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CN119198610A - Automatic zero-calibration Fourier infrared gas analyzer and its analysis method - Google Patents

Automatic zero-calibration Fourier infrared gas analyzer and its analysis method Download PDF

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Publication number
CN119198610A
CN119198610A CN202411746289.1A CN202411746289A CN119198610A CN 119198610 A CN119198610 A CN 119198610A CN 202411746289 A CN202411746289 A CN 202411746289A CN 119198610 A CN119198610 A CN 119198610A
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zeroing
filter
sampling
area
electromagnetic valve
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CN202411746289.1A
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CN119198610B (en
Inventor
张涵
于志伟
何妙兴
陈晨
郭杰
陈少华
章成钢
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Hangzhou Zetian Chunlai Technology Co ltd
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Hangzhou Zetian Chunlai Technology Co ltd
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3504Investigating 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
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01Arrangements or apparatus for facilitating the optical investigation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/359Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N2021/3595Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using FTIR
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
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  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
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  • Pathology (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

The invention belongs to the technical field of analysis and detection, and particularly relates to an automatic zero correction type Fourier infrared gas analyzer and an analysis method thereof. The gas analyzer comprises a sample gas analysis flow path formed by a sample gas sampling head, a bag filter, a three-way filter, a sampling electromagnetic valve, a sampling pump, a flowmeter and an infrared gas chamber which are sequentially connected, wherein an air zeroing branch is connected between the sampling electromagnetic valve and the sampling pump and comprises the air sampling head, a condensing filter, a zeroing adsorption tube and a zeroing electromagnetic valve which are sequentially connected, and the zeroing adsorption tube comprises a gas purification area, a CO 2 absorption area, an active carbon area, an ammonia removal area and a molecular sieve area which are sequentially distributed along the air inlet direction, wherein two ends of each area are respectively packaged by absorbent cotton. The invention has comprehensive adsorption effect through the cooperative cooperation of the bag filter, the three-way filter and the condensing filter, can adsorb particles with different molecular sizes, simultaneously remove water vapor, and is beneficial to improving the detection precision of the analyzer and prolonging the service life.

Description

Automatic zero-correction Fourier infrared gas analyzer and analysis method thereof
Technical Field
The invention belongs to the technical field of analysis and detection, and particularly relates to an automatic zero calibration type Fourier infrared gas analyzer and an analysis method thereof.
Background
The Fourier infrared analyzer is easily influenced by factors such as ambient temperature, data drift is generated, clean air is required to be regularly introduced to calibrate the instrument in order to obtain accurate concentration data, the process is often influenced by the purity of the sample air, manual monitoring and zero calibration are required, an automatic zero calibration mechanism can be set if the purity of the sample air is high, and the operation and maintenance labor cost is reduced. At present, active carbon is mainly used for adsorbing impurity gas in ambient air, but the removal degree is limited, the impurity content after removal reaches ppm level, and the purity of zero calibration air still needs to be further improved in order to further improve the detection accuracy. Moreover, the degree of water removal of the sample air has an influence on the detection accuracy.
In addition, because the detection working condition is often around the severe environments such as chemical plants, smoke discharge or drain, and the like, during sample injection, particles are doped in the sample gas, the particle size of the particles is in the micron level, the molecular size of the gas is in the micron level, the particles enter the analyzer to be unfavorable for gas detection, influence the detection result, and the analyzer is seriously possibly damaged, so that long-term effective monitoring is unfavorable. Therefore, it is necessary to remove particulate matter in the sample gas in advance.
Disclosure of Invention
Based on the above-mentioned drawbacks and deficiencies of the prior art, it is an object of the present invention to at least solve one or more of the above-mentioned problems of the prior art, in other words, to provide an auto zero-correction type fourier infrared gas analyzer and an analyzing method thereof which meet one or more of the above-mentioned needs.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
An automatic zero calibration type Fourier infrared gas analyzer comprises a sample gas analysis flow path formed by a sample gas sampling head, a bag filter, a three-way filter, a sampling electromagnetic valve, a sampling pump, a flowmeter and an infrared gas chamber which are connected in sequence;
an air zeroing branch is connected between the sampling electromagnetic valve and the sampling pump and comprises an air sampling head, a condensing filter, a zeroing adsorption tube and a zeroing electromagnetic valve which are sequentially connected;
The zeroing adsorption tube comprises a gas purification area, a CO 2 absorption area, an activated carbon area, an ammonia removal area and a molecular sieve area which are distributed in sequence along the air inlet direction, wherein two ends of each area are respectively packaged by absorbent cotton.
As a preferable scheme, the pore diameters of the CO 2 absorption zone, the activated carbon zone, the ammonia removal zone and the analysis screen zone are sequentially reduced.
Preferably, the activated carbon region is used for filtering substances with the pore diameter of more than 50nm, and the molecular sieve region is used for filtering substances with the pore diameter of more than 0.5 nm.
Preferably, the ammonia removal zone is filled with anhydrous potassium dihydrogen phosphate.
Preferably, the molecular sieve zone is filled with 5A molecular sieve.
Preferably, the capsule filter adopts a hydrophobic polytetrafluoroethylene filter membrane for filtering particles with a particle size of more than 0.2 μm.
As a preferable scheme, the three-way filter is of a columnar structure, gas enters from the upper part and flows out from the side, and a water outlet is arranged at the lower part and is connected with a peristaltic pump;
The three-way filter adopts a PE filter core for filtering the particles with the particle size of more than 0.1 mu m.
The invention also provides an analysis method of the automatic zero-correction Fourier infrared gas analyzer, which comprises the following steps:
S1, opening a zeroing electromagnetic valve and closing a sampling electromagnetic valve;
s2, starting a sampling pump, and collecting a zero spectrum;
s3, closing the zeroing electromagnetic valve and opening the sampling electromagnetic valve;
S4, collecting a measurement spectrum of the sample gas to be measured, and calculating according to the zero point spectrum and the measurement spectrum to obtain the measurement concentration of the sample gas to be measured;
s5, judging whether a zeroing period is reached, if so, turning to step S1.
As a preferred solution, the step S4 specifically includes:
s41, calculating and measuring absorbance according to the zero point spectrum and the measured spectrum :
;
Wherein, Is a zero-point spectrum of light,In order to measure the spectrum of light,The absorbance spectrum is preset for saturated steam at 40 ℃, and T is the condensation temperature of a condensation filter;
s42, according to the measured absorbance And standard absorbance of the i-th sample gas to be testedStandard concentration corresponding to the concentrationCalculating to obtain the measured concentration of the ith sample gas to be measured:
;
Wherein, the proportionality coefficient of the ith sample gas to be testedAccording toAnd (5) calculating to obtain the product.
Preferably, the ratio coefficientCalculated by a least square method.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention has comprehensive adsorption effect through the cooperative coordination of the bag filter, the three-way filter and the condensing filter, can adsorb particles with different molecular sizes, and simultaneously remove water vapor, thereby being beneficial to improving the detection precision of an analyzer and prolonging the service life;
(2) The zeroing adsorption tube sequentially distributes a gas purification area, a CO 2 absorption area, an activated carbon area, an ammonia removal area and a molecular sieve area along the air inlet direction, and enables volatile substances in air to generate oxidation reaction through the gas purification area, so that the molecular size of the volatile substances is improved, the subsequent substance filtration is facilitated;
(3) The method and the device are combined with the condensing temperature of the condensing filter and the preset absorbance spectrum of saturated steam at 40 degrees to correct the measured absorbance, so that the accuracy of the measured concentration of the sample gas to be measured is effectively improved.
Drawings
FIG. 1 is a gas flow diagram of an auto-zeroing Fourier infrared gas analyzer of example 1 of the present invention;
FIG. 2 is a schematic cross-sectional view of a zeroing adsorption tube according to embodiment 1 of the present invention;
fig. 3 is a flowchart of an analysis method of the auto-zeroing type fourier infrared gas analyzer of embodiment 1 of the present invention.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention, specific embodiments of the present invention will be described below with reference to the accompanying drawings. It is evident that the drawings in the following description are only examples of the invention, from which other drawings and other embodiments can be obtained by a person skilled in the art without inventive effort.
Example 1:
As shown in fig. 1, the automatic zero-correction fourier infrared gas analyzer of this embodiment includes a sample gas analysis flow path and an air zero-setting branch, where a light source and a detector of the gas analyzer are not described herein, and only needs to refer to the prior art.
Specifically, the sample gas analysis flow path includes a sample gas sampling head 1, a bag filter 2, a three-way filter 3, a sampling solenoid valve 4, a sampling pump 5, a flow meter 6, and an infrared gas chamber 7, which are connected in this order. Wherein, draw forth the air between sampling solenoid valve 4 and the sampling pump 5 and zeroing the branch road, the air zeroing the branch road is including air sampling head 8, condensing filter 9, zeroing adsorption tube 10 and zeroing solenoid valve 11 that connect gradually.
The zeroing adsorption tube 10 of this embodiment is divided into five filling areas according to the air conveying direction, the first filling area is an air purifying area, and the filling materials of the other areas are all physical filter layers. As shown in fig. 2, the device specifically comprises a gas purification zone 10a, a CO 2 absorption zone 10b, an activated carbon zone 10c, an ammonia removal zone 10d and a molecular sieve zone 10e which are sequentially distributed along the air inlet direction, wherein both ends of each zone are respectively encapsulated by absorbent cotton 10 f. Wherein, the aperture of CO 2 absorption zone, active carbon zone, ammonia removal zone and analysis sieve zone reduces in proper order, can promote air filtration purity.
The gas purification area is filled with the conventional gas purifying agent, the conventional gas in the ambient air can be oxidized, the CO 2 absorption area is filled with the CO 2 absorbent for absorbing CO 2 in the air, the active carbon area is used for filtering substances with the aperture larger than 50nm, the ammonia removal area is filled with anhydrous potassium dihydrogen phosphate as the ammonia removal agent, and the molecular sieve area is filled with a 5A molecular sieve for filtering substances with the aperture larger than 0.5 nm.
The capsule filter of the embodiment adopts a disc type design, the inlet and the outlet are vertically symmetrically distributed, the specific structure can refer to the prior art, the volume is small, the weight is light, the diameter is 64 mm, the filtering area is 20cm 2, a 6mm pipeline is connected for use, a hydrophobic polytetrafluoroethylene PTFE filter membrane is adopted, and the ambient air can filter particles with the size of more than 0.2 mu m through the capsule filter.
The three-way filter is made of glass with a columnar structure, gas enters from the upper part, flows out from the side, a water outlet is arranged at the lower part and is connected with the peristaltic pump 12, wherein the three-way filter adopts a PE filter core, and can filter particles with the particle size of more than 0.1 mu m.
The drain outlet of the condensing filter 9 of the embodiment is connected with a peristaltic pump 13, which is convenient for draining.
Based on above-mentioned air zeroing branch road to the filtration of ambient air and dewatering, can guarantee the purity of zeroing air, can realize automatic zeroing, need not the manual supervision.
As shown in fig. 3, the analysis method of the automatic zeroing type fourier infrared gas analyzer of this embodiment includes the following steps:
(1) Opening a zeroing electromagnetic valve and closing a sampling electromagnetic valve;
(2) Starting a sampling pump to collect a zero spectrum;
specifically, after starting the sampling pump, the zero point spectrum is acquired after waiting for several minutes (e.g., 2 minutes);
(3) Closing the zeroing electromagnetic valve and opening the sampling electromagnetic valve;
(4) Collecting a measurement spectrum of the sample gas to be measured, and calculating to obtain the measurement concentration of the sample gas to be measured according to the zero point spectrum and the measurement spectrum;
specifically, absorbance is measured by first calculating from the zero point spectrum and the measured spectrum :
;
Wherein, Is a zero-point spectrum of light,In order to measure the spectrum of light,The absorbance spectrum is preset for saturated steam at 40 ℃, and T is the condensation temperature of a condensation filter;
Then according to the measured absorbance And standard absorbance of the i-th sample gas to be testedStandard concentration corresponding to the concentrationCalculating to obtain the measured concentration of the ith sample gas to be measured:
;
Wherein, the proportionality coefficient of the ith sample gas to be testedAccording toCalculated by a least square method;
(5) Judging whether a zeroing period is reached, if so, turning to the step (1).
In order to verify the effectiveness of the analysis method of the automatic zero calibration fourier infrared gas analyzer, in this embodiment, three different types of gases are analyzed and verified to compare measured concentrations before and after automatic zero calibration, and the result is shown in table 1, and the accuracy of the measured concentration after automatic zero calibration is effectively improved through the analysis method of this embodiment.
Table 1 measured concentrations of three different kinds of gases
Example 2:
The automatic zero calibration type fourier infrared gas analyzer of this embodiment is different from embodiment 1 in that:
The zeroing adsorption tube can further increase the filling areas of the activated carbon and the molecular sieve on the basis of five filling areas according to actual application requirements, so that the air filtering precision is further improved, and the cleanliness of the air is improved;
other structures may be referred to embodiment 1.
The foregoing is only illustrative of the preferred embodiments and principles of the present invention, and changes in specific embodiments will occur to those skilled in the art upon consideration of the teachings provided herein, and such changes are intended to be included within the scope of the invention as defined by the claims.

Claims (10)

1. An automatic zero calibration type Fourier infrared gas analyzer is characterized by comprising a sample gas analysis flow path formed by a sample gas sampling head, a bag filter, a three-way filter, a sampling electromagnetic valve, a sampling pump, a flowmeter and an infrared gas chamber which are connected in sequence;
an air zeroing branch is connected between the sampling electromagnetic valve and the sampling pump and comprises an air sampling head, a condensing filter, a zeroing adsorption tube and a zeroing electromagnetic valve which are sequentially connected;
The zeroing adsorption tube comprises a gas purification area, a CO 2 absorption area, an activated carbon area, an ammonia removal area and a molecular sieve area which are distributed in sequence along the air inlet direction, wherein two ends of each area are respectively packaged by absorbent cotton.
2. The auto-zeroing fourier infrared gas analyzer of claim 1, wherein the apertures of the CO 2 absorption zone, activated carbon zone, ammonia removal zone, and analysis screen zone decrease in sequence.
3. The auto-zeroing fourier infrared gas analyzer of claim 2, wherein the activated carbon region is configured to filter material having a pore size greater than 50nm and the molecular sieve region is configured to filter material having a pore size greater than 0.5 nm.
4. An auto-zeroing fourier infrared gas analyzer according to any of claims 1-3, wherein the ammonia removal zone is filled with anhydrous potassium dihydrogen phosphate.
5. The auto-zeroing fourier infrared gas analyzer of any of claims 1-3, wherein the molecular sieve zone is filled with a 5A molecular sieve.
6. An auto-zeroing fourier infrared gas analyzer according to any of claims 1-3, wherein the capsule filter is a hydrophobic polytetrafluoroethylene filter membrane for filtering particulate matter above 0.2 μm.
7. The automatic zero-correction type fourier infrared gas analyzer according to any one of claims 1 to 3, wherein the three-way filter has a columnar structure, gas enters from above and flows out from a side, and a water outlet is arranged below and connected with a peristaltic pump;
The three-way filter adopts a PE filter core for filtering the particles with the particle size of more than 0.1 mu m.
8. The method of analysis of an automatic zero-correction fourier infrared gas analyzer of any of claims 1-7, comprising the steps of:
S1, opening a zeroing electromagnetic valve and closing a sampling electromagnetic valve;
s2, starting a sampling pump, and collecting a zero spectrum;
s3, closing the zeroing electromagnetic valve and opening the sampling electromagnetic valve;
S4, collecting a measurement spectrum of the sample gas to be measured, and calculating according to the zero point spectrum and the measurement spectrum to obtain the measurement concentration of the sample gas to be measured;
s5, judging whether a zeroing period is reached, if so, turning to step S1.
9. The method according to claim 8, wherein the step S4 specifically includes:
s41, calculating and measuring absorbance according to the zero point spectrum and the measured spectrum :
;
Wherein, Is a zero-point spectrum of light,In order to measure the spectrum of light,The absorbance spectrum is preset for saturated steam at 40 ℃, and T is the condensation temperature of a condensation filter;
s42, according to the measured absorbance And standard absorbance of the i-th sample gas to be testedStandard concentration corresponding to the concentrationCalculating to obtain the measured concentration of the ith sample gas to be measured:
;
Wherein, the proportionality coefficient of the ith sample gas to be testedAccording toAnd (5) calculating to obtain the product.
10. The method of claim 9, wherein the scaling factorCalculated by a least square method.
CN202411746289.1A 2024-12-02 2024-12-02 Automatic zero-correction Fourier infrared gas analyzer and analysis method thereof Active CN119198610B (en)

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聂伟;许振宇;阚瑞峰;阮俊;姚路;王斌;张步强;何亚柏;: "可调谐二极管激光吸收光谱技术测量低温流场水汽露点温度", 光学精密工程, vol. 26, no. 08, 31 August 2018 (2018-08-31), pages 1862 - 1869 *

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