CN111521581B - Method and device for judging components of carbon monoxide and methane and detecting concentration of components of carbon monoxide and methane and application of method and device - Google Patents
Method and device for judging components of carbon monoxide and methane and detecting concentration of components of carbon monoxide and methane and application of method and device Download PDFInfo
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- CN111521581B CN111521581B CN202010334381.2A CN202010334381A CN111521581B CN 111521581 B CN111521581 B CN 111521581B CN 202010334381 A CN202010334381 A CN 202010334381A CN 111521581 B CN111521581 B CN 111521581B
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Abstract
The invention provides a method, a device and an application for judging components of carbon monoxide and methane and detecting the concentration of the components of carbon monoxide and methane, and mainly solves the problem that a large amount of gas exists in a coal mine and the detection of carbon monoxide is interfered. The judging method comprises the following steps: and obtaining a second harmonic signal of concentration detection, taking the trough width of the second harmonic as an evaluation function, and correcting the trough width according to the real-time temperature value. And judging whether carbon monoxide and methane or a carbon monoxide and methane mixed gas exists in the components of the mixed gas to be detected according to the corrected width of the wave trough. And finally, according to the component judgment result, giving concentration results to different components according to concentration scale factors with different concentrations. The detection device is provided with a judgment and concentration detection algorithm. The detection/judgment method and the detection device solve the problem that the traditional 1568nm and 2330.18nm wavelength carbon monoxide absorption line is covered by ethylene, ethane and methane, and are suitable for the actual use of multi-component detection.
Description
Technical Field
The invention relates to the field of trace gas multi-parameter detection, in particular to a detection device for coal mine underground multi-component gas components and a carbon monoxide and methane component judgment and concentration detection method based on harmonic detection.
Background
The tunable semiconductor laser absorption spectrum technology has the advantages that a narrow linewidth laser is adopted to output light beams aiming at gas characteristic absorption peaks, and the gas to be detected is accurately detected. Compared with the infrared absorption technology and other technologies, the infrared absorption technology and other technologies adopt an infrared light source and a filter plate (the bandwidth is dozens of nm), and the infrared absorption technology and other technologies are less prone to cross interference of other gases and water vapor. Compared with direct absorption technology and the like, the method adopts a wavelength modulation technology (WMS) harmonic detection mode, has high signal-to-noise ratio, and is easier to realize high-sensitivity gas detection. In the laboratory, a common literature reports that a 1568nm or 2330.18nm laser is adopted to realize carbon monoxide detection, but in the case of high-concentration gas existing underground a coal mine, the absorption peaks in the above wave bands are easily interfered by gases such as carbon dioxide, methane, ethylene and ethane. The line intensity difference between the characteristic absorption peak of the gas and the carbon monoxide absorption peak is large, if the gas concentration in the air is low, the influence is small, but in the semi-closed environment under the coal mine, the gas concentration is high, and the carbon monoxide detection is greatly interfered.
Disclosure of Invention
The technical problem solved by the invention is as follows: the characteristic absorption peak of carbon monoxide at 1568nm or 2330.18nm has cross interference with the absorption peaks of methane, carbon dioxide, ethylene, ethane and other gases, although the line strength difference between the absorption peaks and the absorption peak of carbon monoxide is 1-5 orders of magnitude, high-concentration methane, ethane and other gases exist in the underground coal mine operation environment, and a detection method capable of avoiding the interference of other gas components is needed for realizing the high-sensitivity detection of the carbon monoxide concentration in the environment with low carbon monoxide concentration. The fact that the absorption peak of carbon monoxide in the 2330.18nm waveband is 17.7 times stronger than the absorption peak line of methane means that when methane with the concentration 17.7 times that of carbon monoxide exists, the carbon monoxide concentration value with the same concentration is displayed, and the component and the concentration value cannot be accurately judged.
In order to overcome the defects in the prior art, the inventor of the invention carries out intensive research and provides a method and a device for judging components of carbon monoxide and methane and detecting the concentration of the components of carbon monoxide and methane, and a 2330.18nm laser is selected as a characteristic absorption peak for detecting carbon monoxide by comparing spectral lines of various gases in a database. The characteristic absorption peak of the carbon monoxide in the waveband is only interfered by methane, and accurate judgment and concentration detection of carbon monoxide and methane gas components are realized through a harmonic signal analysis processing method based on a wavelength modulation technology according to an evaluation function aiming at the width of a wave trough, so that the invention is completed.
The technical scheme provided by the invention is as follows:
in a first aspect, a method for determining the composition of carbon monoxide and methane includes: and performing tunable semiconductor laser absorption spectrum detection on the gas to be detected, and judging components in the gas to be detected by taking the wave trough width of the second harmonic as an evaluation function.
In a second aspect, a method for detecting components of carbon monoxide and methane includes the steps of: and performing tunable semiconductor laser absorption spectrum detection on the gas to be detected, and judging the components in the gas to be detected by taking the wave trough width of the second harmonic as an evaluation function.
In a third aspect, an apparatus for detecting carbon monoxide and methane components, the apparatus comprising:
the laser driving module enables the laser to emit light beams with the central wavelength of 2330.18nm by controlling the temperature and the working current of the TEC, receives sawtooth and sine superposition modulation signals emitted by the digital phase-locked module, applies the sawtooth and sine superposition modulation signals to the laser and controls the wavelength scanning range and the frequency modulation parameters of the laser light beams;
the laser emits modulated laser beams with the central wavelength of 2330.18nm into the air chamber;
the gas chamber is used for filling gas to be measured;
the detector is used for converting an optical signal absorbed by gas to be detected in the gas chamber into an electric signal and transmitting the electric signal to the digital phase-locked module;
the digital phase-locked module comprises a modulation signal generating unit and a phase-sensitive detecting unit, wherein the modulation signal generating unit sends out a controllable modulation signal and outputs the controllable modulation signal to the laser driving module, and the phase-sensitive detecting unit extracts an electric signal transmitted by the detector and multiplies the modulation signal of the modulation signal generating unit in a phase-sensitive manner to form a second harmonic signal;
the main control unit judges the components in the gas to be detected according to the wave trough width of the second harmonic signal; and obtaining the concentration value of each component in the gas to be detected according to the peak value of the second harmonic signal.
In a fourth aspect, the judgment method in the first aspect, the detection method in the second aspect, and the detection device in the third aspect are applied to the detection of carbon monoxide in an underground coal mine.
According to the method, the device and the application for judging the components of the carbon monoxide and the methane and detecting the concentration of the components of the carbon monoxide and the methane, the following beneficial effects are achieved:
(1) The method adopts the wave trough width of the second harmonic as an evaluation function to judge the components, and solves the problem that the carbon monoxide concentration detection and the component judgment cannot be realized in the coal mine environment with high-concentration gas;
(2) The invention provides a specific method for judging components by taking the width of a wave trough as the component, which is characterized in that the modulation coefficient m is different according to the difference of the widths of spectral lines, so that the accurate judgment of the components is realized by influencing the line type of a second harmonic wave;
(3) According to the method, the actual measurement result is combined, the spectral line broadening influence judgment is caused by the temperature, the temperature correction function is deduced to correct the evaluation function, the accuracy of the detection result is ensured, and the deduced correction function can be corrected by converting the temperature change into the trough width percentage.
Drawings
FIG. 1 is a schematic diagram of the present invention for determining carbon monoxide and methane composition and concentration based on second harmonic trough width;
FIG. 2 is a flow chart of the method for determining/detecting the composition and concentration of a gas to be measured according to the present invention.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
According to a first aspect of the present invention, there is provided a carbon monoxide and methane composition determination method, comprising: and performing tunable semiconductor laser absorption spectrum detection on the gas to be detected, and judging the components in the gas to be detected by taking the wave trough width of the second harmonic as an evaluation function.
Furthermore, the detection line is a line with a central wavelength of 2330.18 nm.
In the present invention, the detection of the tunable semiconductor laser absorption spectrum is performed by a detection apparatus based on the tunable semiconductor laser absorption spectrum technique, the apparatus comprising:
the laser driving module enables the laser to emit light beams with the central wavelength of 2330.18nm by controlling the temperature and the working current of a TEC (semiconductor cooler), receives sawtooth and sine superposition modulation signals emitted by the digital phase-locked module, applies the sawtooth and sine superposition modulation signals to the laser and controls the wavelength scanning range and the frequency modulation parameters of the laser light beams;
the laser emits modulated laser beams with the central wavelength of 2330.18nm into the air chamber;
the gas chamber is used for filling gas to be measured;
the detector is used for converting an optical signal absorbed by gas to be detected in the gas chamber into an electric signal and transmitting the electric signal to the digital phase-locked module;
the digital phase-locked module comprises a modulation signal generating unit and a phase-sensitive detecting unit, wherein the modulation signal generating unit sends out a controllable modulation signal and outputs the controllable modulation signal to the laser driving module, and the phase-sensitive detecting unit extracts an electric signal transmitted by the detector and multiplies the modulation signal of the modulation signal generating unit in a phase-sensitive manner to form a second harmonic signal;
the main control unit judges the components in the gas to be detected according to the wave trough width of the second harmonic signal; and obtaining the concentration value of each component in the gas to be detected according to the peak value of the second harmonic signal.
The inventor researches and discovers that carbon monoxide (CO) and methane (CH) 4 ) The width of the absorption peak of the gas at 2330.18nm is different, so that the modulation coefficient m is different, the second harmonic signal waveforms are different, an evaluation function is provided to judge the components, and the concentration value is obtained according to the wave peak value of the second harmonic.
The evaluation function is the width of the second harmonic trough. By inquiring an HITRAN database, three superposed spectral lines of methane near 2330.18nm are obtained, and the absorption coefficient is calculated to be 0.0122cm -1 atm -1 The half height and half width gamma of the absorption line is 0.1918cm -1 . The absorption coefficient of CO is 0.216cm near 2330.19nm -1 atm -1 The half height and half width gamma of the absorption line is 0.2469cm -1 The line intensities differed by a factor of 17.7 (0.216/0.0122). Although the peak deviation is 0.1cm -1 However, actually, due to the wavelength drift of the laser, the spectral line wavelength variation cannot be resolved, and the only thing that can be resolved is the spectral line width, which determines the frequency variation range of the wavelength scanning of the laser.
It is also known that the modulation factor m is the number of harmonic signals generated by the modulation of the spectral techniqueAccording to an important parameter in the analysis and curve fitting process, the ratio of the frequency variation range of the wavelength scanning of the laser to the half-height and half-width gamma of a spectral line is obtained. In order to obtain a higher signal-to-noise ratio and improve the detection sensitivity and accuracy of the system, when the second harmonic detection is adopted, the adopted modulation factor is 2.2, namely the amplitude of the sawtooth wave signal applied to the laser is obtained according to the current wavelength coefficient of the laser. In the invention, the modulation factor m of the CO spectral line is determined to be 2.2, and for CH 4 For this line, the modulation factor m is greater than 2.2 (CH) 4 Half height and half width gamma values are low), then the line type of the second harmonic is different. When high concentrations of CH are present 4 And when the mixed gas is CO, the modulation factor m is lower than 2.2 due to the spectral broadening caused by the existence of two spectral lines. The wave trough widths of the second harmonic waves caused by the difference of the modulation coefficients m can be used as a judgment basis for the components of the mixed gas, and the CO and CH in the gas to be detected are judged under the condition of not considering spectral line broadening caused by temperature 4 And (3) components.
Therefore, the method for judging the components of the carbon monoxide and the methane further comprises the following steps:
determining the width range of the wave trough of the second harmonic of the carbon monoxide;
when only CO gas exists in the gas to be detected, the width of the wave trough is a set range, if only methane gas exists in the gas to be detected, the width of the wave trough can be widened and exceeds the range determined when only CO gas exists, and if a mixed gas of high-concentration methane and carbon monoxide exists, the width of the wave trough is narrowed to be smaller than the range determined when only CO gas exists.
The inventor finds that the actually measured second harmonic signal shows that: different environmental temperatures also have influence on spectral line broadening, and can influence the trough width which is an evaluation function, so that the influence of the temperature on the spectral line width is needed to be calculated for accurately judging the components and the concentration, and the trough width is corrected by introducing an actually measured temperature value. The correction function is according to the formula
Wherein gamma is the full width at half maximum of the absorption line, gamma 0 The full width at half maximum of the spectral line at room temperature 296K, T is the temperature of the gas to be measured, T 0 Set to 296K at normal temperature, P is atmospheric pressure, P 0 Is 1 atm. From equation (1), it can be seen that the line width is affected by temperature, narrowing as the temperature increases. Performing first-order fitting on the formula (1) to obtain a line width variation curve along with temperature, and calculating according to the normal temperature range (-30-50 ℃), wherein the half-height width of the absorption line along with the temperature is in a relation:
in order to obtain an accurate detection result, the temperature sensor is added into the detection air chamber to obtain the temperature information T of the gas to be detected, and the temperature information T is used as a correction factor of an evaluation function.
The valley width can be corrected simply by converting the temperature change amount to a percentage of the valley width change according to equation (2). Therefore, whether the gas to be detected is carbon monoxide, methane or a carbon monoxide methane mixed gas is judged through the evaluation function.
According to a second aspect of the present invention, there is provided a method for detecting components of carbon monoxide and methane, comprising the step of determining the components of a gas to be detected according to the first aspect: and performing tunable semiconductor laser absorption spectrum detection on the gas to be detected, and judging the components in the gas to be detected by taking the wave trough width of the second harmonic as an evaluation function.
According to the method, the concentration value of each component in the gas to be detected is determined according to the peak value of the second harmonic signal.
The derivation of the concentration values from the harmonic peaks or the temperature-corrected harmonic peaks can be carried out by reference to methods known in the art, obtaining a concentration scaling function when only CO is present, or only CH is present, respectively 4 Time scale function of concentration, or CO and CH 4 And (4) a function of the concentration scale, and then obtaining the corresponding component concentration.
According to a third aspect of the present invention, there is provided an apparatus for detecting the composition of carbon monoxide and methane, the apparatus comprising:
the laser driving module enables the laser to emit light beams with the central wavelength of 2330.18nm by controlling the temperature and the working current of the TEC, receives sawtooth and sine superposition modulation signals emitted by the digital phase-locked module, applies the sawtooth and sine superposition modulation signals to the laser and controls the wavelength scanning range and the frequency modulation parameters of the laser light beams;
the laser device emits a modulated laser beam with the central wavelength of 2330.18nm and enters the air chamber;
the gas chamber is used for filling gas to be measured;
the detector is used for converting an optical signal absorbed by gas to be detected in the gas chamber into an electric signal and transmitting the electric signal to the digital phase-locked module;
the digital phase-locked module comprises a modulation signal generating unit and a phase-sensitive detecting unit, wherein the modulation signal generating unit sends out a controllable modulation signal and outputs the controllable modulation signal to the laser driving module, and the phase-sensitive detecting unit extracts an electric signal transmitted by the detector and multiplies the modulation signal of the modulation signal generating unit in a phase-sensitive manner to form a second harmonic signal;
the main control unit judges the components in the gas to be detected according to the wave trough width of the second harmonic signal; and obtaining the concentration value of each component in the gas to be detected according to the peak value of the second harmonic signal.
In the invention, the gas chamber is also provided with a temperature sensor for obtaining the temperature T of the gas to be measured, which is used as a correction factor of an evaluation function to correct the width of the wave trough according to the percentage of the change of the temperature change amount converted into the change of the width of the wave trough.
In a fourth aspect, the invention provides the judging method in the first aspect, the detecting method in the second aspect and the detecting device in the third aspect, and the application of the method in detecting carbon monoxide in an underground coal mine is provided.
Examples
Example 1
The invention provides a carbon monoxide and methane component detection device, which is provided with a carbon monoxide and methane component judgment and detection algorithm, wherein a laser driving module in the detection device controls a laserThe center wavelength realizes the wavelength scanning and frequency modulation of the laser beam, so that the semiconductor laser emits a modulated laser beam with the center wavelength of 2330.18nm, and the scanning is directed at CO and CH 4 After the laser beam enters the gas chamber to be detected, the gas absorbs the light beam to generate light intensity and frequency change, the optical signal is converted into an electrical signal through the photoelectric conversion of the detector and then is output, the electrical signal is subjected to signal extraction through the phase-locked detection circuit, a harmonic signal related to the gas concentration is obtained and is output to the main control unit, and meanwhile, the temperature sensor in the gas chamber outputs the temperature signal to the main control unit in real time. As shown in fig. 1, the main control unit evaluates that the component is carbon monoxide, methane or a mixture of carbon monoxide and methane according to the temperature-corrected width of the trough as an evaluation function; the concentration values are then calculated based on the magnitude of the harmonic peaks and the concentration scaling factors of the corresponding gas components. Wherein the correction of the harmonic peak in dependence on the temperature to derive the concentration value can be carried out by reference to methods known in the art to obtain a concentration scaling function 1 when only CO is present, or CH is present, respectively 4 Time scale function 2, or CO and CH 4 And (3) a function of the concentration scale, and thus the corresponding component concentrations. Fig. 2 shows a flowchart of a specific determination method.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are well known in the art.
Claims (7)
1. A method for judging the components of carbon monoxide and methane is characterized by comprising the following steps: performing tunable semiconductor laser absorption spectrum detection on the gas to be detected, wherein the detection spectral line is a spectral line with the central wavelength of 2330.18nm, the modulation coefficient of the carbon monoxide spectral line is 2.2, determining the wave trough width range of the second harmonic of the carbon monoxide, and judging the components in the gas to be detected by taking the wave trough width of the second harmonic as an evaluation function;
when only carbon monoxide exists in the gas to be detected, the width of the wave trough is a set range, if only methane gas exists in the gas to be detected, the width of the wave trough is widened and exceeds the range determined when only carbon monoxide exists, and if high-concentration methane and carbon monoxide mixed gas exists, the width of the wave trough is narrowed and is smaller than the range determined when only carbon monoxide exists;
and (3) introducing an actual temperature value to correct the width of the wave trough, specifically, converting the temperature variation into the percentage of the change of the width of the wave trough to correct the width of the wave trough according to the following formula:
wherein gamma is the full width at half maximum of the absorption spectrum line, and T is the temperature of the gas to be detected during detection.
2. A method for detecting carbon monoxide and methane components, characterized by comprising the steps of the judging method according to claim 1:
and performing tunable semiconductor laser absorption spectrum detection on the gas to be detected, and judging the components in the gas to be detected by taking the wave trough width of the second harmonic as an evaluation function.
3. The detection method according to claim 2, wherein the concentration value of each component in the gas to be detected is determined according to the peak value of the second harmonic signal.
4. A carbon monoxide and methane component detection apparatus, the apparatus comprising:
the laser driving module enables the laser to emit light beams with the central wavelength of 2330.18nm by controlling the temperature and the working current of the TEC, receives sawtooth and sine superposition modulation signals emitted by the digital phase-locked module, applies the sawtooth and sine superposition modulation signals to the laser and controls the wavelength scanning range and the frequency modulation parameters of the laser light beams;
the laser emits modulated laser beams with the central wavelength of 2330.18nm into the air chamber;
the gas chamber is used for filling gas to be measured; a temperature sensor is arranged in the gas chamber and used for obtaining the temperature T of the gas to be measured, the temperature T is used as a correction factor of an evaluation function, and the width of the wave trough is corrected according to the percentage of the change of the wave trough width converted from the temperature change;
wherein gamma is the full width at half maximum of the absorption spectrum line, and T is the temperature of the gas to be detected during detection;
the detector is used for converting an optical signal absorbed by gas to be detected in the gas chamber into an electric signal and transmitting the electric signal to the digital phase-locked module;
the digital phase-locked module comprises a modulation signal generating unit and a phase-sensitive detecting unit, wherein the modulation signal generating unit sends out a controllable modulation signal and outputs the controllable modulation signal to the laser driving module, and the phase-sensitive detecting unit extracts an electric signal transmitted by the detector and multiplies the modulation signal of the modulation signal generating unit in a phase-sensitive manner to form a second harmonic signal;
the main control unit judges the components in the gas to be detected according to the wave trough width of the second harmonic signal; and obtaining the concentration value of each component in the gas to be detected according to the peak value of the second harmonic signal.
5. The method of claim 1 applied to detecting carbon monoxide in an underground coal mine.
6. The use of the detection method of claim 2 or 3 for detecting carbon monoxide in a coal mine.
7. The use of the device of claim 4 for detecting carbon monoxide in a coal mine.
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