which passes through the one of shut-off valve 1 Side is connected on transformer vacuum degasser, is then turned off on the gas channels of valve 1 and is connected with particulate matter filter device in turn 2, gas drier 3, electromagnetic switch valve 1, pressure sensor 5, reference gas chamber 11 to be measured, electromagnetic switch valve 26, velocity of sound spray Mouth 7, vacuum pump 8, characteristic gas pass sequentially through above-mentioned module and are discharged eventually by vacuum pump 8;Detection device includes quantum stage Join laser array module 9, spectroscope module 10, reference gas chamber 11 to be measured, difference resonance photoacoustic cell 12, acoustic-electric conversion module 13, insulating box 14, optical power detector 15, delustring pond 16, locking phase amplifying circuit 17 and industrial personal computer 18.
The quantum cascade laser array module 9 includes laser driving and temperature control module 91, quantum cascade laser battle array Column 92, light path calibration laser 93, all-wave length total reflective mirror 94, specific wavelength total reflective mirror 95-98.Quantum cascade laser array 92 wraps Include three quantum cascade laser 921-923, each quantum cascade laser 921-923 can inspire for it is single one or more The super-narrow line width laser of transformer decomposed gas component absorption peak, and pass through specific wavelength after being focused by condenser lens 924-926 Total reflective mirror 95-98 and all-wave length total reflective mirror 94 are injected in spectroscope module 10 after converging to same optical path.Quantum cascade laser 921-923 inspires the laser of different wave length, can by the photoacoustic signal that laser of the detection under test gas to different wave length generates To be finally inversed by the concentration of each component under test gas.Light path calibration laser 93 is the laser of naked eyes visible wavelength, is equally passed through Specific wavelength total reflective mirror 95-98 and all-wave length total reflective mirror 94 inject spectroscope module 10 after converging, and swash for calibrating quanta cascade The optical path of light device array module 9 is not used in excitation under test gas and generates photoacoustic signal.In quantum cascade laser array module 9 Laser driving and temperature control module 91 can freely adjust the size of electric current according to the actual situation, output voltage range 0-20V, defeated Electric current 0-1A out, current stability 0.1mA can realize kHz modulation output, in conjunction with semiconductor cooler (TEC) as needed It realizes chip temperature control, precisely adjusts chip wavelength.Laser driving and temperature control mould in quantum cascade laser array module 9 Block 91 switches over each quantum cascade laser 921-923 using analog switch mode, to realize different wavelength output. Specifically, the visible light that the light path calibration laser 93 in quantum cascade laser array module 9 is 0.55 μm of wavelength.All-wave length is complete Anti- mirror 94, specific wavelength total reflective mirror 95-98 angle can be manually adjusted by pedestal.
Quantum cascade laser array 92 in the quantum cascade laser array module 9 can realize that single laser detection is more The function of gas composition, wherein the tunable wave length range of quantum cascade laser 1 is 7.10 μm -7.38 μm, and wavelength is contained Cover C2H4、CH4、C2H2The characteristic absorption peak of three kinds of gas, as shown in Fig. 2, selected C2H4、CH4、C2H2Characteristic absorption peak wavelength point It Wei Yu not be 7.10 μm, 7.38 μm, 7.37 μm;The tunable wave length range of quantum cascade laser 2 922 is 4.34 μm of -4.54 μ M, wavelength cover CO, CO2The characteristic absorption peak of two kinds of gas, as shown in figure 3, selected CO, CO2Characteristic absorption peak wavelength distinguishes position In 4.54 μm, 4.34 μm;The wavelength of quantum cascade laser 3 923 is 3.35 μm, covers C2H6The characteristic absorption peak of gas, such as Shown in Fig. 4, selected C2H6Characteristic absorption peak wavelength is located at 3.35 μm.
The spectroscope module 10 includes one piece of semi-transparent semi-reflecting lens 101 and one piece of total reflective mirror 102, will be by quanta cascade laser The laser induced breakdown that device array module 9 is injected is the identical laser of two beam energies, and the semi-transparent semi-reflecting lens 101 in spectroscope module 10 are Broadband semi-transparent semi-reflecting lens.Semi-transparent semi-reflecting lens 101 and the angle of total reflective mirror 102 can be manually adjusted by pedestal.
The reference gas chamber 11 to be measured is the cylindrical chamber of the two identical sizes hollowed out in a square piece, respectively to Survey gas chamber 117 and reference gas chamber 118.The material of reference gas chamber 11 to be measured is brass, and gas chamber to be measured 117 and reference gas chamber 118 Inner wall is coated with gold, and gas chamber 117 to be measured is identical as 118 size of reference gas chamber, diameter 20mm, length 100mm.Air inlet 111 Positioned at gas chamber to be measured at the 10mm of entering light side, diameter 3mm, long 4mm, gas outlet 112 is located at gas chamber to be measured apart from light emission side At 10mm, diameter 3mm, long 4mm.Diaphragm 1 and diaphragm 2 114 are respectively with corrosion resistant seal glue in gas to be measured The entering light of room 117 and reference gas chamber 118 is surveyed, can be by diaphragm with the laser guaranteed in quantum cascade laser array module 9 Gas chamber 117 to be measured is injected with reference gas chamber 118, diaphragm 3 115 and diaphragm 4 116 use corrosion resistant seal glue respectively In the flash ranging out of gas chamber 117 to be measured and reference gas chamber 118, to guarantee that the laser for passing through gas chamber 117 to be measured and reference gas chamber 118 can To inject in photoacoustic cell 125,126, the material of diaphragm is made of the quartz material of light transmittance >=99%.Reference gas chamber 118 by The pure N of inflating port one 119 preliminary filling2
The difference resonance photoacoustic cell 12 is assembly after the cylindrical chamber for digging out identical size respectively in two square pieces Made of single piece, which forms photoacoustic cell 1, photoacoustic cell 2 126.The junction of two square pieces hollows out The horn-like cavity of acoustic-electric conversion module 13, the company of horn-like cavity and photoacoustic cell 1, photoacoustic cell 2 126 can be placed out Connecing place's diameter is 2mm, is 7mm with 13 connected component diameter of acoustic-electric conversion module.The material of difference resonance photoacoustic cell 12 is brass, And photoacoustic cell 1,2 126 inner wall of photoacoustic cell are coated with gold, photoacoustic cell 1,2 126 diameter of photoacoustic cell are 8mm, and length is 100mm, draw ratio 25:2.Diaphragm 5 121 and diaphragm 6 122 are respectively with corrosion resistant seal glue in photoacoustic cell one 125 survey with the entering light of photoacoustic cell 2 126, with guarantee can be by diaphragm by the laser of gas chamber 117 to be measured and reference gas chamber 118 It injects in photoacoustic cell 1 and photoacoustic cell 2 126, diaphragm 7 123 and diaphragm 8 124 use corrosion resistant seal glue respectively In the flash ranging out of photoacoustic cell 1 and photoacoustic cell 2 126, to guarantee that the laser for passing through photoacoustic cell 1 and photoacoustic cell 2 126 can To inject in optical power detector 15 and delustring pond 16, the material of diaphragm is made of the quartz material of light transmittance >=99%.Difference Resonance photoacoustic cell 12 is divided to pass through 2 127 preliminary filling of inflating port C2H4、CH4、C2H2、CO、CO2、C2H6And N2Seven kinds of gases, and body Product ratio is respectively 7%, 0.7%, 0.5%, 0.05%, 0.05%, 0.01%, 91.69%.
The acoustic-electric conversion module 13 is to be passed using the condenser type of titanium film for detecting difference photoacoustic signal, acoustic-electric conversion module Sensor, the acoustic-electric conversion module 13 are arranged at the central axis of difference resonance photoacoustic cell 12, are connected to photoacoustic cell 1 With the central closing of photoacoustic cell 2 126, junction is bell shape, diameter 7mm at wide opening, diameter 2mm at slot.Acoustic-electric 13 diameter 14mm of conversion module, the use titanium metal material film of acoustic-electric conversion module diaphragm 131, diameter 12mm, 10 μm of thickness.Acoustic-electric Conversion module 13 is dense under test gas to obtain for detecting the difference photoacoustic signal that under test gas generates in two groups of metal tubes The acoustical signal of degree linearly, sensitivity 10mV/Pa-50mV/Pa.
The insulating box 14 is Resistant heating insulating box, and reference gas chamber 11 to be measured places it with difference resonance photoacoustic cell 12 In, to guarantee that reference gas chamber 11 to be measured maintains 50 DEG C with temperature in difference resonance photoacoustic cell 12.
The optical power detector 15 is used to detect the power excursion of laser, and laser drift signal Real-time Feedback is driven to laser Dynamic and temperature control module 91, by realizing laser driving and the adjustment of 91 parameter of temperature control module to quantum cascade laser array 92 output wavelengths and energy are modified.
The delustring pond 16 is used to absorb the laser energy for being not used for excitation photoacoustic signal, is full of high concentration in delustring pond 16 C2H4、CH4、C2H2、CO、CO2、C2H6Six kinds of gases, and volume ratio coefficient is respectively 85%, 7%, 3%, 2%, 2%, 1%.
The locking phase amplifying circuit 17 and industrial personal computer 18 is for extracting specific wavelength frequency signal, locking phase amplifying circuit 17 and work Control machine 18 may filter that the noise signal other than 1kHz-4kHz, and the noise of conversion to input terminal is 50nV, temperature drift≤ 10ppm/ DEG C, the amplification factor adjustable extent of amplifier is not less than 104
Present invention applicant combines Figure of description to be described in detail and describe implementation example of the invention, but ability Field technique personnel it should be understood that more than implement example be only the preferred embodiments of the invention, in detail explanation be intended merely to help Reader is helped to more fully understand spirit of that invention, and it is not intended to limit the protection scope of the present invention, on the contrary, any based on of the invention Any improvement or modification made by spirit should all be fallen within the scope and spirit of the invention.

Claims (28)

1.一种采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,该装置包括截止阀(1)、颗粒物过滤装置(2)、气体干燥装置(3)、电磁开关阀一(4)、压力传感器(5)、电磁开关阀二(6)、音速喷嘴(7)、真空泵(8)、量子级联激光器阵列模块(9)、分光镜模块(10)、待测参比气室(11)、差分共振光声池(12)、声电转换模块(13)、恒温箱(14)、光功率检测器(15)、消光池(16)、锁相放大电路(17)和工控机(18);1. a photoacoustic spectrum detection device that adopts single photoacoustic cell to measure multicomponent gas, it is characterized in that, this device comprises stop valve (1), particle filter device (2), gas drying device (3), electromagnetic switch Valve one (4), pressure sensor (5), electromagnetic switch valve two (6), sonic nozzle (7), vacuum pump (8), quantum cascade laser array module (9), beam splitter module (10), to be tested Reference gas chamber (11), differential resonance photoacoustic cell (12), acousto-electrical conversion module (13), incubator (14), optical power detector (15), extinction cell (16), lock-in amplifier circuit ( 17) and industrial computer (18); 其中,待测气体经过的气路通道依次为截止阀(1)、颗粒物过滤装置(2)、气体干燥装置(3)、电磁开关阀一(4)、压力传感器(5)、待测参比气室(11)、电磁开关阀二(6)、音速喷嘴(7)和真空泵(8);Among them, the gas passages through which the gas to be measured passes are the stop valve (1), the particulate filter device (2), the gas drying device (3), the electromagnetic switch valve one (4), the pressure sensor (5), and the reference to be measured. Air chamber (11), electromagnetic switch valve two (6), sonic nozzle (7) and vacuum pump (8); 激光由量子级联激光器阵列模块(9)产生,经过分光镜模块(10)进入待测参比气室(11),所述量子级联激光器阵列模块(9)将多束激光耦合到一束光路中。The laser light is generated by a quantum cascade laser array module (9), and enters the reference gas chamber (11) to be measured through a beam splitter module (10), and the quantum cascade laser array module (9) couples multiple laser beams into one beam in the light path. 2.如权利要求1所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述量子级联激光器阵列模块(9)包括激光器驱动及温控模块(91)、量子级联激光器阵列(92)、光路校准激光(93)、全波长全反镜(94)和特定波长全反镜(95-98)。2. the photoacoustic spectrum detection device that adopts single photoacoustic cell to measure multicomponent gas as claimed in claim 1 is characterized in that, described quantum cascade laser array module (9) comprises laser drive and temperature control module (91 ), a quantum cascade laser array (92), an optical path calibration laser (93), an all-wavelength total reflection mirror (94) and a specific wavelength total reflection mirror (95-98). 3.如权利要求2所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述量子级联激光器阵列(92)包括多个量子级联激光器和多个聚焦透镜。3. the photoacoustic spectrum detection device that adopts single photoacoustic cell to measure multicomponent gas as claimed in claim 2 is characterized in that, described quantum cascade laser array (92) comprises multiple quantum cascade lasers and multiple focusing lens. 4.如权利要求3所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,量子级联激光器和聚焦透镜均设置为三个,每个量子级联激光器(921-923)激发针对待测气体中单一或多种组分吸收峰的超窄线宽激光,并由聚焦透镜(924-926)聚焦后通过所述特定波长全反镜(95-98)与所述全波长全反镜(94)汇聚到同一光路后射入所述分光镜模块(10)中。4. the photoacoustic spectrum detection device that adopts single photoacoustic cell to measure multicomponent gas as claimed in claim 3 is characterized in that, quantum cascade laser and focusing lens are all set to three, and each quantum cascade laser ( 921-923) to excite an ultra-narrow linewidth laser aiming at the absorption peaks of single or multiple components in the gas to be tested, and focus it by a focusing lens (924-926) and then pass through the specific wavelength total reflection mirror (95-98) and The full-wavelength total reflection mirror (94) is converged into the same optical path and then injected into the beam splitter module (10). 5.如权利要求4所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述量子级联激光器(921-923)之间采用模拟开关模式进行切换,实现不同的波长输出。5. the photoacoustic spectrum detection device that adopts single photoacoustic cell to measure multicomponent gas as claimed in claim 4, is characterized in that, adopts analog switch mode to switch between described quantum cascade lasers (921-923), To achieve different wavelength output. 6.如权利要求2所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述量子级联激光器阵列模块(9)中激光器驱动及温控模块(91)可根据实际情况自由调节电流的大小以及根据需要实现kHz调制输出,结合半导体制冷器实现芯片温度控制,准确调节芯片波长。6. the photoacoustic spectrum detection device that adopts single photoacoustic cell to measure multicomponent gas as claimed in claim 2, is characterized in that, in described quantum cascade laser array module (9), laser drives and temperature control module (91) ) can freely adjust the size of the current according to the actual situation and realize the kHz modulation output according to the needs, realize the chip temperature control and accurately adjust the chip wavelength in combination with the semiconductor refrigerator. 7.如权利要求3所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述量子级联激光器阵列模块(9)中的量子级联激光器阵列(92)可实现单个激光器检测多气体组份的功能,7. the photoacoustic spectrum detection device that adopts single photoacoustic cell to measure multicomponent gas as claimed in claim 3 is characterized in that, the quantum cascade laser array (92) in the described quantum cascade laser array module (9) ) can realize the function of detecting multiple gas components with a single laser, 用于检测变压器时:量子级联激光器一(921)的波长可调谐范围为7.10μm-7.38μm,波长涵盖C2H4、CH4、C2H2三种气体的特征吸收峰,所选C2H4、CH4、C2H2气体特征吸收峰波长分别位于7.10μm、7.38μm、7.37μm;量子级联激光器二(922)的波长可调谐范围为4.34μm-4.54μm,波长涵盖CO、CO2两种气体的特征吸收峰,所选CO、CO2气体特征吸收峰波长分别位于4.54μm、4.34μm;量子级联激光器三(923)的波长为3.35μm,涵盖C2H6气体的特征吸收峰,所选C2H6气体特征吸收峰波长位于3.35μm。When used to detect transformers: the wavelength tunable range of quantum cascade laser one (921) is 7.10μm-7.38μm, and the wavelength covers the characteristic absorption peaks of C 2 H 4 , CH 4 , and C 2 H 2 three gases. The characteristic absorption peak wavelengths of C 2 H 4 , CH 4 , and C 2 H 2 gases are located at 7.10 μm, 7.38 μm, and 7.37 μm, respectively; the wavelength tunable range of quantum cascade laser two (922) is 4.34 μm-4.54 μm, and the wavelengths cover The characteristic absorption peaks of CO and CO 2 gases, the wavelengths of the selected CO and CO 2 gas characteristic absorption peaks are located at 4.54 μm and 4.34 μm respectively; the wavelength of quantum cascade laser three (923) is 3.35 μm, covering C 2 H 6 The characteristic absorption peak of the gas, the wavelength of the characteristic absorption peak of the selected C 2 H 6 gas is located at 3.35 μm. 8.如权利要求3所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述量子级联激光器阵列模块(9)中的量子级联激光器阵列(92)可实现单个激光器检测多气体组份的功能,8. the photoacoustic spectrum detection device that adopts single photoacoustic cell to measure multicomponent gas as claimed in claim 3 is characterized in that, the quantum cascade laser array (92) in the described quantum cascade laser array module (9) ) can realize the function of detecting multiple gas components with a single laser, 用于检测GIS装备SF6分解气体时:量子级联激光器一(921)的波长为7.07μm,波长涵盖H2S气体的特征吸收峰,所选H2S气体特征吸收峰波长位于7.07μm;量子级联激光器二(922)的波长可调谐范围为4.34μm-4.54μm,波长涵盖CO、CO2两种气体的特征吸收峰,所选CO、CO2气体特征吸收峰波长分别位于4.54μm、4.34μm;量子级联激光器三(923)的波长可调谐范围为7.43μm-7.87μm,波长涵盖SO2、CF4、SO2F2三种气体的特征吸收峰,所选SO2、CF4、SO2F2气体特征吸收峰波长分别位于7.43μm、7.79μm、7.87μm。When used to detect SF 6 decomposed gas in GIS equipment: the wavelength of quantum cascade laser one (921) is 7.07μm, the wavelength covers the characteristic absorption peak of H 2 S gas, and the wavelength of the selected characteristic absorption peak of H 2 S gas is at 7.07 μm; The wavelength tunable range of quantum cascade laser two (922) is 4.34μm-4.54μm, and the wavelength covers the characteristic absorption peaks of CO and CO 2 gases. The selected CO and CO 2 gas characteristic absorption peak wavelengths are located at 4.54 μm, 4.34μm; the wavelength tunable range of quantum cascade laser three (923) is 7.43μm-7.87μm, the wavelength covers the characteristic absorption peaks of SO 2 , CF 4 , SO 2 F 2 three gases, SO 2 , CF 4 are selected , SO 2 F 2 gas characteristic absorption peak wavelengths are located at 7.43μm, 7.79μm, 7.87μm, respectively. 9.如权利要求3所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述量子级联激光器阵列模块(9)中的量子级联激光器阵列(92)可实现单个激光器检测多气体组份的功能,9. the photoacoustic spectrum detection device that adopts single photoacoustic cell to measure multicomponent gas as claimed in claim 3, is characterized in that, the quantum cascade laser array (92) in described quantum cascade laser array module (9) ) can realize the function of detecting multiple gas components with a single laser, 用于检测石化天然气质量控制中气体时:量子级联激光器一(921)的波长为7.07μm-7.43μm,波长涵盖H2S、SO2两种气体的特征吸收峰,所选H2S、SO2气体特征吸收峰波长分别位于7.07μm、7.43μm;量子级联激光器二(922)的波长为4.34μm,波长涵盖CO2气体的特征吸收峰,所选CO2气体特征吸收峰波长位于4.34μm;量子级联激光器三(923)的波长可调谐范围为4.83μm,波长涵盖COS气体的特征吸收峰,所选COS气体特征吸收峰波长位于4.83μm。When used for gas detection in petrochemical natural gas quality control: the wavelength of quantum cascade laser one (921) is 7.07μm - 7.43μm, and the wavelength covers the characteristic absorption peaks of H 2 S and SO 2 gases. The characteristic absorption peak wavelengths of SO 2 gas are located at 7.07 μm and 7.43 μm, respectively; the wavelength of quantum cascade laser two (922) is 4.34 μm, which covers the characteristic absorption peak of CO 2 gas, and the selected CO 2 gas characteristic absorption peak wavelength is located at 4.34 μm μm; the wavelength tunable range of quantum cascade laser three (923) is 4.83 μm, the wavelength covers the characteristic absorption peak of COS gas, and the wavelength of the selected characteristic absorption peak of COS gas is located at 4.83 μm. 10.如权利要求3所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述量子级联激光器阵列模块(9)中的量子级联激光器阵列(92)可实现单个激光器检测多气体组份的功能,10. the photoacoustic spectrum detection device that adopts single photoacoustic cell to measure multicomponent gas as claimed in claim 3, is characterized in that, the quantum cascade laser array (92) in described quantum cascade laser array module (9) ) can realize the function of detecting multiple gas components with a single laser, 用于检测石化甲醇生产装备转换合成效率时监控气体:量子级联激光器一(921)的波长为7.54μm,波长涵盖CH4气体的特征吸收峰,所选CH4气体特征吸收峰波长位于7.54μm;量子级联激光器二(922)的波长可调谐范围为4.34μm-4.54μm,波长涵盖CO、CO2二种气体的特征吸收峰,所选CO、CO2气体特征吸收峰波长分别位于4.54μm、4.34μm。Used to monitor the conversion and synthesis efficiency of petrochemical methanol production equipment: the wavelength of quantum cascade laser one (921) is 7.54μm, the wavelength covers the characteristic absorption peak of CH 4 gas, and the wavelength of the selected CH 4 gas characteristic absorption peak is located at 7.54 μm ; The wavelength tunable range of quantum cascade laser 2 (922) is 4.34μm-4.54μm, and the wavelength covers the characteristic absorption peaks of CO and CO 2 gases. The wavelengths of the selected CO and CO 2 gas characteristic absorption peaks are respectively located at 4.54 μm , 4.34μm. 11.如权利要求2所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述光路校准激光(93)为肉眼可见波长的激光,其通过所述特定波长全反镜(95-98)与所述全波长全反镜(94)汇聚后射入所述分光镜模块(10)。11. The photoacoustic spectrum detection device for measuring multi-component gases using a single photoacoustic cell according to claim 2, wherein the optical path calibration laser (93) is a laser with a wavelength visible to the naked eye, which passes through the specific The wavelength total reflection mirrors (95-98) converge with the total wavelength total reflection mirror (94) and then enter the beam splitter module (10). 12.如权利要求11所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述光路校准激光(93)为波长0.38μm-0.78μm的可见光。12. The photoacoustic spectrum detection device using a single photoacoustic cell to measure multi-component gas according to claim 11, wherein the optical path calibration laser (93) is visible light with a wavelength of 0.38 μm-0.78 μm. 13.如权利要求2所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述全波长全反镜(94)和所述特定波长全反镜(95-98)的角度可以通过底座进行手动调节。13. The photoacoustic spectrum detection device for measuring multi-component gas using a single photoacoustic cell as claimed in claim 2, wherein the all-wavelength total reflection mirror (94) and the specific wavelength total reflection mirror (95) The angle of -98) can be adjusted manually through the base. 14.如权利要求1所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述的分光镜模块(10)包括一块半透半反镜(101)以及一块全反镜(102),将由量子级联激光器阵列模块(9)射入的激光分解为两束能量相同的激光。14. The photoacoustic spectrum detection device for measuring multi-component gas using a single photoacoustic cell according to claim 1, wherein the spectroscopic module (10) comprises a half mirror (101) and A total reflection mirror (102) decomposes the laser light injected by the quantum cascade laser array module (9) into two laser beams with the same energy. 15.如权利要求14所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述半透半反镜(101)为宽带半透半反镜,或由驱动电机控制的窄带半透半反镜转盘构成,转盘根据发射的激光波长转换特定波段的半透半反镜。15. The photoacoustic spectrum detection device for measuring multi-component gas using a single photoacoustic cell according to claim 14, wherein the half mirror (101) is a broadband half mirror, or is formed by It is composed of a narrow-band half-mirror turntable controlled by a driving motor, and the turntable converts the half-mirror of a specific wavelength band according to the emitted laser wavelength. 16.如权利要求14所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述半透半反镜(101)与所述全反镜(102)的角度可以通过底座进行手动调节。16. The photoacoustic spectrum detection device for measuring multi-component gas using a single photoacoustic cell according to claim 14, characterized in that, the difference between the half mirror (101) and the total mirror (102) The angle can be adjusted manually through the base. 17.如权利要求1所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述的待测参比气室(11)包括待测气室(117)与参比气室(118),待测气体通过进气口(111)进入所述待测气室(117),所述参比气室(118)由充气口一(119)预充N2、He、Ar或空气。17. The photoacoustic spectrum detection device for measuring multi-component gas using a single photoacoustic cell according to claim 1, wherein the reference gas chamber (11) to be measured comprises a gas chamber to be measured (117) With the reference air chamber (118), the gas to be tested enters the test air chamber (117) through the air inlet (111), and the reference air chamber (118) is prefilled with N2 by the air inlet (119). , He, Ar or air. 18.如权利要求1所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述差分共振光声池(12)为一阶纵向共振光声池,用于产生光声信号;所述声电转换模块(13)用于检测该差分光声信号。18. The photoacoustic spectrum detection device using single photoacoustic cell to measure multi-component gas as claimed in claim 1, is characterized in that, described differential resonance photoacoustic cell (12) is a first-order longitudinal resonance photoacoustic cell, using for generating a photoacoustic signal; the acousto-electric conversion module (13) is used for detecting the differential photoacoustic signal. 19.如权利要求18所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,用于检测变压器时:所述差分共振光声池(12)通过充气口二(127)预充C2H4、CH4、C2H2、CO、CO2、C2H6以及N2七种气体,其中C2H4、CH4、C2H2、CO、CO2、C2H6的比例与其吸收系数成正比,预充的这六种气体体积浓度比例系数为700:70:50:5:5:1。19. The photoacoustic spectrum detection device using a single photoacoustic cell to measure multi-component gas as claimed in claim 18, characterized in that, when used to detect a transformer: the differential resonance photoacoustic cell (12) passes through the gas-filled port two. (127) Precharge seven gases of C 2 H 4 , CH 4 , C 2 H 2 , CO, CO 2 , C 2 H 6 and N 2 , wherein C 2 H 4 , CH 4 , C 2 H 2 , CO, The ratio of CO 2 , C 2 H 6 is proportional to its absorption coefficient, and the volume concentration ratio coefficient of the six pre-charged gases is 700:70:50:5:5:1. 20.如权利要求18所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,用于检测变压器时:用于检测GIS装备SF6分解气体时:所述差分共振光声池(12)通过充气口二(127)预充H2S、CO、CO2、SO2、CF4、SO2F2以及N2七种气体,其中C2H4、CH4、C2H2、CO、CO2、C2H6的比例与其吸收系数成正比,预充的这六种气体体积浓度比例系数为60000:80:80:120:1:10。20. The photoacoustic spectrum detection device for measuring multi-component gas using a single photoacoustic cell as claimed in claim 18, characterized in that, when used to detect transformers: when used to detect GIS equipment SF 6 decomposed gas: the differential The resonant photoacoustic cell (12) is pre-filled with seven gases of H 2 S, CO, CO 2 , SO 2 , CF 4 , SO 2 F 2 and N 2 through the gas filling port two (127), wherein C 2 H 4 , CH 4 The ratio of , C 2 H 2 , CO, CO 2 , and C 2 H 6 is proportional to its absorption coefficient, and the volume concentration ratio coefficient of the six pre-charged gases is 60000:80:80:120:1:10. 21.如权利要求18所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,用于检测石化天然气质量控制中气体时:所述差分共振光声池(12)通过充气口二(127)预充H2S、SO2、CO2、COS以及N2五种气体,其中H2S、SO2、CO2、COS的比例与其吸收系数成正比,预充的这四种气体体积浓度比例系数为4000:10:5:1。21. The photoacoustic spectrum detection device using single photoacoustic cell to measure multi-component gas as claimed in claim 18, is characterized in that, when being used to detect gas in petrochemical natural gas quality control: the differential resonance photoacoustic cell (12 ) Pre-charge H 2 S, SO 2 , CO 2 , COS and N 2 five gases through the charging port two (127), wherein the proportion of H 2 S, SO 2 , CO 2 , COS is proportional to its absorption coefficient, and the pre-charge The volume concentration ratio of these four gases is 4000:10:5:1. 22.如权利要求18所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,用于检测石化甲醇生产装备转换合成效率监控气体时:所述差分共振光声池(12)通过充气口二(127)预充CH4、CO、CO以及N2四种气体,其中CH4、CO、CO2的比例与其吸收系数成正比,预充的这三种气体体积浓度比例系数为10:1:1。22. The photoacoustic spectrum detection device for measuring multi-component gas using a single photoacoustic cell as claimed in claim 18, is characterized in that, when detecting the conversion synthesis efficiency monitoring gas of petrochemical methanol production equipment: the differential resonance photoacoustic The pool (12) is pre-filled with four gases of CH 4 , CO, CO and N 2 through the gas inlet two (127), wherein the ratio of CH 4 , CO and CO 2 is proportional to its absorption coefficient, and the volume of these three gases pre-filled The concentration scaling factor is 10:1:1. 23.如权利要求1所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述待测参比气室(11)与所述差分共振光声池(12)放置于所述恒温箱(14)以维持一恒定温度。23. The photoacoustic spectrum detection device of using single photoacoustic cell to measure multicomponent gas as claimed in claim 1, is characterized in that, described reference gas chamber (11) to be measured and described differential resonance photoacoustic cell ( 12) Place in the incubator (14) to maintain a constant temperature. 24.如权利要求2所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述光功率检测器(15)用于检测激光的功率漂移,并将功率漂移信号实时反馈给所述激光器驱动及温控模块(91),通过对所述激光器驱动及温控模块(91)参数的调整实现对所述量子级联激光器阵列(92)输出波长和能量进行修正。24. The photoacoustic spectrum detection device for measuring multi-component gas using a single photoacoustic cell according to claim 2, wherein the optical power detector (15) is used to detect the power drift of the laser, and the power The drift signal is fed back to the laser drive and temperature control module (91) in real time, and the output wavelength and energy of the quantum cascade laser array (92) are adjusted by adjusting the parameters of the laser drive and temperature control module (91). Correction. 25.如权利要求1所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述的消光池(16)用于吸收未用于激发光声信号的激光能量。25. The photoacoustic spectrum detection device for measuring multi-component gas using a single photoacoustic cell as claimed in claim 1, wherein the extinction cell (16) is used for absorbing laser light that is not used to excite the photoacoustic signal energy. 26.如权利要求19-22任一项所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述消光池(16)内充满高浓度的与所述差分共振光声池(12)同种类的气体组份。26. The photoacoustic spectrum detection device for measuring multi-component gas using a single photoacoustic cell according to any one of claims 19-22, wherein the extinction cell (16) is filled with The differential resonance photoacoustic cell (12) has the same gas composition. 27.如权利要求1所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述锁相放大电路(17)和所述工控机(18)用于提取特定波长频率信号,测量频率范围1kHz-4kHz。27. The photoacoustic spectrum detection device for measuring multi-component gases using a single photoacoustic cell according to claim 1, wherein the lock-in amplifier circuit (17) and the industrial computer (18) are used to extract Specific wavelength frequency signal, measuring frequency range 1kHz-4kHz. 28.如权利要求26所述的采用单光声池测量多组分气体的光声光谱检测装置,其特征在于,所述锁相放大电路(17)和所述工控机(18)可过滤掉1kHz-4kHz以外的噪声信号,折算到输入端的噪音为50nV,温度漂移≤10ppm/℃,放大器的放大倍数可调范围不低于10428. The photoacoustic spectrum detection device for measuring multi-component gas using a single photoacoustic cell according to claim 26, wherein the lock-in amplifier circuit (17) and the industrial computer (18) can filter out the For noise signals other than 1kHz-4kHz, the noise converted to the input terminal is 50nV, the temperature drift is less than or equal to 10ppm/℃, and the adjustable range of the amplifier's magnification is not less than 10 4 .
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