CN114486808A - Gas detection method for enhancing spectral line absorption intensity - Google Patents
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Abstract
A gas detection method for enhancing spectral line absorption intensity belongs to the technical field of laser gas detection. The method uses a pumping light source with the wavelength selected according to the wavelength of a detection light source, the pumping light source generates laser, the laser is input into a gas chamber, gas molecules to be detected are pumped from a ground state energy level to a lower energy level where characteristic absorption of the detection light occurs, the number of molecules on the lower energy level where the characteristic absorption occurs is increased, and therefore the characteristic absorption of the gas to be detected on the detection light is improved. The invention has the obvious advantages that the pump light source is used to enhance the spectral line absorption intensity of the gas to be detected to the detection light, increase the absorption of the gas to be detected to the detection light and improve the detection limit and sensitivity of the system.
Description
Technical Field
The invention relates to a gas detection method for enhancing spectral line absorption intensity, and belongs to the technical field of laser gas detection.
Background
In recent years, with the increasing greenhouse effect of the atmosphere, a series of problems such as global warming have been caused. The greenhouse effect is derived from greenhouse gases, and a large amount of greenhouse gases are generated in the processes of industrial production, automobile exhaust, energy collection and transportation and the like, so that the monitoring of trace greenhouse gases in the atmosphere is very important. Meanwhile, the trace gas detection technology has very important application in the fields of medicine, mine production safety, electric industry safety monitoring and the like.
In a methane gas spectrum detection method research based on a mid-infrared DFG light source, published in 2018, 9.5 of the university of Nanjing information engineering, Changjianhua et al, in volume 39, of optical journal, pump light and signal light are used to generate a mid-infrared light source through a Difference Frequency Generation (DFG) technology to detect the concentration of methane gas, but the detection method does not change the spectral line absorption intensity of the gas to be detected in principle, and a limit selected on the spectral line absorption intensity exists, so that the precision of trace gas detection is limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a gas detection method for enhancing spectral line absorption intensity, which aims to solve the problems of low gas detection precision, small light absorption signal of trace gas and high signal processing difficulty.
The invention is realized by the following technical scheme:
a gas detection method of enhancing spectral line absorption intensity is realized by a system which comprises a temperature control current source A, a temperature control current source B, a pumping laser, a detection laser, an air chamber, an optical filter, a photoelectric detector, a current-to-voltage conversion module, a data acquisition card and a computer, wherein the temperature control current source A and the temperature control current source B respectively comprise a temperature control part and a driving current control part, the temperature control current source A and the temperature control current source B are respectively connected with the pumping laser and the detection laser, the output ends of the detection laser and the pumping laser are coupled through an optical fiber and then input into the air chamber, and the air chamber is coupled and connected to the input end of the photoelectric detector through the optical filter and the optical fiber which take the detection laser wavelength as a central wave band; the output end of the photoelectric detector is connected to the current-to-voltage module, the current-to-voltage module is connected with the input end of the data acquisition card, and the output end of the data acquisition card is connected to the computer; the method comprises the following steps:
1) connecting the system, turning on the power supply of the photoelectric detector, the current-to-voltage conversion module, the data acquisition card and the computer, and injecting the gas to be detected into the gas chamber;
2) firstly, turning on power supplies of a pumping laser and a temperature control current source A, controlling the temperature and the input current through the temperature control current source A to control the frequency and the light intensity of the output laser of the pumping laser, so that the output frequency of the pumping laser meets the requirement that gas molecules to be detected are transited from a ground state energy level to a frequency of a lower energy level absorbed by a detection light generation characteristic, and the output light intensity is kept constant;
3) then, a power supply of the detection laser and a temperature control current source B is turned on, the temperature control part is adjusted to control the temperature of the detection laser, and the driving current control part of the temperature control current source B is adjusted to enable the detection laser to output laser corresponding to the absorption peak value of the measured gas spectral line, namely the laser at the central frequency;
4) the detection laser and the pump laser output laser are coupled by optical fibers and then input into the air chamber, and the output end of the air chamber is coupled and connected to the input end of the photoelectric detector by the optical fibers through the optical filter;
5) the output current of the photoelectric detector is converted into a voltage signal by a current-to-voltage conversion module, the voltage signal is acquired by a data acquisition card and then input into a computer for data processing and analysis, and the concentration result of the gas to be detected is obtained by the computer.
The detection principle of the method of the invention is as follows:
light emitted by the pump laser is input into the air chamber through optical fiber coupling, and the molecular number of each energy level of gas to be detected in the air chamber conforms to the Boltzmann distribution:
wherein n isiAnd N1Respectively the number of molecules of a gas characteristic absorption lower energy level and a ground state energy level, and g' is the energy E of an i energy level of the gas characteristic absorption lower energy level in absorption transitioniQ (T) is a partition function of the absorption gas at a temperature T, EiIs the energy of the lower energy level at the time of the absorption transition, k is BoltzmannA constant.
The number of molecules n of the lower energy level of the gas characteristic absorption according to the Boltzmann distributioniIs the number of molecules N smaller than the ground state energy level1Most of the gas molecules to be detected are in the ground state energy level, and by consulting the HITRAN database, when most of the gas is absorbed, the absorbed energy of the lower energy level is higher than the ground state energy level, so that the Boltzmann distribution of the gas to be detected can be broken through injecting energy by pumping laser, the number of the absorbed molecules of the lower energy level is increased, and the absorption of the gas to be detected on the detection laser can be enhanced.
The method has the advantages that:
a pumping laser device is introduced, the absorption of the gas to be detected on the detection laser is enhanced by breaking the Boltzmann distribution of the gas to be detected, and the detection sensitivity of the whole system on the gas to be detected is improved.
Drawings
FIG. 1 is a schematic view of the overall structure of the detection method of the present invention.
In the figure: 1-temperature control current source A, 2-temperature control current source B, 3-pumping laser, 4-detection laser, 5-air chamber, 6-photoelectric detector, 7-current-to-voltage module, 8-data acquisition card, 9-computer and 10-optical filter.
FIG. 2 is a diagram showing the energy level transition of the methane molecule for the characteristic absorption of probe light when the energy of the pump light is injected in example 1 of the present invention.
In the figure, a pump laser is used for generating 7533.49nm laser to pump part of methane gas molecules from a ground state energy level to 1327cm-1Energy level, then using a probe laser to generate 7610.92nm laser, which generates characteristic absorption with the excited methane molecules, pumping the methane molecules to 2641cm-1An energy level; according to HITRAN, when characteristic absorption occurs between laser with the wavelength of 7610.92nm and methane molecules, the lower energy level energy of the absorption is 2641cm-1。
FIG. 3 is a diagram illustrating the energy level transition of the carbon dioxide molecule for the characteristic absorption of probe light when the energy of the pump light is injected in example 2 of the present invention.
In the figure makePumping part of carbon dioxide gas molecules from ground state to 2292cm by using 4361.9075nm laser generated by pump laser-1Energy level, using a probe laser to generate 4396.87nm laser light, which generates characteristic absorption with excited methane molecules, pumping carbon dioxide molecules to 4566cm-1An energy level; according to HITRAN, when characteristic absorption between laser with the wavelength of 4396.87nm and carbon dioxide molecule occurs, the lower energy level energy of the absorption is 2292cm-1。
Detailed Description
The invention is further described below, but not limited to, with reference to the following figures and examples.
Example 1:
a gas detection method of enhanced spectral line absorption intensity is realized by a system which comprises a temperature control current source A1, a temperature control current source B2, a pump laser 3, a detection laser 4, an air chamber 5, a photoelectric detector 6, a current voltage conversion module 7, a data acquisition card 8, a computer 9 and an optical filter 10, wherein the temperature control current source A1 and the temperature control current source B2 are respectively connected with the pump laser 3 and the detection laser 4, the temperature control current source B2 of the detection laser 4 is composed of a temperature control circuit and a drive current control part, the light frequency output by the detection laser 4 is ensured to be at the central frequency required by measuring the concentration of gas to be detected by controlling the temperature and the injection current, the temperature control current source A1 of the pump laser 3 is composed of a temperature control circuit and a drive current control part, and the light frequency output by the pump laser 3 is ensured to be stable by controlling the temperature and the injection current so as to meet the requirement of jumping the gas to be detected from the ground state energy level Moving to the frequency of the lower energy level absorbed by the generation characteristics of the detection laser, and keeping the output light energy constant; the output ends of the detection laser 4 and the pump laser 3 are connected with the air chamber 5 through optical fiber coupling, and the air chamber 5 is connected with the input end of the photoelectric detector 6 through an optical filter 10 taking the detection laser wavelength as a central wave band and the optical fiber coupling; the output end of the photoelectric detector 6 is connected to a current-to-voltage conversion module 7, the current-to-voltage conversion module 7 is connected with the input end of a data acquisition card 8, the data acquisition card 8 is connected to a computer 9 to read data of the data acquisition card, and the method comprises the following steps:
1) connecting the system, opening a detection laser, a pumping laser, a temperature control current source A, a temperature control current source B, a computer and power supplies of all modules, and injecting methane gas into a gas chamber;
2) the temperature control current source A of the pump laser controls the central frequency of the output light of the pump laser to be near the wavelength of 7533.49nm by controlling the temperature and the injection current, and the light intensity is kept constant;
light emitted by the pump laser is input into the gas chamber through optical fiber coupling, and the molecular number of each energy level of methane in the gas chamber conforms to Boltzmann distribution:
wherein n isiAnd N1Respectively the number of molecules of a gas characteristic absorption lower energy level and a ground state energy level, and g' is the energy E of an i energy level of the gas characteristic absorption lower energy level in absorption transitioniQ (T) is a partition function of the absorption gas at a temperature T, EiIs the energy level at the lower energy level at the time of the absorption transition, and k is the boltzmann constant.
The number of molecules n of the lower energy level of the gas characteristic absorption according to the Boltzmann distributioniIs the number of molecules N smaller than the ground state energy level1Most of the gas molecules to be detected are in the ground state energy level, and by consulting the HITRAN database, when most of the gas is absorbed, the absorbed energy of the lower energy level is higher than the ground state energy level, so that the Boltzmann distribution of the gas to be detected can be broken through injecting energy by pumping laser, the number of the absorbed molecules of the lower energy level is increased, and the absorption of the gas to be detected on the detection laser can be enhanced.
3) The temperature control current source B of the detection laser controls the output wavelength of the output light of the detection laser to be about 7610.92nm by controlling the temperature and the injection current;
the light emitted by the detection laser is input into the air chamber through optical fiber coupling, and is subjected to characteristic absorption with the gas to be detected excited to the lower energy level of the detection laser characteristic absorption, and then is connected to the input end of the photoelectric detector through optical fiber coupling after passing through an optical filter with the central wavelength of 7610.92nm at the output end of the air chamber; the light signal is converted into a current signal through the photoelectric detector, the current signal is converted into a voltage signal through the current-to-voltage conversion module and then is collected by the data collection card, and the computer processes and analyzes the voltage signal collected by the data collection card to obtain the concentration content of the methane gas.
As shown in FIG. 2, which is a schematic diagram of energy level transition of methane molecules for characteristic absorption of probe light when pump light energy is injected, in this embodiment, a laser with a wavelength of 7610.92nm is selected for the probe laser, and it can be known by referring to a HITRAN database that when the laser with the wavelength is absorbed by methane gas characteristics, the energy difference between the lower energy level and the ground state energy level is represented by wave number, and the value is 1327.308cm-1Therefore, the energy difference between the lower energy level and the ground state level when absorption occurs can be expressed as:
wherein h is 6.626 × 10-34(J.s) is the Planck constant, c 3X 1010(cm·s-1) It is the speed of light that is,
is the wave number. And the energy of the laser can be expressed as:
wherein h is 6.626 × 10-34(J.s) is the Planck constant, c 3X 1010(cm·s-1) It is the speed of light that is,
is the wave number. Therefore, in order to pump methane gas from the ground state level to the lower level of the absorption characteristic of the detection laser by the pump laser, the energy difference between the lower level of the absorption and the ground state level is equal to the energy of the pump laser, and the pump laserWave number of 1327.405cm is selected-1I.e. a laser with a wavelength of 7533.49 nm. The line intensities S at the wavelengths 7610.92nm and 7533.49nm are known by consulting the HITRAN databaseijAre respectively 1.968 multiplied by 10-22(cm-1/(molecule·cm-2) And 1.16X 10-22(cm-1/(molecule·cm-2) Both smaller).
Deducing the particle number n of pumping laser pumping gas molecules from a ground level to a high level from a pump laser through an Einstein coefficient relational expressioni' is:
wherein n isi' and N1The number of molecules of the energy level under gas characteristic absorption and the ground state energy level respectively, and g' is the low state i energy level energy E during absorption transitioniG' is the energy E of the high j energy level at the absorption transitionjDegree of degeneracy of A21Is the Einstein coefficient of spontaneous transition, rhovIs the pump laser energy density.
For the line intensity SijThe expression of (a) is:
wherein n isiAnd N1The particle numbers of the lower energy level and the ground state energy level which are respectively absorbed by the generation characteristics of the gas to be detected are increased, the spectral line intensity can be enhanced by increasing the particle number of the lower energy level absorbed by the generation characteristics of methane molecules, and the increased intensity can be ni’/niExpressed as:
so by using the method, the energy rho is fixed in the pump laservCan inject a fixed number of particles ni' pumped to a characteristic lower absorption level, canThe fixed increase in line intensity at the wavelength of 7610.92nm enhances the characteristic absorption of methane gas for this wavelength of laser light.
And for the trace gas concentration to be measured, the correlation expression of the gas concentration and the absorption light intensity in the gas chamber is as follows:
Ia＝I0SijPLg(v,v0)C (7)
wherein I0Is the incident light intensity, IaIs to absorb the light intensity, SijIs the spectral line intensity, and C is the gas concentration to be measured in the gas chamber. It can be seen that the gas concentration in the gas chamber and the gas absorption intensity are in linear relationship, and the coefficient and the spectral line intensity S thereofijIn relation to, so that the line intensity S is enhancedijThen, the intensity of the absorption light corresponding to a certain concentration is also enhanced, so that the detection sensitivity of the whole system to methane gas is improved.
Example 2:
as in example 1, except that the gas to be measured was carbon dioxide gas,
FIG. 3 is a schematic diagram showing energy level transition of carbon dioxide molecules for characteristic absorption of probe light when pump light energy is injected, the probe laser selects a laser with a wavelength of 4396.87nm, and it can be known by referring to a HITRAN database that when the laser with the wavelength is absorbed by methane gas characteristics, the energy difference between the lower energy level and the ground state energy level is represented by wave number, and the value is 2292.6453cm-1。
The wave number of the pump laser is selected to be 2292.574963cm-1I.e. a laser with a wavelength of 4361.9075 nm. The line intensities S at the wavelengths 4396.87nm and 4361.9075nm are known by consulting the HITRAN databaseijAre respectively 3.176X 10-22(cm-1/(molecule·cm-2) And 9.018 x 10-22(cm-1/(molecule·cm-2) By use of the present method, pump laser energy injection can enhance the line intensity at a wavelength of 4396.87 nm. The characteristic absorption of the carbon dioxide gas to the laser with the wavelength is enhanced, and the detection sensitivity of the whole system to the carbon dioxide gas is improved.
Claims (1)
1. A gas detection method of enhancing spectral line absorption intensity is realized by a system which comprises a temperature control current source A, a temperature control current source B, a pumping laser, a detection laser, an air chamber, an optical filter, a photoelectric detector, a current-to-voltage conversion module, a data acquisition card and a computer, wherein the temperature control current source A and the temperature control current source B respectively comprise a temperature control part and a driving current control part, the temperature control current source A and the temperature control current source B are respectively connected with the pumping laser and the detection laser, the output ends of the detection laser and the pumping laser are coupled through an optical fiber and then input into the air chamber, and the air chamber is coupled and connected to the input end of the photoelectric detector through the optical filter and the optical fiber which take the detection laser wavelength as a central wave band; the output end of the photoelectric detector is connected to the current-to-voltage module, the current-to-voltage module is connected with the input end of the data acquisition card, and the output end of the data acquisition card is connected to the computer; the method comprises the following steps:
1) connecting the system, turning on the power supply of the photoelectric detector, the current-to-voltage conversion module, the data acquisition card and the computer, and injecting the gas to be detected into the gas chamber;
2) firstly, turning on power supplies of a pumping laser and a temperature control current source A, controlling the temperature and the input current through the temperature control current source A to control the frequency and the light intensity of the output laser of the pumping laser, so that the output frequency of the pumping laser meets the requirement that gas molecules to be detected are transited from a ground state energy level to a frequency of a lower energy level absorbed by a probe light generation characteristic, and the output light intensity is kept constant;
3) then, a power supply of the detection laser and a temperature control current source B is turned on, the temperature control part is adjusted to control the temperature of the detection laser, and the driving current control part of the temperature control current source B is adjusted to enable the detection laser to output laser corresponding to the absorption peak value of the measured gas spectral line, namely the laser at the central frequency;
4) the detection laser and the pump laser output laser are coupled by optical fibers and then input into the air chamber, and the output end of the air chamber is coupled and connected to the input end of the photoelectric detector by the optical fibers through the optical filter;
5) the output current of the photoelectric detector is converted into a voltage signal by a current-to-voltage conversion module, the voltage signal is acquired by a data acquisition card and then input into a computer for data processing and analysis, and the concentration result of the gas to be detected is obtained by the computer.
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| CN214374280U (en) * | 2021-02-03 | 2021-10-08 | 深圳市美思先端电子有限公司 | Gas concentration detection device |
| CN113406036A (en) * | 2021-06-17 | 2021-09-17 | 桂林电子科技大学 | Portable greenhouse gas detection system based on spectrum reconstruction technology |
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