CN114112956A - Gas detection method and device - Google Patents
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- CN114112956A CN114112956A CN202111394661.3A CN202111394661A CN114112956A CN 114112956 A CN114112956 A CN 114112956A CN 202111394661 A CN202111394661 A CN 202111394661A CN 114112956 A CN114112956 A CN 114112956A
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- 238000001514 detection method Methods 0.000 title claims abstract description 31
- 238000005259 measurement Methods 0.000 claims abstract description 55
- 238000002835 absorbance Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 235000013405 beer Nutrition 0.000 claims abstract description 11
- 238000010521 absorption reaction Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 197
- 230000009102 absorption Effects 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 7
- 238000004364 calculation method Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000009530 blood pressure measurement Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 description 4
- 238000005086 pumping Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004868 gas analysis Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
Abstract
The application provides a gas detection method and a detection device, wherein the method generates different light energy absorption by changing the gas pressure in a measurement gas chamber of a photometer to obtain different absorbances; and calculating the concentration of the gas to be detected by combining the beer Lambert constant rate.
Description
Technical Field
The application belongs to the field of gas detection, and particularly relates to a gas detection method and device.
Background
Non-dispersive infrared and non-dispersive ultraviolet are two important gas detection technologies, have the advantages of high signal-to-noise ratio, large dynamic range, simple structure and low cost, and are widely used in the field of gas analysis.
Commonly used technical solutions for non-dispersive infrared and non-dispersive ultraviolet gas analyzers are the single wavelength dual beam and dual wavelength single beam methods. The single-wavelength double-beam method generally adopts a measurement gas chamber and a reference gas chamber, the measurement gas chamber is filled with measured sample gas, gas (such as nitrogen) which is not absorbed by the sample gas is sealed in the reference gas chamber, and the concentration of the measured gas is calculated by detecting the attenuation degree of light beams with the same wavelength after passing through the measurement gas chamber and the reference gas chamber. The dual-wavelength single-beam method adopts two wavelengths, the measured sample gas has absorption to one wavelength of light, and has no absorption to the other wavelength of light, and the concentration of the sample gas is calculated by detecting the absorption condition of the measured sample gas to the two wavelength light beams. The calculations for both of the above methods are based on beer lambert law. In practical applications, both of the above methods have the condition of drift. For the single-wavelength double-beam method, the measurement gas chamber and the reference gas chamber experience different physical and chemical environments, and the pollution conditions are different, so that absorbance drift is generated, and the drift of the detection result is generated. For the dual-wavelength single-beam method, the power of the light source changes, the spectrum of the light source changes, and the states of the reference wavelength and the measurement wavelength change, thereby causing the drift of the detection result. In addition, if dual light sources or dual detectors are used, inconsistencies between the two light sources or the two detectors may also cause drift.
Disclosure of Invention
Aiming at some problems in the prior art, the application provides a gas detection method and a gas detection device, which can eliminate the drift of a photometer to a greater extent and ensure the long-term working stability and accuracy.
A first aspect of the present application provides a gas detection method that produces different absorbances of light energy by changing the gas pressure in a measurement gas chamber of a photometer, resulting in different absorbances; the gas concentration was calculated in combination with the beer lambert ratio.
More specifically, the gas detection method, according to beer Lambert's law, standard atmospheric pressure P0Introducing gas G (gas) with lower volume concentration C into a measuring gas chamber of a photometer, wherein when the gas pressure in the measuring gas chamber is P, the absorbance generated by the gas G is A,
the gas pressure in the measuring gas chamber is P1In the case of (2), the absorbance A of the gas G1Comprises the following steps:
the gas pressure in the measuring gas chamber is P2In the case of (2), the absorbance A of the gas G2Comprises the following steps:
in the formula I1＝I2The value of the intensity of the light of the gas G detected by the detector assuming no absorption, I1' for measuring the pressure P after gas G is introduced into the gas chamber1The value of light intensity detected by the time detector, I2' for measuring the pressure P after gas G is introduced into the gas chamber2The light intensity value detected by the detector.
The formula (1) and (2) can be used for obtaining:
due to I1＝I2Therefore lnI1-lnI2＝0
Therefore, it is not only easy to use
In the closed measuring gas chamber, the absorbance ratio of the gas G under the two pressure states is equal to the pressure ratio under the two pressure states; namely:
the synthesis of (3) and (4) can obtain
According to the beer Lambert law, the volume concentration C of a gas G is proportional to the absorbance AFrom which the gas concentration at standard atmospheric pressure can be obtained
The method can be obtained by the formula (5), and two or more groups of detection are carried out by detecting the pressure values in two pressure states in the measurement air chamber and the light intensity value detected by the detector, and after the calibration coefficient R is obtained, the calibration coefficient R is obtained
The volume concentration value C of the gas G under the standard atmospheric pressure can be calculated.
Alternatively,
the calibration coefficient R is obtained by reversely calculating the pressure and light intensity values of the gas to be measured with known concentration in two pressure states, or a plurality of calibration coefficients R are obtained by respectively reversely calculating the pressure and light intensity values of a plurality of gases to be measured with known concentration in two pressure states, and then a fitting curve is obtained by fitting a plurality of R values.
Optionally, the gas detection method comprises:
(1) determination of the scaling factor R:
measuring the pressure value and the light intensity value of a gas G with known concentration under two pressure states; by passing
Carrying out inverse calculation to obtain a calibration coefficient R;
(2) calculating the volume concentration of the gas to be measured:
measuring pressure values and light intensity values of gas G with unknown concentration under two pressure states; by the formula knowing the scaling factor R
And calculating to obtain a concentration value C of the gas G with unknown concentration.
Further, in the determination process of the calibration coefficient R in step (1), pressure values and light intensity values of a plurality of known gases G with different concentrations under two pressure states are respectively measured to obtain a plurality of different calibration coefficients R, and R is obtained by fitting a curve, so as to determine the calibration coefficient R.
Optionally, the photometer employs a single wavelength, a single detector, and a single measurement gas cell; the reference gas chamber may not be provided.
The single wavelength refers to that the light entering the measurement gas chamber is light with a single wavelength, or the light entering the measurement gas chamber is light with multiple wavelengths, and the light with the single wavelength is detected at the detector.
A second aspect of the present application provides a gas detection apparatus having a photometer including a light source for emitting light, a measurement gas cell for passing the light emitted by the light source, and a detector for detecting a light intensity value of the light transmitted through the measurement gas cell; the measurement air chamber is provided with an air inlet for the gas to be measured to enter and an air outlet for discharging the gas to be measured; the air pressure in the measuring air chamber is adjustable and can be stably measured.
Optionally, in the measurement gas chamber, different light energy absorption can be generated by changing the pressure of the gas to be measured in the measurement gas chamber, different light intensity values are detected, and different absorbances are obtained; and calculating the concentration of the gas to be detected by combining the beer Lambert constant rate.
Optionally, the air inlet is located at the front of the measurement plenum and the air outlet is located at the rear of the measurement plenum. And a valve is arranged at the air inlet and used for controlling the gas to be detected to enter. The air outlet is provided with an air pump for pumping in or pumping out the gas to be measured.
Optionally, the photometer is not provided with a reference gas cell.
The measuring gas chamber is provided with a pressure measuring device, preferably a pressure sensor, capable of detecting the pressure of the gas to be measured therein.
Optionally, the photometer employs a single wavelength, a single detector, and a single measurement gas cell.
The front end of the measurement air chamber is provided with an optical filter or a grating for enabling the light entering the measurement air chamber to be single-wavelength light. Or, the front end of the detector is provided with an optical filter for enabling the light intensity value of the single-wavelength light detected by the detector.
Compared with the prior art, the beneficial effects of this application are:
according to at least one embodiment of the method, the detection result drift of the optical gas analyzer caused by factors such as light source attenuation, pollution of a measurement gas chamber, inconsistent aging of a detector and the like can be eliminated, the long-term stability of the analyzer is ensured, and the zero calibration and calibration frequency is reduced.
Drawings
FIG. 1 is a schematic view of a gas measurement device according to one embodiment;
FIG. 2 is a schematic view of a gas measurement device according to one embodiment;
FIG. 3 shows SO concentrations2A gas raw output signal;
FIG. 4 is a graph of signal values after extraction of a portion of the raw data based on FIG. 3;
FIG. 5 is a plot of absorbance versus concentration.
Detailed Description
The technical solutions of the present application are explained in detail below with reference to specific embodiments, however, it should be understood that elements, structures and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.
In the description of the present application, it is to be noted that, unless otherwise explicitly specified or limited, the terms "connected" and "connected" are to be interpreted broadly, e.g., as being fixed or detachable or integrally connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The terms "front" and "rear" in this application are primarily with respect to the path of travel of the light. The specific meaning of the above terms in the present application can be understood in a specific case by those of ordinary skill in the art.
As shown in fig. 1 and 2, a first embodiment of the present application provides a gas detection apparatus having a gas analysis photometer 1, which may be an ultraviolet, visible, or infrared photometer.
As shown in fig. 1, the photometer comprises a light source 11 for emitting light, a measurement gas cell 12 for passing the light emitted by the light source 11, and a detector 13 for detecting the light intensity value I of the light transmitted through the measurement gas cell 12. The light source 11 and the detector 13 in the present application may be implemented by a device in the prior art. The measurement gas chamber 12 is provided with a gas inlet 121 for the gas to be measured to enter and a gas outlet 122 for the gas to be measured to exit, so that the gas to be measured can pass through or stay in the measurement gas chamber 12; wherein the air inlet 121 is located at the front of the measurement air chamber, and the air outlet 122 is located at the rear of the measurement air chamber. The air pressure in the measuring air chamber is adjustable and stabilizable.
In the embodiment, different light energy absorption is generated by changing the pressure of the gas to be measured in the measurement gas chamber 12, different light intensity values are detected, and different absorbances are obtained; and calculating the concentration of the gas to be detected by combining the beer Lambert constant rate.
The photometer is not provided with a conventional reference gas chamber; the embodiment can realize the measurement of the concentration of the gas to be measured under the condition of not arranging the reference gas chamber.
The measurement gas chamber 12 is provided with a pressure measurement device 123, preferably a pressure sensor, capable of detecting the pressure of the gas to be measured therein.
The photometer 1 adopts a single wavelength, a single detector and a single measuring gas chamber.
The single wavelength means that the light entering the measurement gas cell 12 is single wavelength light, or the light entering the measurement gas cell 12 is light of a plurality of wavelengths, but the light of the single wavelength is detected at the detector 13. The former can be realized by arranging an optical filter or a grating at the front end of the measurement gas chamber for light splitting, or can be realized by arranging an optical filter at the front end of the detector for filtering. In other words, optionally, a filter or a grating is arranged at the front end of the measurement gas cell 12 to make the light entering the measurement gas cell 12 be single-wavelength light. Or, a filter is arranged at the front end of the detector 13, so that the light intensity value of the single-wavelength light detected by the detector 13 is obtained.
Optionally, the gas detection device is further provided with a gas pump 14 for the suction or extraction of the gas to be detected. Preferably, the air pump 14 is disposed at the air outlet 122.
Optionally, a valve 15 is disposed at the gas inlet 121 for controlling the inlet of the gas to be measured. Preferably, the valve 15 is a three-way solenoid valve.
The working steps of the method for detecting gas by the gas detection device comprise:
1. determination of the scaling factor R:
(11) the electromagnetic valve 15 is opened, the air pump 14 is opened, and the standard atmospheric pressure P is achieved0Pumping the gas to be measured with the known volume concentration C into the measuring air chamber 12, closing the electromagnetic valve 15, stopping the air pump 14, and recording the pressure P after the pressure is stable1Recording the photodetector signal I1′；
(12) The air pump 14 is turned off after a short period of time, and the pressure P is recorded after the pressure is stabilized2Simultaneously recording the photodetector signal I2′；
(13) By gas concentration formula
And calculating the scaling coefficient R reversely.
In this embodiment, in order to obtain a more accurate scaling coefficient R, it is further possible to:
(14) opening the electromagnetic valve 15, respectively introducing gases with different known concentrations for a plurality of times, and repeating the steps (11) and (12), wherein the pressure P can be completely different from that in the steps (11) and (12); therefore, more R can be back calculated through the gas concentration formula, and a plurality of R are fitted to obtain a fitting curve, so that a more accurate calibration coefficient R can be obtained.
2. And (3) detecting the concentration of the gas to be detected:
(21) the electromagnetic valve 15 is opened, the air pump 14 is opened, the gas to be measured with unknown volume concentration under the standard atmospheric pressure is pumped into the measurement air chamber 12, then the electromagnetic valve 15 is closed, the air pump 14 stops working, and the pressure P is recorded after the pressure is stable11Recording the photodetector signal I1′1；
(22) The air pump 14 is turned off after a short period of time, and the pressure P is recorded after the pressure is stabilized12Simultaneously recording the photodetector signal I1′2；
(23) According to the gas obtained in step (13) or (14)Formula of concentration
Since the scaling factor R is known, the volume concentration C of the gas to be measured is calculated.
It is noted that in the above step, P2Pressure of less than P1Due to the air pump 14 being at P1After the pressure, continue to pump (like vacuum) so that P2Less than P1(ii) a However, in practical application, the same gas to be measured may be continuously filled into the measurement gas chamber 12, so that P is2Greater than P1These are all understood.
Example (b):
this embodiment selects and uses for detecting SO2The present application is further described with reference to the accompanying drawings.
1. For measuring standard atmospheric pressure P0Lower same concentration of SO2The light intensity values of the gas in two different pressure states are obtained, so as to obtain corresponding absorbance, and the air intake method of the embodiment adopts the air pump 14 to pump in. The gas circuit connection is shown in FIG. 2, wherein the gas inlet of the photometer is connected with the standard gas bottle (filled with SO)2Gas) are connected through a three-way electromagnetic valve 15, and the air pump 14 is positioned behind the measuring air chamber of the photometer 1, and the time interval of the gas flowing into the measuring air chamber of the photometer are controlled by controlling the three-way electromagnetic valve 15.
2. Setting the flow of an air pump to be 1L/min, introducing standard gas with the known concentration of 20ppm for 10s, and measuring the pressure and the corresponding light intensity value of the gas chamber to be measured after the gas chamber to be measured is stable; the air pump stops after continuously working for 10s, and the pressure and the corresponding light intensity value of the air chamber to be measured are measured again after the air chamber to be measured is stable; the air pump stops for 5 seconds and then enters the next ventilation process.
3. SO with the concentration of 40ppm, 60ppm and 80ppm is respectively introduced into a photometer2Standard gas, repeat step 2, to obtain SO of different concentrations2The raw gas data are shown in FIG. 3 (note that for the image in FIG. 3 to be clearly visible, concentrations of 40ppm, 60ppm and 80ppm, SO2The light intensity AD has a magnitude 1000, 4000 and 10000 less than the true value, respectively).
4. The raw data analysis was preprocessed and absorbance calculations were performed to fit a curve, as shown in fig. 4 and 5, with a linearity error of less than ± 0.5%, thus allowing determination of
The coefficient R in (1).
5. When it is necessary to measure SO of unknown concentration2When gaseous, it is only necessary to introduce the SO2The gas is pumped into the photometer, and then the corresponding light intensity value is obtained under two different pressures, so that the photometer can pass through
Obtaining the unknown concentration of SO2Concentration value of the gas.
The embodiments described above are merely preferred embodiments of the present application, and are not intended to limit the scope of the present application, and various modifications and improvements made to the technical solutions of the present application by those skilled in the art without departing from the spirit of the present application should fall within the protection scope defined by the claims of the present application.
Claims (10)
1. A gas detection method is characterized in that different light energy absorptions are generated by changing the gas pressure in a measuring gas chamber of a photometer, so as to obtain different absorbances; the gas concentration was calculated in combination with the beer lambert ratio.
2. The gas detection method of claim 1, wherein the standard atmospheric pressure P is in accordance with beer lambert's law0Introducing gas G (gas) with lower volume concentration C into a measuring gas chamber of a photometer, wherein when the gas pressure in the measuring gas chamber is P, the absorbance generated by the gas G is A,
the gas pressure in the measuring gas chamber is P1In the case of (2), the absorbance A of the gas G1Comprises the following steps:
the gas pressure in the measuring gas chamber is P2In the case of (2), the absorbance A of the gas G2Comprises the following steps:
in the formula I1＝I2The value of the intensity of the light of the gas G detected by the detector assuming no absorption, I1' for measuring the pressure P after gas G is introduced into the gas chamber1The value of light intensity detected by the time detector, I2' for measuring the pressure P after gas G is introduced into the gas chamber2The light intensity value detected by the detector.
The formula (1) and (2) can be used for obtaining:
due to I1＝I2Therefore lnI1-lnI2＝0
Therefore, it is not only easy to use
In the closed measuring gas chamber, the absorbance ratio of the gas G under the two pressure states is equal to the pressure ratio under the two pressure states; namely:
the synthesis of (3) and (4) can obtain
The volume concentration C of the gas G is proportional to the absorbance A according to the beer Lambert law, whereby the gas concentration at normal atmospheric pressure can be obtained
The method can be obtained by the formula (5), and two or more groups of detection are carried out by detecting the pressure values in two pressure states in the measurement air chamber and the light intensity value detected by the detector, and after the calibration coefficient R is obtained, the calibration coefficient R is obtained
The volume concentration value C of the gas G under the standard atmospheric pressure can be calculated.
3. The gas detection method of claim 1, wherein the formula is
Wherein the calibration coefficient R is obtained by back-calculating the pressure and light intensity values of a gas to be measured with known concentration under two pressure states; or respectively carrying out inverse calculation on the pressure and light intensity values of a plurality of gases to be detected with known concentration in two pressure states to obtain a plurality of calibration coefficients R, and then fitting a plurality of R values to obtain a fitting curve.
4. The gas detection method according to claim 1 or 2, characterized in that the gas detection method comprises:
(1) determination of the scaling factor R:
measuring the pressure value and the light intensity value of a gas G with known concentration under two pressure states; by passing
Carrying out inverse calculation to obtain a calibration coefficient R;
(2) calculating the volume concentration of the gas to be measured:
measuring pressure values and light intensity values of gas G with unknown concentration under two pressure states; by the formula knowing the scaling factor R
And calculating to obtain a concentration value C of the gas G with unknown concentration.
5. The gas detection method according to claim 4, wherein in the determination of the calibration coefficient R in step (1), the pressure values and the light intensity values of a plurality of known gases G with different concentrations in two pressure states are respectively determined to obtain a plurality of different calibration coefficients R, and R is obtained by fitting a curve to determine the calibration coefficient R.
6. The method of any one of claims 1,2,3, and 5, wherein the photometer employs a single wavelength, a single detector, and a single measurement gas cell; no reference gas chamber is configured; the single wavelength refers to that the light entering the measurement gas chamber is light with a single wavelength, or the light entering the measurement gas chamber is light with multiple wavelengths, and the light with the single wavelength is detected at the detector.
7. A gas detection apparatus having a photometer including a light source for emitting light, a measurement gas chamber for passing the light emitted from the light source, and a detector for detecting a light intensity value of the light transmitted through the measurement gas chamber; the measurement air chamber is provided with an air inlet for the gas to be measured to enter and an air outlet for discharging the gas to be measured; the air pressure in the measuring air chamber is adjustable and can be stably measured.
8. The gas detection device according to claim 7, wherein the measurement gas chamber is capable of generating different light energy absorptions by changing the pressure of the gas to be detected therein, detecting different light intensity values and obtaining different absorbances; and calculating the concentration of the gas to be detected by combining the beer Lambert constant rate.
9. The gas detection apparatus according to claim 7 or 8, wherein the gas inlet is located at a front portion of the measurement gas chamber and the gas outlet is located at a rear portion of the measurement gas chamber; a valve is arranged at the air inlet and used for controlling the gas to be detected to enter; an air pump is arranged at the air outlet to pump in or out the gas to be detected; the photometer is not provided with a reference gas chamber; the measurement air chamber is provided with a pressure measurement device capable of detecting the pressure of the gas to be measured in the measurement air chamber.
10. The gas detection apparatus of claim 7 or 8, wherein the photometer employs a single wavelength, a single detector, and a single measurement gas cell; the front end of the measurement air chamber is provided with an optical filter or a grating for enabling light entering the measurement air chamber to be single-wavelength light; or, the front end of the detector is provided with an optical filter for enabling the light intensity value of the single-wavelength light detected by the detector.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116952884A (en) * | 2023-06-25 | 2023-10-27 | 青岛崂应海纳光电环保集团有限公司 | Gas concentration calculation method for non-dispersive infrared gas detection |
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