CN108760653A - A kind of method that spectrometer accurately measures concentration of SO 2 gas - Google Patents

A kind of method that spectrometer accurately measures concentration of SO 2 gas Download PDF

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CN108760653A
CN108760653A CN201810320284.0A CN201810320284A CN108760653A CN 108760653 A CN108760653 A CN 108760653A CN 201810320284 A CN201810320284 A CN 201810320284A CN 108760653 A CN108760653 A CN 108760653A
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laser
speculum
lights
light
sample cell
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CN108760653B (en
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李林军
白云峰
申英杰
潘伟平
许聪
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Heilongjiang Institute of Technology
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    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry

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Abstract

The present invention relates to a kind of methods that dual wavelength narrow spaces accurately measure concentration of SO 2 gas, include the following steps:A branch of pump light is incident to the first resonant cavity, forms the first detection laser;Another beam pump light is incident to the second resonant cavity, forms the second detection laser;First, second detection laser is transmitted directly to sample cell (22), after the sample cell (22) interior multiple reflections, it is projected from the optical emission exit (23) of the sample cell (22), it is converged in absorption spectrometer (25) through adjustable convergent lens (24), the optical signal of reception is converted into electric signal and passes to computer (26) by the spectrometer (25), and computer (26) calculates the measured value N of the first detection laser by analyzing1With the measured value N of the second detection laser2, obtain accurate gas concentration value N.The present invention is measured by using dual wavelength, is mutually carried out pulsewidth check and correction as with reference to standard, is obtained accurate measurement result, and the detection of the lower sulfur dioxide gas of high-precision is met.

Description

A kind of method that spectrometer accurately measures concentration of SO 2 gas
Technical field
The present invention relates to a kind of detection method of concentration of SO 2 gas, especially a kind of dual wavelength narrow spaces are accurately surveyed The method for measuring concentration of SO 2 gas.
Background technology
Industry and business usually require accurately to measure the pernicious gas in certain space, to ensure this space model Enclose interior safety.It is desirable to which the pernicious gas prevented includes SO2、H2S, CO etc..Whether the pernicious gas told meets spy Whether the discharge for determining purity limit and/or these gases meets environment regulations.Such as process control, discharge and environmental monitoring, peace The typical case of full property and air conditioning etc needs accurate measurement of concetration.
Wavelength modulation spectroscopy is a kind of mode of the sensitivity of enhancing gasmetry, especially heavy when measuring smaller concentration It wants.Generally use measures the spectral intensity of incident light and emergent light, calculates the concentration of tested gas.But existing measurement method Precision is not high, still receives in the case of some are of less demanding, but for some to the higher environment of required precision, it is existing Measurement method tend not to accurately measure the harmful gas concentration in the space, therefore, develop a kind of system accurately measured Method very it is necessary to.
Invention content
The present invention measures inaccurate technical problem to solve existing concentration of SO 2 gas.Propose a kind of double wave The method that long narrow spaces accurately measure concentration of SO 2 gas, includes the following steps:
The optical fiber laser 1 that breadth of spectrum line is 0.1nm exports 1064nm linearly polarized lasers, through 1064nm half-reflecting half mirrors 2 It is divided into two beam pump lights;
A branch of pump light is incident to the first resonant cavity, first resonant cavity include the first speculum 4, the second speculum 9, Third speculum 3 and the 4th speculum 10, incident light are transferred to first crystal 8 through the first speculum 4;By adjusting temperature control Device makes the first crystal 8 generate 3980nm ideler frequency lights, 1452nm signal lights;The 3980nm ideler frequency lights, 1452nm signal lights With 1064nm pump lights in first internal oscillation;It further include the first optoisolator the 5, the 1st in first resonant cavity 2 wave plates 6, the first Fabry-Perot etalon 7, first optoisolator 5 control the transmission direction of light, the one 1/2 wave Piece 6 controls the polarization direction of pump light 1064nm laser, and first Fabry-Perot etalon 7 controls 3980nm ideler frequency lights Breadth of spectrum line be 0.0001nm, the 3980nm ideler frequency lights project from the second speculum 9, form first and detect laser;
The first detection laser is transmitted directly to the first entrance port 11 of sample cell 22, in the sample cell 22 repeatedly After reflection, projects, converged in absorption spectrometer 25 through adjustable convergent lens 24, institute from the optical emission exit 23 of the sample cell 22 It states spectrometer 25 optical signal of reception is converted into electric signal and pass to computer 26, using following formula to SO2Gas concentration Calculate and obtains SO2Gas concentration N1,
I(λ1)=A (λ1)I01)eσ1N1+B(L1)(1)
σ in formula1For absorption cross-section of the SO2 gases to be measured in the case where wavelength is 3980nm laser, A (λ1) be first interference because Son, B (L1) it is the second interference factor, I01) it is incident intensity, I (λ1) it is output intensity, L1The light for being laser in sample cell Journey;
Another beam pump light is incident to the second resonant cavity after half-reflecting half mirror 2 is reflected into 1064nm total reflective mirrors 12, described Second resonant cavity includes the 5th speculum 13, the 6th speculum 19, the 7th speculum 14 and the 8th speculum 20, and incident light is through the Five speculums 13 are transferred to the second crystal 16;Second crystal 16 is set to generate 2466nm ideler frequencies by adjusting temperature controller Light, 1871nm signal lights;The 2466nm ideler frequency lights, 1871nm signal lights and 1064nm pump lights shake in second resonant cavity It swings;Further include the second optoisolator 15, the 2nd 1/2 wave plate 17, the second Fabry-Perot etalon in second resonant cavity 18, second optoisolator 15 controls the transmission direction of light, the 2nd 1/2 wave plate 17 control pump light 1064nm laser Polarization direction, the breadth of spectrum line that second Fabry-Perot etalon 18 controls 2466nm ideler frequency lights is 0.0001nm, described 2466nm ideler frequency lights are projected from the 6th speculum 19, form the second detection laser;
The second detection laser is transmitted directly to the second entrance port 21 of sample cell 22, in the sample cell 22 repeatedly After reflection, projects, converged in absorption spectrometer 25 through adjustable convergent lens 24, institute from the optical emission exit 23 of the sample cell 22 It states spectrometer 25 optical signal of reception is converted into electric signal and pass to computer 26, using following formula to SO2Gas concentration Calculate and obtains SO2Gas concentration N2,
σ in formula2For absorption cross-section of the SO2 gases to be measured in the case where wavelength is 2466nm laser, A (λ2) be first interference because Son, B (L2) it is the second interference factor, I02) it is incident intensity, I (λ2) it is output intensity, L2The light for being laser in sample cell Journey;
The computer 26 calculates the measured value N of the first detection laser by analyzing1With the measured value of the second detection laser N2, obtain accurate gas concentration value N.
Further, further include following steps:
Adjustment is under different absorption peaks, the measured value I (λ of different wave length1)、I(λ2), and then determine the first interference factor A (λ1)、A(λ2) value;
Convolution (1) (2) and above-mentioned first interference factor A (λ1)、A(λ2) value SO under different wave length is calculated2Gas Concentration N1、N2
Accurate SO2 gas concentrations N is found out by weighted average.
Further, weighted average coefficients 0.5, i.e. N=0.5N1+0.5N2
Further, by increasing light path L of the detection light in measuring gas1Or L2So that measurement result is more accurate.
Further, temperature control device is controlled by computer, makes control temperature accurately at 0.01 DEG C, to ensure that detection swashs The stability of the wavelength of light, and then ensure to measure the accuracy of concentration.
Beneficial effects of the present invention:The present invention is measured by using dual wavelength, mutually carries out arteries and veins as with reference to standard Width check and correction obtains accurate pulsewidth alignment detection, and by repeatedly measuring, can eliminate corresponding interference factor, and pass through Temperature controller accurately controls detection optical maser wavelength and obtains accurate measurement result, meets the inspection of the lower sulfur dioxide gas of high-precision It surveys.Compared to the measurement of single wavelength, this method is more accurate.
Description of the drawings
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment Attached drawing is briefly introduced, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this For the those of ordinary skill in field, without having to pay creative labor, it can also be obtained according to these attached drawings His attached drawing.
Fig. 1 is the structural schematic diagram of sulfur dioxide gas detection device of the present invention.
Specific implementation mode
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with attached drawing to the present invention make into It is described in detail to one step, it is clear that described embodiments are only a part of the embodiments of the present invention, rather than whole implementation Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts All other embodiment, shall fall within the protection scope of the present invention.
The preferred embodiment that the invention will now be described in detail with reference to the accompanying drawings.
As shown in Figure 1, the present invention measures inaccurate technical problem to solve existing concentration of SO 2 gas.It proposes A kind of method that dual wavelength narrow spaces accurately measure concentration of SO 2 gas, includes the following steps:
The optical fiber laser 1 that breadth of spectrum line is 0.1nm exports 1064nm linearly polarized lasers, through 1064nm half-reflecting half mirrors 2 It is divided into two beam pump lights;
A branch of pump light is incident to the first resonant cavity, first resonant cavity include the first speculum 4, the second speculum 9, Third speculum 3 and the 4th speculum 10, incident light are transferred to first crystal 8 through the first speculum 4;By adjusting temperature control Device makes the first crystal 8 generate 3980nm ideler frequency lights, 1452nm signal lights;The 3980nm ideler frequency lights, 1452nm signal lights With 1064nm pump lights in first internal oscillation;It further include the first optoisolator the 5, the 1st in first resonant cavity 2 wave plates 6, the first Fabry-Perot etalon 7, first optoisolator 5 control the transmission direction of light, the one 1/2 wave Piece 6 controls the polarization direction of pump light 1064nm laser, and first Fabry-Perot etalon 7 controls 3980nm ideler frequency lights Breadth of spectrum line be 0.0001nm, the 3980nm ideler frequency lights project from the second speculum 9, form first and detect laser;
The first detection laser is transmitted directly to the first entrance port 11 of sample cell 22, in the sample cell 22 repeatedly After reflection, projects, converged in absorption spectrometer 25 through adjustable convergent lens 24, institute from the optical emission exit 23 of the sample cell 22 It states spectrometer 25 optical signal of reception is converted into electric signal and pass to computer 26, using following formula to SO2Gas concentration Calculate and obtains SO2Gas concentration N1,
σ in formula1For absorption cross-section of the SO2 gases to be measured in the case where wavelength is 3980nm laser, A (λ1) be first interference because Son, B (L1) it is the second interference factor, I01) it is incident intensity, I (λ1) it is output intensity, L1The light for being laser in sample cell Journey;
Another beam pump light is incident to the second resonant cavity after half-reflecting half mirror 2 is reflected into 1064nm total reflective mirrors 12, described Second resonant cavity includes the 5th speculum 13, the 6th speculum 19, the 7th speculum 14 and the 8th speculum 20, and incident light is through the Five speculums 13 are transferred to the second crystal 16;Second crystal 16 is set to generate 2466nm ideler frequencies by adjusting temperature controller Light, 1871nm signal lights;The 2466nm ideler frequency lights, 1871nm signal lights and 1064nm pump lights shake in second resonant cavity It swings;Further include the second optoisolator 15, the 2nd 1/2 wave plate 17, the second Fabry-Perot etalon in second resonant cavity 18, second optoisolator 15 controls the transmission direction of light, the 2nd 1/2 wave plate 17 control pump light 1064nm laser Polarization direction, the breadth of spectrum line that second Fabry-Perot etalon 18 controls 2466nm ideler frequency lights is 0.0001nm, described 2466nm ideler frequency lights are projected from the 6th speculum 19, form the second detection laser;
The second detection laser is transmitted directly to the second entrance port 21 of sample cell 22, in the sample cell 22 repeatedly After reflection, projects, converged in absorption spectrometer 25 through adjustable convergent lens 24, institute from the optical emission exit 23 of the sample cell 22 It states spectrometer 25 optical signal of reception is converted into electric signal and pass to computer 26, using following formula to SO2Gas concentration Calculate and obtains SO2Gas concentration N2,
σ in formula2For absorption cross-section of the SO2 gases to be measured in the case where wavelength is 2466nm laser, A (λ2) be first interference because Son, B (L2) it is the second interference factor, I02) it is incident intensity, I (λ2) it is output intensity, L2The light for being laser in sample cell Journey;
The computer 26 calculates the measured value N of the first detection laser by analyzing1With the measured value of the second detection laser N2, obtain accurate gas concentration value N.
45 degree faces of the laser through resonator high reflective mirror 4 be coated with 1064nm high thoroughly, 2000-4300nm high-reflecting films, first, Second crystal is Nonlinear M gO:PPLN crystal.
Above-mentioned first detection light, the second detection light pulsewidth are 0.001nm, so that more matching sulfur dioxide gas Absorption peak, it is accurate to absorb, and reduces other interference for absorbing gases, ensure that the accuracy of measurement.By accurately controlling first, The angle and thickness and precision of second Fabry-Perot etalon make it meet the compression of pulsewidth, and usual incident angle control is 45 Degree, thickness 3-4mm.
In addition, further including following steps:
By adjusting spectrometer, make it under different absorption peaks, obtains the measured value I (λ of different wave length1)、I(λ2), into And the first interference factor A (λ are obtained by successive ignition1)、A(λ2) value, computational accuracy 0.001.
In conjunction with formula (1) (2) and above-mentioned first interference factor A (λ1)、A(λ2) value SO under different wave length is calculated2Gas Bulk concentration N1、N2
Accurate SO2 gas concentrations N is found out by weighted average.Weighted average coefficients are between 0.495-0.505, preferably It is 0.5, i.e. N=0.5N1+0.5N2
In further method, by increasing light path L of the detection light in measuring gas1Or L2So that measurement result is more Accurately, L can usually be set1Or L2Length be 0.5-5 meters.
In addition, controlling temperature control device by computer, make control temperature accurately at 0.01 DEG C, to ensure to detect laser The stability of wavelength, and then ensure to measure the accuracy of concentration.
Breadth of spectrum line is that the testing laser of two wavelength of 3980.0nm and 2466.0nm of 0.1pm tests SO2 gases simultaneously, For the laser of one wavelength as testing light source, the laser of another wavelength, which is used as, refers to light source, not only can effectively distinguish a variety of SO2 gases are effectively identified in gas, and can also improve the precision of test gas to 0.1ppb.
The absorption intensity value for testing latter two SO2 gas is shown on computer software, compares SO2 gas standard intensity Value, using spectrometer as the scaled values of means of testing, so that it may to obtain the concentration of SO2 gases.
Beneficial effects of the present invention:The present invention is measured by using dual wavelength, mutually carries out arteries and veins as with reference to standard Width check and correction obtains accurate pulsewidth alignment detection, and by repeatedly measuring, can eliminate corresponding interference factor, and pass through Temperature controller accurately controls detection optical maser wavelength and obtains accurate measurement result, meets the inspection of the lower sulfur dioxide gas of high-precision It surveys.
The apparatus embodiments described above are merely exemplary, wherein the unit illustrated as separating component can It is physically separated with being or may not be, the component shown as unit may or may not be physics list Member, you can be located at a place, or may be distributed over multiple network units.It can be selected according to the actual needs In some or all of module achieve the purpose of the solution of this embodiment.
Finally it should be noted that:The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations;Although Present invention has been described in detail with reference to the aforementioned embodiments, it will be understood by those of ordinary skill in the art that:It still may be used With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features; And these modifications or replacements, various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution spirit and Range.

Claims (5)

1. a kind of method that dual wavelength narrow spaces accurately measure concentration of SO 2 gas, it is characterised in that include the following steps:
The optical fiber laser (1) that breadth of spectrum line is 0.1nm exports 1064nm linearly polarized lasers, through 1064nm half-reflecting half mirrors (2) It is divided into two beam pump lights;
A branch of pump light is incident to the first resonant cavity, first resonant cavity include the first speculum (4), the second speculum (9), Third speculum (3) and the 4th speculum (10), incident light are transferred to first crystal (8) through the first speculum (4);Pass through adjusting Temperature controller makes the first crystal (8) generate 3980nm ideler frequency lights, 1452nm signal lights;The 3980nm ideler frequency lights, 1452nm signal lights and 1064nm pump lights are in first internal oscillation;Further include the first light in first resonant cavity every From device (5), the one 1/2 wave plate (6), the first Fabry-Perot etalon (7), the biography of the first optoisolator (5) control light Defeated direction, the polarization direction of the one 1/2 wave plate (6) the control pump light 1064nm laser, the first Fabry-Perot mark The breadth of spectrum line of quasi- tool (7) control 3980nm ideler frequency lights is 0.0001nm, and the 3980nm ideler frequency lights are penetrated from the second speculum (9) Go out, forms the first detection laser;
The first detection laser is transmitted directly to the first entrance port (11) of sample cell (22), more in the sample cell (22) After secondary reflection, is projected from the optical emission exit (23) of the sample cell (22), absorption spectrum is converged to through adjustable convergent lens (24) In instrument (25), the optical signal of reception is converted into electric signal and passes to computer (26) by the spectrometer (25), utilizes following public affairs Formula is to SO2Gas concentration, which calculate, obtains SO2Gas concentration N1,
σ in formula1For absorption cross-section of the SO2 gases to be measured in the case where wavelength is 3980nm laser, A (λ1) it is the first interference factor, B (L1) it is the second interference factor, I01) it is incident intensity, I (λ1) it is output intensity, L1The light path for being laser in sample cell;
Another beam pump light is incident to the second resonant cavity after half-reflecting half mirror (2) is reflected into 1064nm total reflective mirrors (12), described Second resonant cavity includes the 5th speculum (13), the 6th speculum (19), the 7th speculum (14) and the 8th speculum (20), is entered It penetrates light and is transferred to the second crystal (16) through the 5th speculum (13);Second crystal (16) is set to produce by adjusting temperature controller Raw 2466nm ideler frequency lights, 1871nm signal lights;The 2466nm ideler frequency lights, 1871nm signal lights and 1064nm pump lights are described Second internal oscillation;Further include the second optoisolator (15), the 2nd 1/2 wave plate (17), the second method in second resonant cavity F-P etalon (18), the transmission direction of the second optoisolator (15) control light, the 2nd 1/2 wave plate (17) The polarization direction of pump light 1064nm laser is controlled, second Fabry-Perot etalon (18) controls 2466nm ideler frequency lights Breadth of spectrum line be 0.0001nm, the 2466nm ideler frequency lights project from the 6th speculum (19), and it is sharp to form the second detection Light;
The second detection laser is transmitted directly to the second entrance port (21) of sample cell (22), more in the sample cell (22) After secondary reflection, is projected from the optical emission exit (23) of the sample cell (22), absorption spectrum is converged to through adjustable convergent lens (24) In instrument (25), the optical signal of reception is converted into electric signal and passes to computer (26) by the spectrometer (25), utilizes following public affairs Formula is to SO2Gas concentration, which calculate, obtains SO2Gas concentration N2,
σ in formula2For SO to be measured2Absorption cross-section of the gas in the case where wavelength is 2466nm laser, A (λ2) it is the first interference factor, B (L2) it is the second interference factor, I02) it is incident intensity, I (λ2) it is output intensity, L2The light path for being laser in sample cell;
The computer (26) calculates the measured value N of the first detection laser by analyzing1With the measured value N of the second detection laser2, Obtain accurate gas concentration value N.
2. according to the method described in claim 1, it is characterized in that, further including following steps:
Adjustment is under different absorption peaks, the measured value I (λ of different wave length1)、I(λ2), and then determine the first interference factor A (λ1)、A(λ2) value;
Convolution (1) (2) and above-mentioned first interference factor A (λ1)、A(λ2) value SO under different wave length is calculated2Gas concentration N1、N2
Accurate SO is found out by weighted average2Gas concentration N.
3. according to the method described in claim 2, it is characterized in that, weighted average coefficients be 0.5, i.e. N=0.5N1+0.5N2
4. according to the method described in claim 3, it is characterized in that, by increasing light path L of the detection light in measuring gas1Or L2So that measurement result is more accurate.
5. according to the method described in claim 4, it is characterized in that, by computer control temperature control device, keep control temperature smart Really at 0.01 DEG C, to ensure detect laser wavelength stability, and then ensure measure concentration accuracy.
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H. TIAN: "Continuous-Wave Frequency-Shifted Interferometry Cavity Ring-Down Gas Sensing With Differential Optical Absorption", 《IEEE PHOTONICS JOURNAL》 *
WANG, QIANG: "Dual-beam wavelength modulation spectroscopy for sensitive detection of water vapor", 《APPLIED PHYSICS B-LASERS AND OPTICS》 *
刘丽力: "基于多次再入射光学谐振腔的甲烷气体传感器的研究", 《中国优秀博硕士学位论文全文数据库(硕士)信息科技辑》 *
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CN115372264A (en) * 2022-10-26 2022-11-22 哈尔滨翰奥科技有限公司 Method for measuring mixed gas of ammonia gas and sulfur dioxide

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