CN108760653B - Method for accurately measuring concentration of sulfur dioxide gas by spectrometer - Google Patents
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- CN108760653B CN108760653B CN201810320284.0A CN201810320284A CN108760653B CN 108760653 B CN108760653 B CN 108760653B CN 201810320284 A CN201810320284 A CN 201810320284A CN 108760653 B CN108760653 B CN 108760653B
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Abstract
The invention relates to a method for accurately measuring the concentration of sulfur dioxide gas by dual-wavelength narrow pulse width, which comprises the following steps: a beam of pump light is incident to the first resonant cavity to form first detection laser; the other beam of pump light is incident to the second resonant cavity to form second detection laser; the first detection laser and the second detection laser are directly transmitted to a sample cell (22), after multiple reflections in the sample cell (22), the first detection laser and the second detection laser are emitted from a light exit port (23) of the sample cell (22), and are converged into an absorption spectrometer (25) through an adjustable converging lens (24), the spectrometer (25) converts a received light signal into an electric signal and transmits the electric signal to a computer (26), and the computer (26) calculates a measured value N of the first detection laser through analysis1And a measured value N of the second detection laser2And obtaining an accurate gas concentration value N. According to the invention, the dual wavelengths are adopted for measurement, and the dual wavelengths are mutually used as reference standards for pulse width calibration, so that an accurate measurement result is obtained, and the detection of sulfur dioxide gas under high precision is met.
Description
Technical Field
The invention relates to a method for detecting sulfur dioxide gas concentration, in particular to a method for accurately measuring sulfur dioxide gas concentration by dual-wavelength narrow pulse width.
Background
Industry and commerce often require accurate measurements of hazardous gases in a space to ensure safety in this space. Currently, harmful gases to be prevented include SO2、H2S, CO, etc. Whether the hazardous gases in question meet certain purity limits and/or whether the emissions of these gases comply with environmental regulations. Typical applications such as process control, emissions and environmental monitoring, safety, and air conditioning require accurate concentration measurements.
Wavelength modulation spectroscopy is a way to enhance the sensitivity of gas measurements, and is especially important when measuring smaller concentrations. The concentration of the gas to be measured is usually calculated by measuring the spectral intensity of the incident light and the emitted light. However, the existing measuring method is not high in precision and is acceptable in some situations with low requirements, but in some environments with high requirements for precision, the existing measuring method cannot accurately measure the concentration of harmful gas in the space, so that it is necessary to develop a system method for accurate measurement.
Disclosure of Invention
The invention aims to solve the technical problem that the existing sulfur dioxide gas concentration measurement is inaccurate. A method for accurately measuring the concentration of sulfur dioxide gas by dual-wavelength narrow pulse width is provided, which comprises the following steps:
the optical fiber laser 1 with the spectral line width of 0.1nm outputs 1064nm linear polarization laser, and is divided into two beams of pump light by a 1064nm half-reflecting and half-transmitting mirror 2;
a beam of pump light is incident to a first resonant cavity, the first resonant cavity comprises a first reflector 4, a second reflector 9, a third reflector 3 and a fourth reflector 10, and the incident light is transmitted to a first crystal 8 through the first reflector 4; enabling the first crystal 8 to generate 3980nm idler frequency light and 1452nm signal light by adjusting a temperature controller; the 3980nm idler frequency light, 1452nm signal light and 1064nm pump light oscillate in the first resonant cavity; the first resonant cavity further comprises a first optical isolator 5, a first 1/2 wave plate 6 and a first Fabry-Perot etalon 7, wherein the first optical isolator 5 controls the transmission direction of light, the first 1/2 wave plate 6 controls the polarization direction of pump light 1064nm laser, the first Fabry-Perot etalon 7 controls the spectral line width of 3980nm idle frequency light to be 0.0001nm, and the 3980nm idle frequency light is emitted from a second reflector 9 to form first detection laser;
the first detection laser is directly transmitted to the first entrance port 11 of the sample cell 22, and after multiple reflections in the sample cell 22, the first detection laser is emitted from the light exit port 23 of the sample cell 22 and converged into the absorption spectrometer 25 through the adjustable converging lens 24, the spectrometer 25 converts the received optical signal into an electric signal to be transmitted to the computer 26, and the SO is subjected to SO measurement by using the following formula2Calculating the gas concentration to obtain SO2Gas concentration N1，
Sigma in the formula1Is the absorption cross section of the SO2 gas to be measured under the laser with the wavelength of 3980nm, A (lambda)1) Is a first interference factor, B (L)1) Is a second interference factor, I0(λ1) I (λ) is the incident light intensity1) For the intensity of the emitted light, L1The optical path of the laser in the sample cell;
the other beam of pumping light is reflected to a 1064nm total reflector 12 through the half-reflecting and half-transmitting mirror 2 and then enters a second resonant cavity, the second resonant cavity comprises a fifth reflector 13, a sixth reflector 19, a seventh reflector 14 and an eighth reflector 20, and the incident light is transmitted to a second crystal 16 through the fifth reflector 13; adjusting a temperature controller to enable the second crystal 16 to generate 2466nm idler frequency light and 1871nm signal light; the 2466nm idler frequency light, 1871nm signal light and 1064nm pump light oscillate in the second resonant cavity; the second resonant cavity further comprises a second optical isolator 15, a second 1/2 wave plate 17 and a second fabry-perot etalon 18, the second optical isolator 15 controls the transmission direction of light, the second 1/2 wave plate 17 controls the polarization direction of pump light 1064nm laser, the second fabry-perot etalon 18 controls the spectral line width of 2466nm idler light to be 0.0001nm, and the 2466nm idler light is emitted from the sixth reflecting mirror 19 to form second detection laser;
the second detection laser is directly transmitted to the second entrance port 21 of the sample cell 22, and after multiple reflections in the sample cell 22, the second detection laser is emitted from the light exit port 23 of the sample cell 22 and converged into the absorption spectrometer 25 through the adjustable converging lens 24, the spectrometer 25 converts the received optical signal into an electrical signal to be transmitted to the computer 26, and the SO is subjected to the following formula2Calculating the gas concentration to obtain SO2Gas concentration N2，
Sigma in the formula2Is the absorption cross section of the SO2 gas to be measured under the laser with the wavelength of 2466nm, A (lambda)2) Is a first interference factor, B (L)2) Is a second interference factor, I0(λ2) I (λ) is the incident light intensity2) For the intensity of the emitted light, L2The optical path of the laser in the sample cell;
the computer 26 calculates the measured value N of the first detection laser by analysis1And a measured value N of the second detection laser2And obtaining an accurate gas concentration value N.
Further, the method also comprises the following steps:
adjusting the measured value I (lambda) of different wavelengths under different absorption peaks1)、I(λ2) And further determining a first interference factor A (lambda)1)、A(λ2) A value of (d);
combination of formulas (1) and (2) and the first interference factor A (lambda)1)、A(λ2) Calculating the values of (A) to obtain SO at different wavelengths2Gas concentration N1、N2；
The exact SO2 gas concentration N was found by weighted averaging.
Further, the weighted average coefficient is 0.5, i.e., N is 0.5N1+0.5N2。
Further, by increasing the light in the measurement gas for detecting the lightRange L1Or L2And the measurement result is more accurate.
Furthermore, the temperature controller is controlled by the computer, so that the control temperature is accurate to 0.01 ℃, the stability of the wavelength of the detection laser is ensured, and the accuracy of the measured concentration is further ensured.
The invention has the beneficial effects that: according to the invention, the dual-wavelength measurement is adopted, the pulse width calibration is carried out by taking the dual-wavelength measurement as a reference standard, the accurate pulse width alignment detection is obtained, the corresponding interference factor can be eliminated through multiple measurements, the laser wavelength is accurately controlled through the temperature controller to obtain an accurate measurement result, and the detection of the sulfur dioxide gas under high precision is met. Compared with the measurement of a single wavelength, the method is more accurate.
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In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise.
Fig. 1 is a schematic structural diagram of a sulfur dioxide gas detection device according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention will be described in further detail with reference to the accompanying drawings, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
As shown in figure 1, the invention aims to solve the technical problem of inaccurate measurement of the concentration of the existing sulfur dioxide gas. A method for accurately measuring the concentration of sulfur dioxide gas by dual-wavelength narrow pulse width is provided, which comprises the following steps:
the optical fiber laser 1 with the spectral line width of 0.1nm outputs 1064nm linear polarization laser, and is divided into two beams of pump light by a 1064nm half-reflecting and half-transmitting mirror 2;
a beam of pump light is incident to a first resonant cavity, the first resonant cavity comprises a first reflector 4, a second reflector 9, a third reflector 3 and a fourth reflector 10, and the incident light is transmitted to a first crystal 8 through the first reflector 4; enabling the first crystal 8 to generate 3980nm idler frequency light and 1452nm signal light by adjusting a temperature controller; the 3980nm idler frequency light, 1452nm signal light and 1064nm pump light oscillate in the first resonant cavity; the first resonant cavity further comprises a first optical isolator 5, a first 1/2 wave plate 6 and a first Fabry-Perot etalon 7, wherein the first optical isolator 5 controls the transmission direction of light, the first 1/2 wave plate 6 controls the polarization direction of pump light 1064nm laser, the first Fabry-Perot etalon 7 controls the spectral line width of 3980nm idle frequency light to be 0.0001nm, and the 3980nm idle frequency light is emitted from a second reflector 9 to form first detection laser;
the first detection laser is directly transmitted to the first entrance port 11 of the sample cell 22, and after multiple reflections in the sample cell 22, the first detection laser is emitted from the light exit port 23 of the sample cell 22 and converged into the absorption spectrometer 25 through the adjustable converging lens 24, the spectrometer 25 converts the received optical signal into an electric signal to be transmitted to the computer 26, and the SO is subjected to SO measurement by using the following formula2Calculating the gas concentration to obtain SO2Gas concentration N1，
Sigma in the formula1Is the absorption cross section of the SO2 gas to be measured under the laser with the wavelength of 3980nm, A (lambda)1) Is a first interference factor, B (L)1) Is a second interference factor, I0(λ1) I (λ) is the incident light intensity1) For the intensity of the emitted light, L1The optical path of the laser in the sample cell;
the other beam of pumping light is reflected to a 1064nm total reflector 12 through the half-reflecting and half-transmitting mirror 2 and then enters a second resonant cavity, the second resonant cavity comprises a fifth reflector 13, a sixth reflector 19, a seventh reflector 14 and an eighth reflector 20, and the incident light is transmitted to a second crystal 16 through the fifth reflector 13; adjusting a temperature controller to enable the second crystal 16 to generate 2466nm idler frequency light and 1871nm signal light; the 2466nm idler frequency light, 1871nm signal light and 1064nm pump light oscillate in the second resonant cavity; the second resonant cavity further comprises a second optical isolator 15, a second 1/2 wave plate 17 and a second fabry-perot etalon 18, the second optical isolator 15 controls the transmission direction of light, the second 1/2 wave plate 17 controls the polarization direction of pump light 1064nm laser, the second fabry-perot etalon 18 controls the spectral line width of 2466nm idler light to be 0.0001nm, and the 2466nm idler light is emitted from the sixth reflecting mirror 19 to form second detection laser;
the second detection laser is directly transmitted to the second entrance port 21 of the sample cell 22, and after multiple reflections in the sample cell 22, the second detection laser is emitted from the light exit port 23 of the sample cell 22 and converged into the absorption spectrometer 25 through the adjustable converging lens 24, the spectrometer 25 converts the received optical signal into an electrical signal to be transmitted to the computer 26, and the SO is subjected to the following formula2Calculating the gas concentration to obtain SO2Gas concentration N2，
Sigma in the formula2Is the absorption cross section of the SO2 gas to be measured under the laser with the wavelength of 2466nm, A (lambda)2) Is a first interference factor, B (L)2) Is a second interference factor, I0(λ2) I (λ) is the incident light intensity2) For the intensity of the emitted light, L2The optical path of the laser in the sample cell;
the computer 26 calculates the measured value N of the first detection laser by analysis1And a measured value N of the second detection laser2And obtaining an accurate gas concentration value N.
The laser is coated with a 1064nm high-transmittance 2000-4300nm high-reflectance film through the 45-degree surface of the resonator high-reflectance mirror 4, and the first crystal and the second crystal are nonlinear MgO PPLN crystals.
Above-mentioned first detection light, second detection light pulse width are 0.001nm to make the absorption peak that matches sulfur dioxide gas more, it is accurate to absorb, reduces other absorption gas's interference, has guaranteed measuring accuracy. The precision of the angle and the thickness of the first Fabry-Perot etalon is precisely controlled to meet the compression of pulse width, the incident angle is usually controlled to be 45 degrees, and the thickness is 3-4 mm.
In addition, the method also comprises the following steps:
the measured value I (lambda) of different wavelengths is obtained by adjusting the spectrometer under different absorption peaks1)、I(λ2) And further obtaining a first interference factor A (lambda) through a plurality of iterations1)、A(λ2) The calculation accuracy was 0.001.
Recombination of formula (1) and (2) and the first interference factor A (lambda)1)、A(λ2) Calculating the values of (A) to obtain SO at different wavelengths2Gas concentration N1、N2；
The exact SO2 gas concentration N was found by weighted averaging. The weighted average coefficient is between 0.495 and 0.505, preferably 0.5, i.e. N is 0.5N1+0.5N2。
In a further method, the optical path length L of the detection light in the measurement gas is increased1Or L2To make the measurement more accurate, L can be usually set1Or L2The length of (A) is 0.5-5 m.
In addition, the temperature controller is controlled by the computer, so that the temperature is accurately controlled to be 0.01 ℃, the stability of the wavelength of the detection laser is ensured, and the accuracy of the measured concentration is further ensured.
The test laser with the spectral line width of 0.1pm and the wavelengths of 3980.0nm and 2466.0nm simultaneously tests the SO2 gas, the laser with one wavelength is used as a test light source, and the laser with the other wavelength is used as a reference light source, SO that the SO2 gas can be effectively distinguished from various gases, and the precision of the test gas can be improved to 0.1 ppb.
The absorption intensity values of the two SO2 gases after the test are displayed on computer software, compared with the standard intensity value of the SO2 gas, and the concentration of the SO2 gas can be obtained by taking a spectrometer as a calibration value of a test means.
The invention has the beneficial effects that: according to the invention, the dual-wavelength measurement is adopted, the pulse width calibration is carried out by taking the dual-wavelength measurement as a reference standard, the accurate pulse width alignment detection is obtained, the corresponding interference factor can be eliminated through multiple measurements, the laser wavelength is accurately controlled through the temperature controller to obtain an accurate measurement result, and the detection of the sulfur dioxide gas under high precision is met.
The above-described embodiments of the apparatus are merely illustrative, and the units described as separate parts may or may not be physically separate, and parts displayed as units may or may not be physical units, may be located in one place, or may be distributed on a plurality of network units. Some or all of the modules may be selected according to actual needs to achieve the purpose of the solution of the present embodiment.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (4)
1. A method for accurately measuring the concentration of sulfur dioxide gas by dual-wavelength narrow pulse width is characterized by comprising the following steps:
the fiber laser (1) with the spectral line width of 0.1nm outputs 1064nm linear polarization laser, and is divided into two beams of pump light by a 1064nm semi-reflecting and semi-transmitting lens (2);
a beam of pumping light is incident to a first resonant cavity, the first resonant cavity comprises a first reflector (4), a second reflector (9), a third reflector (3) and a fourth reflector (10), and the incident light is transmitted to a first crystal (8) through the first reflector (4); enabling the first crystal (8) to generate 3980nm idler frequency light and 1452nm signal light by adjusting a temperature controller; the 3980nm idler frequency light, 1452nm signal light and 1064nm pump light oscillate in the first resonant cavity; the first resonant cavity is internally provided with a first optical isolator (5), a first 1/2 wave plate (6) and a first Fabry-Perot etalon (7), wherein the first optical isolator (5) controls the transmission direction of light, the first 1/2 wave plate (6) controls the polarization direction of pump light 1064nm laser, the first Fabry-Perot etalon (7) controls the spectral line width of 3980nm idle frequency light to be 0.0001nm, and the 3980nm idle frequency light is emitted from a second reflector (9) to form first detection laser;
the first detection laser is directly transmitted to a first incidence port (11) of a sample cell (22), after multiple reflections in the sample cell (22), the first detection laser is emitted from a light emission port (23) of the sample cell (22), and is converged into an absorption spectrometer (25) through an adjustable converging lens (24), the spectrometer (25) converts a received light signal into an electric signal and transmits the electric signal to a computer (26), and SO is subjected to SO conversion by using the following formula2Calculating the gas concentration to obtain SO2Gas concentration N1，
Sigma in the formula1Is the absorption cross section of the SO2 gas to be measured under the laser with the wavelength of 3980nm, A (lambda)1) Is a first interference factor, B (L)1) Is a second interference factor, I0(λ1) I (λ) is the incident light intensity1) For the intensity of the emitted light, L1The optical path of the laser in the sample cell;
the other beam of pumping light is reflected to a 1064nm full reflector (12) through a half-reflecting and half-transmitting mirror (2) and then enters a second resonant cavity, the second resonant cavity comprises a fifth reflector (13), a sixth reflector (19), a seventh reflector (14) and an eighth reflector (20), and the incident light is transmitted to a second crystal (16) through the fifth reflector (13); causing the second crystal (16) to generate 2466nm idler light, 1871nm signal light by adjusting a temperature controller; the 2466nm idler frequency light, 1871nm signal light and 1064nm pump light oscillate in the second resonant cavity; the second resonant cavity is internally provided with a second optical isolator (15), a second 1/2 wave plate (17) and a second Fabry-Perot etalon (18), the second optical isolator (15) controls the transmission direction of light, the second 1/2 wave plate (17) controls the polarization direction of pump light 1064nm laser, the second Fabry-Perot etalon (18) controls the spectral line width of 2466nm idle frequency light to be 0.0001nm, and the 2466nm idle frequency light is emitted from the sixth reflector (19) to form second detection laser;
the second detection laser is directly transmitted to a second incidence port (21) of the sample cell (22), after multiple reflections in the sample cell (22), the second detection laser is emitted from a light emission port (23) of the sample cell (22), and is converged into an absorption spectrometer (25) through an adjustable converging lens (24), the spectrometer (25) converts a received light signal into an electric signal and transmits the electric signal to a computer (26), and the following formula is utilized to carry out SO (SO) detection2Calculating the gas concentration to obtain SO2Gas concentration N2，
Sigma in the formula2To the SO to be measured2Absorption cross section of gas under 2466nm wavelength laser, A (lambda)2) Is a first interference factor, B (L)2) Is a second interference factor, I0(λ2) I (λ) is the incident light intensity2) For the intensity of the emitted light, L2The optical path of the laser in the sample cell;
the computer (26) calculates a measured value N of the first detection laser by analysis1And a measured value N of the second detection laser2Obtaining an accurate gas concentration value N;
also comprises the following steps:
adjusting the measured value I (lambda) of different wavelengths under different absorption peaks1)、I(λ2) And further determining a first interference factor A (lambda)1)、A(λ2) A value of (d);
combination of formulas (1) and (2) and the first interference factor A (lambda)1)、A(λ2) Calculating the values of (A) to obtain SO at different wavelengths2Gas concentration N1、N2；
Determination of the exact SO by weighted averaging2The gas concentration N.
2. The method of claim 1, wherein the weighted average coefficient is 0.5, i.e., N-0.5N1+0.5N2。
3. Method according to claim 2, characterized in that the optical path L of the detection light in the measurement gas is increased by increasing the optical length L of the detection light1Or L2And the measurement result is more accurate.
4. The method of claim 3, wherein the temperature controller is controlled by a computer to accurately control the temperature to 0.01 ℃, thereby ensuring the stability of the wavelength of the detection laser and thus the accuracy of the measured concentration.
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