CN112378873B - Ultraviolet gas analysis method and ultraviolet gas analyzer - Google Patents
Ultraviolet gas analysis method and ultraviolet gas analyzer Download PDFInfo
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- CN112378873B CN112378873B CN202011187579.9A CN202011187579A CN112378873B CN 112378873 B CN112378873 B CN 112378873B CN 202011187579 A CN202011187579 A CN 202011187579A CN 112378873 B CN112378873 B CN 112378873B
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000004868 gas analysis Methods 0.000 title claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 260
- 238000010521 absorption reaction Methods 0.000 claims abstract description 74
- 238000002835 absorbance Methods 0.000 claims abstract description 63
- 238000005259 measurement Methods 0.000 claims abstract description 53
- 238000005070 sampling Methods 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 140
- 238000001228 spectrum Methods 0.000 claims description 81
- 229910052757 nitrogen Inorganic materials 0.000 claims description 70
- 238000012545 processing Methods 0.000 claims description 15
- 238000000862 absorption spectrum Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229910000838 Al alloy Inorganic materials 0.000 claims description 5
- 239000013307 optical fiber Substances 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000007774 longterm Effects 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 65
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 65
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000006477 desulfuration reaction Methods 0.000 description 8
- 230000023556 desulfurization Effects 0.000 description 8
- 238000012423 maintenance Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 229910052946 acanthite Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000012806 monitoring device Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 2
- 229940056910 silver sulfide Drugs 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 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
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
Abstract
The invention provides an ultraviolet gas analysis method and an ultraviolet gas analyzer, wherein a part of wave bands are selected from wave bands with consistent fluctuation trend as sampling wave bands in the absorption wave bands of a gas to be detected; introducing a plurality of measured gases with different known concentrations into the cavity of the gas chamber, selecting a measurement waveband and a reference waveband from sampling wavebands, and calculating the compensation absorbance of the measured gases; obtaining the relation between the compensation absorbance of the measured gas and the concentration of the measured gas through fitting and storing the relation; when the gas to be detected is introduced into the ultraviolet gas analyzer, an absorption curve of the gas to be detected is obtained in real time, and real-time compensation absorbance obtained by dividing the average absorbance of the measurement waveband by the average absorbance of the reference waveband is substituted into a stored concentration formula to obtain real-time concentration data of the gas to be detected. The invention has the beneficial effects that: the reference measurement is realized only by combining a single-channel gas chamber with a software algorithm, long-term drift is eliminated, and the method has the advantages of good stability, low cost and good real-time property.
Description
Technical Field
The invention relates to the technical field of measurement, in particular to an ultraviolet gas analysis method and an ultraviolet gas analyzer.
Background
The biogas is a combustible mixed gas and generally contains methane, carbon dioxide, ammonia gas, hydrogen sulfide and other gases. The existing biogas analyzers are mainly used for detecting the content of index gases such as methane, carbon dioxide, oxygen and the like, and the content of hydrogen sulfide is not concerned, but the hydrogen sulfide in the biogas is a harmful gas which has strong corrosion effect on pipelines, instruments and equipment, and the leakage of the hydrogen sulfide in the air pollutes the atmosphere and is harmful to human health. Therefore, monitoring the hydrogen sulfide content in biogas is also not negligible.
The environmental protection standard of China is strictly specified: when the biogas energy is utilized, the content of H2S in the biogas gas is not more than 20mg/m 3. In fact, the mass concentration of H2S in the biogas before desulfurization is far higher than 20mg/m3 and is higher than the specification of the national environmental protection standard. Therefore, the removal of H2S becomes an essential link before the use of biogas, and a gas analyzer is required to monitor the content of hydrogen sulfide in biogas.
In order to monitor the concentration of H2S in biogas, patent document CN1040866 discloses an electrochemical H2S sensor, in which an electrochemical H2S sensor contacts a gas to be detected through a silver/silver sulfide electrode in the sensor, an electrolyte soaked on the silver/silver sulfide electrode reacts with the gas to be detected and generates an electric signal proportional to the gas concentration, the concentration of the gas to be detected is obtained by measuring the generated electric signal, and the high-concentration hydrogen sulfide gas reacts with the electrolyte to cause continuous consumption of the electrolyte, so that the service life of the electrochemical sensor is short and maintenance and replacement are required.
In order to prolong the service life of the electrochemical sensor and enable the measured gas to be always in the range of the electrochemical sensor, patent document US5569838A discloses a technical scheme of diluting high-concentration sample gas by using diluent gas and then measuring the concentration of the diluted mixed gas by using the electrochemical sensor. Meanwhile, patent document CN202661435U discloses a device for prolonging the service life of an electrochemical H2S sensor, wherein the time ratio of introducing hydrogen sulfide and air into the electrochemical hydrogen sulfide sensor is adjusted by a three-way valve, and this scheme can avoid huge loss of the electrochemical sensor caused by introducing hydrogen sulfide into the device all the time when measuring the concentration of hydrogen sulfide, so as to achieve the purpose of prolonging the service life of the electrochemical sensor, and reduce the maintenance cost of the product.
In order to improve the reliability and real-time performance of H2S concentration measurement, patent document CN108051388A discloses an H2S gas ultraviolet spectrum detection device and a method thereof, wherein the device comprises an ultraviolet light source, a long-optical-path gas absorption cell, an ultraviolet fiber spectrometer and a computer; after ultraviolet light emitted by an ultraviolet light source enters the long-optical-path gas absorption cell, the ultraviolet light is reflected for multiple times by a reflecting mirror arranged in the gas absorption cell and is transmitted to an ultraviolet light fiber spectrometer by an optical fiber; the device adopts long light path gas absorption cell can realize low concentration H2S real-time detection function, but its light path is complicated, contain accurate optical device, in case long light path gas absorption cell is contaminated, the later maintenance cost is high.
In order to provide an online hydrogen sulfide gas monitoring device with good long-term stability, patent document CN109001140A discloses a dual-optical-path ultraviolet differential spectrum gas analyzer, which includes an ultraviolet light source, a chopper wheel, a dual-optical-path gas chamber and an ultraviolet spectrometer, wherein the dual-optical-path gas chamber includes a detection gas chamber and a reference gas chamber arranged up and down, the detection gas chamber is filled with a gas to be detected, the reference gas chamber is filled with nitrogen, and the concentration of the gas to be detected can be obtained by measuring the spectrum of the gas chamber and the spectrum of the reference gas chamber. In addition, patent document CN101526472B discloses an intelligent ultraviolet gas analyzer, which includes an ultraviolet light source and a light cutting wheel, wherein both ends of the light cutting wheel are respectively provided with an optical filter and purple glass. The partial reflection lens divides the incident ultraviolet light into two beams, one part enters the measuring edge, the other part enters the reference edge and is detected by the photoelectric detectors positioned on the measuring edge and the reference edge respectively, and the concentration of the gas to be detected is obtained according to the optical signals of the two channels. The gas analyzer can eliminate long-term drift, but the gas analyzer comprises two photoelectric detectors, a partial reflecting mirror and a light cutting wheel, so that the instrument has poor shock resistance, a complex structure and high cost, and the consistency difference of the two photoelectric detectors can bring errors to gas concentration measurement.
In order to improve the real-time performance of gas measurement and improve the anti-seismic performance of a gas analyzer, patent document CN2589969 discloses an online monitoring device for hydrogen sulfide gas, wherein an ultraviolet light source is emitted to a semi-reflective and semi-transparent mirror through a gas cell to be measured filled with hydrogen sulfide gas, after light passes through the semi-reflective and semi-transparent mirror, 50% of light intensity is transmitted and then received by a photomultiplier through a 228 nm optical filter, and after 50% of light intensity is reflected, the light is received by a photodiode detector through a 361 nm optical filter. Because hydrogen sulfide gas has a significant absorption peak at 228 nm and almost no absorption at 361 nm, the two bands can be respectively used as a measurement channel and a reference channel to form a differential measurement system.
In the prior art, the reference measurement is realized by matching a double-light-path structure with a light-cutting sheet and/or a semi-transparent semi-reflective lens, so that the conventional gas analyzer has poor reliability, complex structure and high cost.
In the background art, only the application scenario of measuring H2S in biogas is illustrated, but in fact, the application scenario is not limited to this, and the ultraviolet gas analyzer disclosed in the present application may also be applied to the measurement of hydrogen sulfide concentration in the application scenarios of natural gas, petroleum, and the like, and may also be applied to the measurement of other gas concentrations.
Disclosure of Invention
In view of this, the present invention provides an ultraviolet gas analysis method and an ultraviolet gas analyzer.
In a first aspect, the present invention provides a method for analyzing ultraviolet gas, which specifically includes the following steps;
s101: selecting a part of wave bands as sampling wave bands in the absorption wave bands of the gas to be detected;
s102: respectively introducing pure nitrogen and a plurality of gases to be detected with different known concentrations into the cavity of the gas chamber to obtain a plurality of gas absorption curves with different concentrations; the gas absorption curve comprises: a pure nitrogen absorption curve and a plurality of measured gas absorption curves with different known concentrations;
s103: selecting a measurement band and a reference band from the sampling bands selected in step S101;
s104: calculating the compensation absorbance corresponding to each gas absorption curve in the measurement waveband and the reference waveband selected in the step S103;
s105: fitting to obtain a relational expression between the compensation absorbance of the gas to be detected and the concentration of the gas to be detected according to the compensation absorbance data of each absorption curve and the corresponding known concentration data, and storing the relation between the compensation absorbance of the gas to be detected and the concentration of the gas to be detected;
s106, introducing pure nitrogen into the ultraviolet gas analyzer, obtaining the spectrum of the pure nitrogen through a spectrometer, and storing the spectrum of the pure nitrogen;
s107, introducing the gas to be detected into the ultraviolet gas analyzer, obtaining the real-time spectrum of the gas to be detected through a spectrometer, and obtaining the real-time absorption curve of the gas to be detected according to the real-time spectrum of the gas to be detected and the nitrogen spectrum stored in the step S106;
s108, calculating the real-time compensation absorbance of the gas to be detected according to the real-time absorption curve of the gas to be detected in the measurement wave band and the sampling wave band selected by the method in the step S103; and substituting the real-time compensation absorbance data of the detected gas into the relational expression between the compensation absorbance of the detected gas and the concentration of the detected gas stored in the step S105 to obtain the real-time concentration of the detected gas.
Step S101 includes the following substeps:
s201: introducing pure nitrogen into the air chamber cavity to obtain a pure nitrogen spectrum which is used as a zero point spectrum D0 at the initial moment; introducing pure nitrogen into the air chamber cavity at preset time intervals to obtain m pure nitrogen spectrums D0, D1, D2 and D3 … … Dm at different time intervals; m is a natural number;
s202: respectively subtracting the plurality of pure nitrogen spectrums D0, D1, D2 and D3 … … Dm spaced at different time intervals from the zero spectrum D0 at the initial moment to obtain a plurality of fluctuation spectrums, and then dividing the plurality of obtained fluctuation spectrums by the zero spectrum D0 to obtain a plurality of fluctuation curves;
s203: and observing the plurality of fluctuation curves, locking the wave bands with the fluctuation changes of the plurality of fluctuation curves consistent with the change trends of the plurality of fluctuation curves in the absorption wave bands of the gas to be detected, and selecting a part of wave bands as sampling wave bands.
The absorption curve of the measured gas in step S102 is obtained by the following method: and respectively subtracting a plurality of measured gas spectrums with different known concentrations from the pure nitrogen spectrum to obtain a plurality of absorption spectrums, dividing the plurality of obtained absorption spectrums by the pure nitrogen spectrum to obtain a plurality of measured gas absorption curves, wherein the pure nitrogen absorption spectrum is divided by the pure nitrogen spectrum to obtain the absorption curve of the pure nitrogen.
Step S103 includes the following substeps:
in the sampling wavelength band selected in step S101, the plurality of absorption curves in step S102 are observed, a section of the absorption curve of any one of the gases with a larger absorbance than other parts of the absorption curve is selected as a measurement wavelength band, and a wavelength band with a smaller absorbance than other parts of the absorption curve is selected as a reference wavelength band.
The ordinate of each point on the gas absorption curve represents the absorbance of the detected gas, and the abscissa represents the wavelength; the compensation absorbance is the average absorbance of the measuring waveband/the average absorbance of the reference waveband, and the real-time compensation absorbance is the real-time average absorbance of the measuring waveband/the real-time average absorbance of the reference waveband.
In a second aspect, the present invention provides an ultraviolet gas analyzer, which employs the ultraviolet gas analyzing method provided in the first aspect of the present invention, and specifically includes: the device comprises an ultraviolet light source, an air chamber cavity, a spectrometer and a data processing unit; the ultraviolet light source, the spectrometer and the air chamber cavity are connected through optical fibers; the spectrometer is electrically connected with the data processing unit; the ultraviolet light source is used for providing ultraviolet light; the spectrometer is used for measuring the gas to be measured and outputting a corresponding spectrum; and the data processing unit is used for processing and calculating to obtain the concentration of the gas to be detected.
The air chamber cavity is made of aluminum alloy, and the inner wall of the air chamber cavity is subjected to black oxidation treatment.
The ultraviolet light source is a xenon lamp light source.
The ultraviolet gas analysis method and the ultraviolet gas analyzer provided by the invention have the beneficial effects that: compared with an electrochemical H2S sensor, the sensor has the advantages of long service life and low later maintenance cost; compared with a double-light-path ultraviolet gas analyzer in the prior art, the reference measurement is realized only by combining a single-channel gas chamber with a software algorithm, the influence of long-term drift on H2S concentration measurement is eliminated, the stability is good, and the later maintenance cost is reduced; a motor and a light-cutting sheet are omitted, the structure of the analyzer is simplified, the cost of the analyzer is reduced, and the shock resistance of the analyzer is improved; the measurement waveband spectrum and the reference waveband spectrum can be collected simultaneously, and the real-time performance of gas measurement is improved.
Because the double-range calibration is carried out, the same gas analyzer can be adopted to detect the H2S concentration in the biogas before and after desulfurization, the gas concentration measurement efficiency is improved, and the gas concentration measurement cost is reduced. The H2S concentration before desulfurization is measured by high range, so that the operation state of the biogas digester can be monitored; the desulfurization efficiency can be monitored by measuring the concentration of the desulfurized H2S with a low range; the gas chamber cavity of the ultraviolet gas analyzer is made of aluminum alloy, the inner wall of the gas chamber cavity is subjected to oxidation treatment, the corrosion resistance of the gas analyzer is enhanced, the service life of the gas analyzer is prolonged, meanwhile, stray light caused by diffuse reflection of ultraviolet light on the inner wall of the gas chamber cavity can be prevented through black oxidation, and the gas concentration measurement precision is improved.
Drawings
FIG. 1 is a main flow diagram of the ultraviolet gas analysis method disclosed in the present invention;
fig. 2 is four pure nitrogen fluctuation curves obtained by introducing pure nitrogen into an ultraviolet gas analyzer on the first day, the third day, the fifth day and the seventh day respectively, acquiring four pure nitrogen spectrums D0, D1, D2 and D3 corresponding to different time intervals by using a spectrometer, subtracting the four pure nitrogen spectrums D0 acquired on the first day from the four pure nitrogen spectrums D3826 at different time intervals to obtain four pure nitrogen fluctuation spectrums corresponding to four time intervals, and dividing the four obtained pure nitrogen fluctuation spectrums by the pure nitrogen spectrum D0 obtained on the first day in the embodiment of the present invention;
fig. 3 is a graph showing five absorption curves obtained by introducing pure nitrogen, 100ppm H2S, 250ppm H2S, 400ppm H2S and 500ppm H2S into an ultraviolet gas analyzer, respectively, acquiring spectra corresponding to five different concentrations of H2S through a spectrometer, and obtaining the spectra of five different concentrations of H2S and the pure nitrogen spectrum in the embodiment of the present invention;
FIG. 4 is a schematic view of the structure of the ultraviolet gas analyzer disclosed in the embodiment of the present invention;
fig. 5 is a graph showing the trend of the concentration indicating error value measured for 7 days continuously after standard gas with a concentration of 0ppm is introduced into the ultraviolet gas analyzer disclosed in the embodiment of the present invention and the conventional single-channel ultraviolet gas analyzer under the same conditions.
1-ultraviolet light source, 2-air chamber cavity, 3-spectrometer, 4-data processing unit and 5-optical fiber
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be further described with reference to the accompanying drawings.
Referring to fig. 1, an ultraviolet gas analysis method specifically includes the following steps:
s101: selecting a part of wave bands as sampling wave bands in the absorption wave bands of the gas to be detected;
in the background and examples of the present application, hydrogen sulfide gas is used for illustration, but not limited thereto; the absorption band of hydrogen sulfide gas to ultraviolet light is known to be 190-240nm, and when other measured gases are measured, the absorption bands of different gases to ultraviolet light can be distinguished.
The sampling wave band is selected in the following way: pure nitrogen is introduced into the gas chamber cavity, a pure nitrogen spectrum is obtained through analysis of a spectrometer, the pure nitrogen spectrum is used as a zero point spectrum D0 at an initial moment and is stored, and pure nitrogen is introduced into the gas chamber cavity at intervals within a period of time to respectively obtain pure nitrogen spectrums D0, D1, D2 and D3 … … Dm (m is a natural number) at different intervals; respectively subtracting a plurality of pure nitrogen spectrums D0, D1, D2 and D3 … … Dm at different time intervals from the zero spectrum D0 at the initial moment to obtain a plurality of fluctuation spectrums, and then dividing the plurality of obtained fluctuation spectrums by the zero spectrum D0 to obtain a plurality of fluctuation curves; by observing a plurality of fluctuation curves, within the absorption band of hydrogen sulfide of 190-.
Referring to fig. 2, fig. 2 is a diagram illustrating that pure nitrogen is respectively introduced into an ultraviolet gas analyzer on the first day, the third day, the fifth day and the seventh day in the embodiment of the present invention, pure nitrogen spectrums corresponding to four time periods are acquired by a spectrometer, which are respectively D0, D1, D2 and D3, four pure nitrogen fluctuation spectrums are obtained by subtracting the pure nitrogen spectrums corresponding to the four time periods from the pure nitrogen spectrum obtained on the first day, and four fluctuation curves are obtained by dividing the obtained four pure nitrogen fluctuation spectrums by the pure nitrogen spectrum obtained on the first day; in fig. 2, the fluctuation trend of each curve is consistent within the range of the band 200-220nm on the left side, that is, the fluctuation rate of each curve is either greater than zero or less than zero or equal to 0, so that 200-220nm is selected as the sampling band of hydrogen sulfide, and of course, only a part of the bands may be selected as the sampling band within the above band, the fluctuation trend of the fluctuation curve D3 obtained at the seventh day varies within the range of the band 220-240nm, and the fluctuation rate starts to be less than zero, so that the fluctuation trend is not used as the sampling band of hydrogen sulfide.
And compared with other wave bands, the long-term drifts corresponding to the wave bands with consistent fluctuation curve variation trends are consistent.
S102: respectively introducing pure nitrogen and a plurality of gases to be detected with different known concentrations into the cavity of the gas chamber to obtain a plurality of gas absorption curves with different concentrations; the gas absorption curve includes: a pure nitrogen absorption curve and a plurality of measured gas absorption curves with different known concentrations; the ordinate of each point on the gas absorption curve represents the absorbance of the measured gas and the abscissa represents the wavelength.
The absorption curve of the measured gas in step S102 is obtained by the following method: and subtracting the measured gas spectrums with different known concentrations from the pure nitrogen spectrum to obtain a plurality of absorption spectra, and dividing the obtained plurality of absorption spectra by the pure nitrogen spectrum to obtain a plurality of measured gas absorption curves, wherein the pure nitrogen absorption spectrum is divided by the pure nitrogen spectrum to obtain a fluctuation curve of the pure nitrogen, which is equivalent to the absorption curve of the measured gas with zero concentration.
Referring to fig. 3, fig. 3 is a diagram illustrating five absorption curves obtained by introducing pure nitrogen (pure nitrogen corresponds to H2S with a concentration of 0), 100ppm H2S, 250ppm H2S, 400ppm H2S and 500ppm H2S into a gas analyzer, respectively, and acquiring spectra corresponding to five different concentrations of H2S through a spectrometer, and according to the spectra of five different concentrations of H2S and the pure nitrogen spectrum in the embodiment of the present invention. In FIG. 3, the absorption curves are from top to bottom for 0ppm H2S, 100ppm H2S, 250ppm H2S, 400ppm H2S and 500ppm H2S, respectively.
S103: selecting a measurement band and a reference band from the sampling bands selected in step S101;
in the sampling band selected in step S101, the plurality of absorption curves in step S102 are observed, a section of the absorption curve of any one of the gases having a larger absorbance than other portions of the absorption curve is selected as a measurement band, and a band having a smaller absorbance than other portions of the absorption curve is selected as a reference band.
In the sampling waveband, a plurality of absorption curves are observed, a part of waveband is selected from the waveband with large absorbance of 200-. Because the variation trend of each absorption curve in the sampling wave band is consistent, the absorbances of a plurality of absorption curves are basically consistent.
S104: calculating the compensation absorbance corresponding to each gas absorption curve in the measurement waveband and the reference waveband selected in the step S103;
in the embodiment of the application, for hydrogen sulfide gas, the average absorbance of each absorption curve is calculated in the selected measurement waveband and is used as the measurement absorbance;
calculating the average absorbance of the gas absorption curve as the reference absorbance within the reference waveband selected in the step S102;
in the embodiment of the application, for hydrogen sulfide gas, the average absorbance of each absorption curve is calculated in the selected reference waveband and is used as the reference absorbance;
compensating absorbance which is the average absorbance of the measuring wave band/the average absorbance of the reference wave band;
s105: and fitting to obtain a relational expression between the compensation absorbance of the gas to be detected and the concentration of the gas to be detected according to the compensation absorbance data of each absorption curve and the corresponding known concentration data, and storing the relation between the compensation absorbance of the gas to be detected and the concentration of the gas to be detected.
S106, when gas measurement is carried out, introducing pure nitrogen into the ultraviolet gas analyzer, obtaining a pure nitrogen spectrum through a spectrometer, and storing the pure nitrogen spectrum;
s107, introducing the gas to be detected into the ultraviolet gas analyzer, obtaining the real-time spectrum of the gas to be detected through a spectrometer, and obtaining the real-time absorption curve of the gas to be detected according to the real-time spectrum of the gas to be detected and the pure nitrogen spectrum stored in the step S106;
s108, calculating the real-time compensation absorbance of the gas to be detected according to the real-time absorption curve of the gas to be detected in the measurement wave band and the sampling wave band selected by the method in the step S103;
compensating absorbance in real time, namely real-time average absorbance of a measurement waveband/real-time average absorbance of a reference waveband;
and substituting the real-time compensation absorbance data of the detected gas into the relational expression between the compensation absorbance of the detected gas and the concentration of the detected gas stored in the step S105 to obtain the real-time concentration of the detected gas.
Referring to fig. 4, fig. 4 is a structural diagram of a gas analyzer according to an embodiment of the present invention; an ultraviolet gas analyzer, comprising: the device comprises an ultraviolet light source 1, an air chamber cavity 2, a spectrometer 3 and a data processing unit 4; the gas chamber cavity 2 is made of aluminum alloy, the inner wall of the gas chamber cavity 2 is subjected to oxidation treatment, the corrosion resistance of the gas analyzer is enhanced, the service life of the gas analyzer is prolonged, meanwhile, stray light caused by diffuse reflection of ultraviolet light on the inner wall of the gas chamber cavity can be prevented through black oxidation treatment, and the gas concentration measurement precision is improved.
In the embodiment of the present invention, the air chamber cavity 2 is a single-channel air chamber, but the type of the air chamber cavity 2 is not limited, and may be a single-channel or multi-channel air chamber.
The ultraviolet light source 1 and the spectrometer 3 are connected with the air chamber cavity 2 through optical fibers 5; the spectrometer 3 is electrically connected with the data processing unit 4; an ultraviolet light source 1 for supplying ultraviolet light; the spectrometer 3 is used for measuring the gas to be measured and outputting a corresponding spectrum; the data processing unit 4 is used for processing and calculating the measured gas concentration. The data processing unit 4 further comprises a memory for storing the zero point spectrum and the relation between the measured gas compensation absorbance and the measured gas concentration.
And the data processing unit finally outputs the concentration of the gas to be detected to the upper computer through an RS232 interface and displays the concentration through an output window of the upper computer.
Furthermore, in order to realize that the same ultraviolet gas analyzer is used for measuring H2S in the biogas before and after desulfurization, the ultraviolet gas analyzer is calibrated in two measuring ranges, namely, one curve is used for low-concentration H2S, the other curve is used for high-concentration H2S, and the concentration of the measured gas is calculated according to the range of the compensation absorbance data of the measured H2S.
The ultraviolet gas analysis method and the ultraviolet gas analyzer provided by the invention have the beneficial effects that: (1) the influence of long-term drift on the measurement of the H2S concentration is eliminated only by adopting a single-air-chamber structure and combining a software algorithm, the stability is good, and the later maintenance cost is reduced; compared with the double-light-path ultraviolet gas analyzer in the prior art, the double-light-path ultraviolet gas analyzer omits a motor and a light-cutting sheet, simplifies the structure of the analyzer and improves the shock resistance of the analyzer; the measurement waveband spectrum and the reference waveband spectrum can be collected simultaneously, and the real-time performance of gas measurement is improved.
(2) Because the double-range calibration is carried out, the same ultraviolet gas analyzer can be used for measuring the H2S concentration in the methane before and after desulfurization, and the H2S concentration before desulfurization is measured in a high range, so that the running state of the methane tank can be monitored; the concentration of the desulfurized H2S is measured by using a low range, so that the desulfurization efficiency can be monitored, the gas concentration measurement efficiency is improved, and the gas concentration measurement cost is reduced.
(3) The gas chamber cavity is made of aluminum alloy, the inner wall of the gas chamber cavity is subjected to oxidation treatment, the corrosion resistance of the gas analyzer is enhanced, the service life of the gas analyzer is prolonged, meanwhile, stray light caused by diffuse reflection of ultraviolet light on the inner wall of the gas chamber cavity can be prevented through black oxidation treatment, and the gas concentration measurement precision is improved.
In order to further verify the technical effects of the ultraviolet gas analysis method and the ultraviolet gas analyzer disclosed by the invention, the ultraviolet gas analyzer disclosed in the embodiment of the invention and a traditional single-channel ultraviolet gas analyzer are subjected to comparison test under the same experimental conditions to analyze the long-term drift size of the ultraviolet gas analyzer, and the performance and advantages of the ultraviolet gas analyzer adopting the ultraviolet gas analysis method disclosed by the invention are further verified.
Under the same detection condition, the same gas with known concentration is respectively introduced into the ultraviolet gas analyzer disclosed by the invention and the traditional single-channel ultraviolet gas analyzer, the gas concentration is measured for seven days continuously, and the data measurement results are recorded to respectively obtain the data in the tables 1 and 2.
First, the ultraviolet gas analyzer disclosed in the embodiment of the present invention was used to perform the test at the zero point (0ppm) and the range point (low range 499ppm and high range 4994ppm) of the concentration, and the concentration data and the drift data are shown in table 1:
TABLE 1
Taking a low-range ultraviolet gas analyzer with a range of 0-499ppm as an example for illustration, respectively introducing standard gases with different known concentrations into the ultraviolet gas analyzer, generally selecting a zero concentration (0ppm) and a range point concentration (499ppm) as examples for measurement, continuously measuring concentration data for 7 days to respectively obtain concentration data at different moments, comparing the concentration data obtained at different moments with the standard gas concentration to obtain a maximum error value of the concentration measurement, and dividing the obtained maximum error value of the concentration by the range value to obtain drift amount data, wherein when the standard gas concentration is 0ppm, the measured maximum error value of the concentration is 4ppm, and the zero drift amount obtained by dividing the maximum error value of 4ppm by the range value 499ppm is 0.8%; similarly, the maximum error value for the concentration was 8ppm and the low range point drift amount was 1.6% when the standard gas concentration was 499ppm, and the maximum error value for the concentration was 66ppm and the high range point drift amount was 1.32% when the standard gas concentration was 4994 ppm.
(II) the concentration of the traditional single-channel ultraviolet gas analyzer is measured at the zero point (0ppm) and the range point (low range 499ppm and high range 4994ppm), and the concentration data and the drift data are shown in Table 2:
TABLE 2
Taking a low-range ultraviolet gas analyzer with a range of 0-499ppm as an example for illustration, respectively introducing standard gases with different known concentrations into the ultraviolet gas analyzer, generally selecting a zero concentration (0ppm) and a range point concentration (499ppm) as examples for measurement, continuously measuring concentration data for 7 days to respectively obtain concentration data at different moments, comparing the concentration data obtained at different moments with the standard gas concentration to obtain a maximum error value of the concentration measurement, dividing the obtained maximum error value of the concentration by the range value to obtain drift amount data, when the table can know that the standard gas concentration is 0ppm, the measured maximum error value of the concentration is 28ppm, and dividing the maximum error value of 28ppm by the range 499ppm to obtain the drift amount of 5.61%; similarly, when the standard gas concentration is 499ppm, the maximum error value of the concentration is 29ppm, and the drift amount of the low-range point is 5.81%; when the standard gas concentration is 4994ppm, the maximum error value of the concentration is 159ppm, and the drift amount of the high range point is 3.18%.
The data in tables 1 and 2 were compared using the zero data as an example, and the obtained data is shown in table 3:
TABLE 3
When standard gas with the concentration of 0 is respectively introduced into the ultraviolet gas analyzer disclosed by the invention and the traditional single-channel ultraviolet gas analyzer, the concentration measurement results of the two ultraviolet gas analyzers are recorded for 7 days continuously, the concentration measurement results minus the standard gas concentration of 0 are obtained to obtain concentration indication error values corresponding to the two ultraviolet gas analyzers, the concentration indication error values are respectively marked as indication error 1 and indication error 2, and the concentration indication error data in the table 3 are drawn into trend lines to obtain a graph 5.
As can be seen from the analysis of table 1, table 2, table 3 and fig. 5, compared with the conventional single-channel ultraviolet gas analyzer, the ultraviolet gas analyzer disclosed in the embodiment of the present invention has the advantages of small long-term drift, high measurement accuracy, high stability of gas concentration measurement data, and obvious advantages.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. An ultraviolet gas analysis method, characterized in that: the method comprises the following steps:
s101: selecting a part of wave bands as sampling wave bands in the absorption wave bands of the gas to be detected;
s102: respectively introducing pure nitrogen and a plurality of measured gases with different known concentrations into the cavity of the gas chamber to obtain a plurality of gas absorption curves with different concentrations; the gas absorption curve comprises: a pure nitrogen absorption curve and a plurality of measured gas absorption curves with different known concentrations;
s103: selecting a measurement band and a reference band from the sampling bands selected in step S101;
s104: calculating the compensation absorbance corresponding to each gas absorption curve in the measurement waveband and the reference waveband selected in the step S103;
s105: fitting to obtain a relational expression between the compensation absorbance of the gas to be detected and the concentration of the gas to be detected according to the compensation absorbance data of each gas absorption curve and the corresponding known concentration data, and storing the relation between the compensation absorbance of the gas to be detected and the concentration of the gas to be detected;
s106: introducing pure nitrogen into the ultraviolet gas analyzer, obtaining the spectrum of the pure nitrogen through a spectrometer, and storing the spectrum of the pure nitrogen;
s107: introducing the gas to be detected into the ultraviolet gas analyzer, obtaining the real-time spectrum of the gas to be detected through the spectrometer, and obtaining the real-time absorption curve of the gas to be detected according to the real-time spectrum of the gas to be detected and the nitrogen spectrum stored in the step S106;
s108: calculating the real-time compensation absorbance of the measured gas according to the real-time absorption curve of the measured gas in the measurement waveband and the sampling waveband selected by the method in the step S103; substituting the real-time compensation absorbance data of the detected gas into the relational expression between the compensation absorbance of the detected gas and the concentration of the detected gas stored in the step S105 to obtain the real-time concentration of the detected gas;
in the sampling wave band selected in the step S101, observing a plurality of gas absorption curves in the step S102, selecting a section of the absorption curve of any one of the gases with a larger absorbance relative to other parts of the absorption curve as a measurement wave band, and selecting a wave band with a smaller absorbance relative to other parts of the absorption curve as a reference wave band;
the ordinate of each point on the gas absorption curve represents the absorbance of the detected gas, and the abscissa represents the wavelength; the compensation absorbance is the average absorbance of the measurement waveband/the average absorbance of the reference waveband, and the real-time compensation absorbance is the real-time average absorbance of the measurement waveband/the real-time average absorbance of the reference waveband;
the absorption curve of the measured gas in step S102 is obtained by the following method: and respectively subtracting a plurality of measured gas spectrums with different known concentrations from the pure nitrogen spectrum to obtain a plurality of absorption spectrums, dividing the plurality of obtained absorption spectrums by the pure nitrogen spectrum to obtain a plurality of measured gas absorption curves, wherein the pure nitrogen absorption spectrum is divided by the pure nitrogen spectrum to obtain the absorption curve of the pure nitrogen.
2. The ultraviolet gas analysis method of claim 1, wherein: step S101 includes the following substeps:
s201: introducing pure nitrogen into the air chamber cavity to obtain a pure nitrogen spectrum which is used as a zero point spectrum D0 at the initial moment; introducing pure nitrogen into the air chamber cavity at preset time intervals to obtain m pure nitrogen spectrums D0, D1, D2 and D3 … … Dm at different time intervals; m is a natural number;
s202: respectively subtracting the plurality of pure nitrogen spectrums D0, D1, D2 and D3 … … Dm spaced at different time intervals from the zero spectrum D0 at the initial moment to obtain a plurality of fluctuation spectrums, and then dividing the plurality of obtained fluctuation spectrums by the zero spectrum D0 to obtain a plurality of fluctuation curves;
s203: and observing the plurality of fluctuation curves, locking the wave bands with the fluctuation changes of the plurality of fluctuation curves consistent with the change trends of the plurality of fluctuation curves in the absorption wave bands of the gas to be detected, and selecting a part of wave bands as sampling wave bands.
3. An ultraviolet gas analyzer using the ultraviolet gas analyzing method as set forth in any one of claims 1 to 2, characterized in that: the method specifically comprises the following steps: the device comprises an ultraviolet light source, an air chamber cavity, a spectrometer and a data processing unit; the ultraviolet light source, the spectrometer and the air chamber cavity are connected through optical fibers; the spectrometer is electrically connected with the data processing unit; the ultraviolet light source is used for providing ultraviolet light; the spectrometer is used for measuring the gas to be measured and outputting a corresponding spectrum; and the data processing unit is used for processing and calculating to obtain the concentration of the gas to be detected.
4. The ultraviolet gas analyzer of claim 3, wherein: the air chamber cavity is made of aluminum alloy, and the inner wall of the air chamber cavity is subjected to black oxidation treatment.
5. The ultraviolet gas analyzer of claim 3, wherein: the ultraviolet light source is a xenon lamp light source.
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