CN110987911A - Ozone analysis method and ozone analyzer based on chemiluminescence method - Google Patents
Ozone analysis method and ozone analyzer based on chemiluminescence method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000004458 analytical method Methods 0.000 title claims abstract description 25
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000007789 gas Substances 0.000 claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims abstract description 23
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000005283 ground state Effects 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims description 11
- 238000001514 detection method Methods 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000005259 measurement Methods 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 8
- 229960003753 nitric oxide Drugs 0.000 description 30
- 239000003570 air Substances 0.000 description 11
- 238000005375 photometry Methods 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
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- 230000009471 action Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
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- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 241000282414 Homo sapiens Species 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
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- GAKLFAZBKQGUBO-UHFFFAOYSA-N 2-methyl-3-nitrophenol Chemical compound CC1=C(O)C=CC=C1[N+]([O-])=O GAKLFAZBKQGUBO-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- -1 particulate matters Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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- 238000003908 quality control method Methods 0.000 description 1
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- 239000005437 stratosphere Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
- G01N21/766—Chemiluminescence; Bioluminescence of gases
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/0039—O3
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Abstract
The application relates to an ozone analysis method and an ozone analyzer based on a chemiluminescence method. The ozone analysis method comprises the following steps: measuring a first fluorescent signal of the sample gas; reacting ozone in the sample gas with excess nitric oxide to generate excited nitrogen dioxide; measuring a second fluorescent signal during the return of the nitrogen dioxide to the ground state; and analyzing the ozone concentration in the sample gas according to the first fluorescence signal and the second fluorescence signal. According to the ozone analysis method, after the ozone and the nitric oxide gas are subjected to chemical reaction, the ozone and the nitric oxide gas emit light, the chemical reaction and the light-emitting characteristic wavelength have high selectivity, so that the problem of interference of coexisting substances can be solved, and the measurement result is more accurate and reliable.
Description
Technical Field
The application relates to the field of environmental monitoring, in particular to an ozone analysis method and an ozone analyzer based on a chemiluminescence method.
Background
The chemical formula of the ozone is O3Also called as triatomic oxygen and superoxide, which are known for their fishy smell like that, they can be reduced to oxygen at room temperature. Has a larger specific gravity than oxygen, is easy to dissolve in water and is easy to decompose. Ozone is an important product of atmospheric photochemical reaction, and the ozone in the stratosphere can absorb ultraviolet rays to prevent human beings from being damaged by the ultraviolet rays; ozone in the troposphere affects human health and the ecological environment.
Ozone is an important pollutant in environmental air, the ozone pollution degree in many places is increasingly increased in recent years, the ozone pollution prevention situation is very severe, and therefore accurate measurement of the concentration of the ozone in the air is very critical. At present, an ozone monitoring method specified in environmental air quality standard (GB3095-2012) is an ultraviolet photometry, and an ultraviolet photometry for measuring ozone in environmental air (HJ590-2010) specifies an ultraviolet photometry measuring method and a quality control measure for ozone in environmental air.
Disclosure of Invention
The purpose of the application is to provide an ozone analysis method and an ozone analyzer based on a chemiluminescence method.
The application provides an ozone analysis method based on a chemiluminescence method, which comprises the following steps: measuring a first fluorescent signal of the sample gas; reacting ozone in the sample gas with excess nitric oxide to generate excited nitrogen dioxide; measuring a second fluorescent signal during return of the nitrogen dioxide to a ground state; and analyzing the concentration of ozone in the sample gas according to the first fluorescence signal and the second fluorescence signal.
Optionally, according to the ozone analysis method described above, the analyzing the concentration of ozone in the sample gas according to the first fluorescence signal and the second fluorescence signal includes: and analyzing the concentration of ozone in the sample gas according to the first fluorescence signal, the second fluorescence signal and a standard curve equation.
Optionally, according to the above ozone analyzing method, before analyzing the ozone concentration in the sample gas according to the first fluorescence signal and the second fluorescence signal, the method further includes establishing the standard curve equation.
Optionally, according to the ozone analysis method, the establishing the standard curve equation includes: respectively measuring third fluorescence signals of standard ozone with different concentrations; respectively reacting standard ozone with different concentrations with excessive nitric oxide to generate excited nitrogen dioxide; respectively measuring a fourth fluorescence signal in the process that the nitrogen dioxide returns to the ground state; and establishing the standard curve equation according to the concentration of the standard ozone, the third fluorescence signal and the fourth fluorescence signal.
The invention also provides an ozone analyzer based on the chemiluminescence method, which comprises the following steps: a reaction chamber comprising a sample gas inlet, a nitric oxide inlet, a gas outlet and a transparent window; the fluorescence detector is used for detecting a fluorescence signal with the wavelength of 600-3000 nm; the detection part of the fluorescence detector is connected with the transparent window.
Optionally, the ozone analyzer further comprises a first flow limiting device, wherein the first flow limiting device is connected with the nitric oxide inlet of the reaction chamber.
Optionally, the ozone analyzer further comprises a second flow limiting device, wherein the second flow limiting device is connected to the sample gas inlet of the reaction chamber.
Optionally, the ozone analyzer further comprises a NO removing device connected to the gas outlet of the reaction chamber; the air pump is connected with the NO removing device.
Optionally, according to the above ozone analyzer, the reaction chamber is made of aluminum.
Optionally, the ozone analyzer further comprises an analyzing unit connected to the fluorescence detector for analyzing the concentration of ozone in the sample gas according to the fluorescence signal.
According to the ozone analysis method based on the chemiluminescence method, ozone and nitric oxide gas emit light after chemical reaction, the chemical reaction and the light-emitting characteristic wavelength have high selectivity, so that the problem of interference of coexisting substances can be solved, and the measurement result is more accurate and reliable.
Drawings
FIG. 1 shows a flow diagram of a chemiluminescence-based ozone analysis method according to one embodiment of the application; and
fig. 2 shows a schematic structural view of a chemiluminescence-based ozone analyzer according to an embodiment of the present application.
Description of reference numerals:
10 NO standard gas steel cylinder
20 first current limiting device
30 second current limiting device
40 reaction chamber
50 fluorescence detector
60 remove NO device
70 air pump
Detailed Description
The following detailed description of the present application, taken in conjunction with the accompanying drawings and examples, is provided to enable the aspects of the present application and its advantages to be better understood. However, the specific embodiments and examples described below are for illustrative purposes only and are not limiting of the present application.
The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The execution sequence of each step in the method mentioned in this application is not limited to the sequence presented in the text unless otherwise specified, that is, the execution sequence of each step may be changed, and other steps may be inserted between two steps as required.
The terms "connected" and "connected" as used herein, unless otherwise expressly specified or limited, are to be construed broadly, as meaning either directly or through an intermediate. In the description of the present application, it is to be understood that the directions or positional relationships indicated by "upper", "lower", "front", "rear", "left", "right", "top", "bottom", and the like are based on the directions or positional relationships shown in the drawings, and are only for convenience of description and simplification of description, and do not indicate or imply that the device or element referred to must have a specific direction, be constructed and operated in a specific direction, and thus, should not be construed as limiting the present application.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The following disclosure provides many different embodiments or examples for implementing different features of the application. In order to simplify the disclosure of the present application, specific example components and arrangements are described below. Of course, they are merely examples and are not intended to limit the present application. Moreover, the present application may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, examples of various specific processes and materials are provided herein, but one of ordinary skill in the art may recognize applications of other processes and/or use of other materials.
The common analysis method of ozone is ultraviolet photometry, and the principle of the method is that a beam of ultraviolet light passes through sample gas, ozone in the gas can absorb the ultraviolet light to cause the attenuation of light intensity, and the absorbance is in direct proportion to the concentration of the ozone in the sample gas.
Although the ultraviolet photometry is widely applied to monitoring ozone, the inventor finds that the method is easily interfered by other pollutants coexisting in the air, such as sulfur dioxide, nitrogen dioxide, particulate matters, volatile organic compounds and the like, in the measurement process, and particularly organic compounds such as styrene, trans-methyl styrene, benzaldehyde, o-cresol, nitrocresol, toluene and the like have remarkable influence on the measurement of ozone, so that the measurement result is higher.
Therefore, the inventor provides an ozone analysis method based on a chemiluminescence method and an ozone analyzer based on the chemiluminescence method, which can solve the problem of interference of coexisting substances and enable a measurement result to be more accurate and reliable.
The chemiluminescence method is a kind of molecular luminescence spectrum analysis method, and is a trace analysis method for determining the content of an object to be detected by utilizing the detection of the chemiluminescence intensity of an instrument on the basis of the principle that the concentration of the object to be detected in a chemical detection system and the chemiluminescence intensity of the system are in a linear quantitative relationship under a certain condition. The essential difference between chemiluminescence and other luminescence analyses is the source of energy absorbed by the system to produce luminescence (light radiation). The system produces chemiluminescence and must have one light-emissive reaction that produces a detectable signal and one chemical reaction that provides a single reaction step at a time with sufficient energy to cause the luminescence phenomenon.
The ozone analysis method adopts the principle that ozone and nitric oxide gas emit light after chemical reaction, and the problem of interference of coexisting substances can be solved due to the fact that the chemical reaction and the light-emitting characteristic wavelength have high selectivity, and the measuring result is more accurate and reliable.
Although ozone and ethylene gas can also generate chemical reaction to emit light, ethylene gas is flammable gas, and if the tail gas is not properly treated, the tail gas has certain dangerousness and possibly interferes with the station in the houseOther instruments (non-methane total hydrocarbons analyzer or VOCs analyzer). In addition, when ethylene gas is used for detecting ozone, NO in the air can be mixed with O3The reaction, the chemical generation wavelength of 1200nm, is not detectable by a photomultiplier tube using the ethylene principle, and therefore results in O3The measurement is low.
In the application, ozone reacts with Nitric Oxide (NO) gas to generate nitrogen dioxide, and redundant nitric oxide can react with carbon monoxide in the sample gas to generate nitrogen and carbon dioxide. NO is an incombustible gas, and is safer than ethylene gas. The luminous wavelength of the reaction of ethylene and ozone is 300-600 nm, and the peak value is 435 nm; the luminous wavelength of the reaction of NO and ozone is 600-3000nm, generally 1200nm, is not in a visible light wave band, is not easily influenced by light leakage, and the condition that the measurement is low due to the fact that the luminous wavelength is not in the detection range of the photomultiplier does not exist.
Fig. 1 shows a flow diagram of a chemiluminescence-based ozone analysis method according to one embodiment of the application.
Referring to fig. 1, the chemiluminescence-based ozone analysis method illustratively includes the steps of:
s11 measures a first fluorescent signal of the sample gas. Since only the sample gas is present at this time, the first fluorescence signal is a background signal.
S12 causes the ozone in the sample gas to react with excess nitric oxide to produce excited nitrogen dioxide.
S13 measures a second fluorescent signal during the return of the nitrogen dioxide to the ground state.
S14 analyzing the concentration of ozone in the sample gas based on the first fluorescence signal and the second fluorescence.
Ozone and nitric oxide can react chemically to generate excited nitrogen dioxide, which can release photons in the process of returning to the ground state, the wavelength is 600-3000nm, and the light intensity is in direct proportion to the concentration of the ozone and nitric oxide participating in the reaction. Therefore, by measuring the chemiluminescence intensity, the ozone concentration can be calculated. The reaction belongs to a specific reaction, the selectivity is strong, and other pollutants basically have no interference to the measurement of ozone. Therefore, compared with the ultraviolet photometry, the chemiluminescence method can more accurately measure the concentration of ozone in the ambient air and truly reflect the ozone pollution condition.
In some embodiments, step S4 is to analyze the concentration of ozone in the sample gas based on the first fluorescence signal and the second fluorescence using a standard curve equation. Therefore, before step S4, the ozone analysis method of the present application may further include establishing a corresponding standard curve equation.
Establishing the corresponding standard curve equation illustratively includes:
s21 respectively measures the third fluorescence signals of standard ozone with different concentrations. For example, different concentrations of standard ozone are 0%, 10%, 20%, 40%, 60%, and 80% standard ozone.
S22 standard ozone at various concentrations reacts with excess nitric oxide to produce excited nitrogen dioxide.
S23 measures a fourth fluorescent signal during the return of nitrogen dioxide to the ground state, respectively.
S24 a standard curve equation is established according to the concentration of the standard ozone, the third fluorescence signal and the fourth fluorescence signal.
The present application also provides an ozone analyzer based on a chemiluminescence method, which includes: a reaction chamber and a fluorescence detector. The reaction chamber includes a sample gas inlet, a nitric oxide inlet, a gas outlet, and a transparent window. And the fluorescence detector is used for detecting the fluorescence signals with the wavelengths of 600-3000 nm. The detection part of the fluorescence detector is connected with the transparent window.
According to some embodiments, the workflow and principles of the ozone analyzer are set forth below.
First, a sample gas is introduced into a reaction chamber through a sample gas inlet, and a fluorescence detector measures a first fluorescence signal, i.e., a background signal, of the sample gas in the reaction chamber. Then, excess nitric oxide is introduced into the reaction chamber through the nitric oxide inlet, and the ozone in the sample gas reacts with the excess nitric oxide to generate excited nitrogen dioxide. The intensity of light, which is proportional to the concentration of ozone and nitric oxide participating in the reaction, is capable of releasing photons when excited nitrogen dioxide returns to the ground state. And measuring a second fluorescence signal in the process that the nitrogen dioxide returns to the ground state through a fluorescence detector. Because the light intensity is in direct proportion to the concentration of the ozone participating in the reaction, the concentration of the ozone in the sample gas can be analyzed according to the first fluorescence signal and the second fluorescence signal obtained by measurement.
The chamber material may be aluminum. The reaction chamber has a large cavity, and the inner surface is oxidized and blackened. The transparent window is a light through hole which is connected with the detection part of the fluorescence detector. The light through hole can be made of quartz glass, so that the light through requirement is ensured, and the sealing of the reaction chamber is also ensured.
Fluorescent detector for detecting NO and O3The reaction releases a fluorescence signal with a wavelength of 600-3000 nm. For example, the fluorescence detector may be a photomultiplier tube.
According to an embodiment of the application, the ozone analyzer further comprises a first flow limiting device. The first flow limiting device is connected with a nitric oxide inlet of the reaction chamber and is used for controlling the flow of nitric oxide. For example, a flow-limiting capillary tube is adopted to realize the constant flow delivery of nitric oxide.
According to this application embodiment, ozone analyzer still includes second current-limiting device, and the sample gas inlet of second current-limiting device connection reaction chamber is used for controlling sample gas flow. For example, a flow restriction orifice may be used to achieve a constant flow delivery of the sample gas.
According to an exemplary embodiment, in order to eliminate unreacted nitric oxide in the reaction chamber to avoid pollution of the atmosphere by NO emissions, the ozone analyzer further comprises a NO removal device and an air pump. The NO removing device is connected with a gas outlet of the reaction chamber. The air pump, such as a vacuum pump, is connected with the NO removing device. The NO device is exemplified by a NO catalytic device which catalytically reduces NO with CO in the sample gas to produce N2And CO2。
According to an exemplary embodiment, the ozone analyzer further comprises an analyzing unit. The analysis unit is connected with the fluorescence detector and is used for analyzing the ozone concentration in the sample gas according to the fluorescence signal.
Fig. 2 shows a schematic structural view of a chemiluminescence-based ozone analyzer according to an embodiment of the present application.
Referring to fig. 2, the ozone analyzer includes a NO standard gas cylinder 10, a first flow restriction device 20, a second flow restriction device 30, a reaction chamber 40, a fluorescence detector 50, a NO removal device 60, and a gas pump 70. The transparent window of the reaction chamber 40 is connected to a fluorescence detector 50. The NO standard gas cylinder 10 is connected to the nitric oxide inlet of the reaction chamber 40 via a first flow restriction device 20. The NO standard gas cylinder 10 is used to supply nitric oxide. The second flow restriction device 30 is connected to the sample gas inlet of the reaction chamber 40. The gas outlet of the reaction chamber 40 is connected to a gas pump 70 via a NO removing device 60. The connecting piping of each unit may be a PTFE or PFA pipe.
The working process of the ozone analyzer comprises the following steps:
1. the sample gas enters the reaction chamber through the sample gas inlet under the action of the gas pump, and the fluorescence detector measures a first fluorescence signal (namely a background signal) in the reaction chamber at the moment.
2. And opening a pressure reducing valve of the NO standard gas steel cylinder to realize the pressure reduction of the nitric oxide gas, wherein the nitric oxide enters the reaction chamber under the action of the first flow limiting device.
3. The nitric oxide in the reaction chamber and the ozone in the sample gas chemically react to generate excited nitrogen dioxide.
4. The fluorescence detector measures a second fluorescence signal during the return of the nitrogen dioxide in the reaction chamber to the ground state.
5. The real-time concentration of ozone in the sample gas can be determined by calculating the difference between the second fluorescence signal and the first fluorescence signal and substituting the difference into a standard curve equation.
6. Unreacted nitric oxide in the reaction chamber is removed by means of a NO removal device.
The ozone analyzer detects the concentration of ozone in sample gas by adopting a chemical reaction luminescence principle. The ozone and the nitric oxide gas emit light after chemical reaction, and the light intensity of the ozone and the nitric oxide gas is in direct proportion to the concentration of the ozone and the nitric oxide gas participating in the reaction. Therefore, by measuring the chemiluminescence intensity, the ozone concentration can be calculated.
And because the chemical reaction and the luminescence characteristic wavelength have higher selectivity, compared with an ultraviolet photometry, the ozone analyzer based on the chemiluminescence method can solve the problem of interference of coexisting substances, so that the measurement result is more accurate and reliable.
Finally, it should be noted that: it should be understood that the above examples are only for clearly illustrating the present application and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of this invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. An ozone analysis method based on a chemiluminescence method, which is characterized by comprising the following steps:
measuring a first fluorescent signal of the sample gas;
reacting ozone in the sample gas with excess nitric oxide to generate excited nitrogen dioxide;
measuring a second fluorescent signal during return of the nitrogen dioxide to a ground state;
and analyzing the concentration of ozone in the sample gas according to the first fluorescence signal and the second fluorescence signal.
2. The ozone analysis method of claim 1, wherein the analyzing the concentration of ozone in the sample gas based on the first and second fluorescent signals comprises:
and analyzing the concentration of ozone in the sample gas according to the first fluorescence signal, the second fluorescence signal and a standard curve equation.
3. The method of claim 2, further comprising establishing the standard curve equation prior to analyzing the concentration of ozone in the sample gas based on the first and second fluorescent signals.
4. The ozone analysis method of claim 3, wherein the establishing the standard curve equation comprises:
respectively measuring third fluorescence signals of standard ozone with different concentrations;
respectively reacting standard ozone with different concentrations with excessive nitric oxide to generate excited nitrogen dioxide;
respectively measuring a fourth fluorescence signal in the process that the nitrogen dioxide returns to the ground state;
and establishing the standard curve equation according to the concentration of the standard ozone, the third fluorescence signal and the fourth fluorescence signal.
5. An ozone analyzer based on a chemiluminescence method, comprising:
a reaction chamber comprising a sample gas inlet, a nitric oxide inlet, a gas outlet and a transparent window;
the fluorescence detector is used for detecting a fluorescence signal with the wavelength of 600-3000 nm;
the detection part of the fluorescence detector is connected with the transparent window.
6. The ozone analyzer of claim 5, further comprising a first flow restriction device connected to the nitric oxide inlet of the reaction chamber.
7. The ozone analyzer of claim 5, further comprising a second flow restriction device connected to a sample gas inlet of the reaction chamber.
8. The ozone analyzer of claim 5, further comprising
The NO removal device is connected with a gas outlet of the reaction chamber;
the air pump is connected with the NO removing device.
9. The ozone analyzer as claimed in claim 5, wherein the reaction chamber is made of aluminum.
10. The ozone analyzer of claim 5, further comprising
And the analysis unit is connected with the fluorescence detector and is used for analyzing the ozone concentration in the sample gas according to the fluorescence signal.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111308025A (en) * | 2020-04-20 | 2020-06-19 | 淄博青禾检测科技有限公司 | Wide-range nitric oxide sensor system |
| CN114136898A (en) * | 2021-11-05 | 2022-03-04 | 中国科学院合肥物质科学研究院 | System and method for measuring photochemical net generation rate of high-precision cavity ozone |
| CN114264646A (en) * | 2021-12-13 | 2022-04-01 | 中国科学院大连化学物理研究所 | Device and method for detecting NO by photodiode with temperature compensation |
| EP4089401A1 (en) * | 2021-05-10 | 2022-11-16 | Siemens Aktiengesellschaft | Measuring device and method for measuring at least two different components of a fluid using raman scattering and chemiluminescence |
| CN117191706A (en) * | 2023-09-15 | 2023-12-08 | 小仙炖霸州食品有限公司 | Azometer |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002054039A2 (en) * | 2001-01-08 | 2002-07-11 | California Analytical Instruments, Inc. | Improved chemiluminescence reaction cell |
| US20040018630A1 (en) * | 2002-07-26 | 2004-01-29 | Birks John W. | Method and apparatus to detect a gas by measuring ozone depletion |
| CN101915743A (en) * | 2010-06-29 | 2010-12-15 | 中国环境科学研究院 | Method for calibrating online ozone analyzer |
| CN202512060U (en) * | 2012-02-15 | 2012-10-31 | 深圳市赛宝伦计算机技术有限公司 | Nox analyzer |
| CN205484056U (en) * | 2016-03-07 | 2016-08-17 | 沈阳富力科技有限公司 | Nitrogen oxide analysis appearance |
| CN212111147U (en) * | 2020-01-06 | 2020-12-08 | 北京雪迪龙科技股份有限公司 | Ozone analyzer based on chemiluminescence method |
-
2020
- 2020-01-06 CN CN202010010722.0A patent/CN110987911A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002054039A2 (en) * | 2001-01-08 | 2002-07-11 | California Analytical Instruments, Inc. | Improved chemiluminescence reaction cell |
| US20040018630A1 (en) * | 2002-07-26 | 2004-01-29 | Birks John W. | Method and apparatus to detect a gas by measuring ozone depletion |
| CN101915743A (en) * | 2010-06-29 | 2010-12-15 | 中国环境科学研究院 | Method for calibrating online ozone analyzer |
| CN202512060U (en) * | 2012-02-15 | 2012-10-31 | 深圳市赛宝伦计算机技术有限公司 | Nox analyzer |
| CN205484056U (en) * | 2016-03-07 | 2016-08-17 | 沈阳富力科技有限公司 | Nitrogen oxide analysis appearance |
| CN212111147U (en) * | 2020-01-06 | 2020-12-08 | 北京雪迪龙科技股份有限公司 | Ozone analyzer based on chemiluminescence method |
Non-Patent Citations (2)
| Title |
|---|
| B. A. RIDLEY ET AL.: "A Small High-Sensitivity, Medium-Response Ozone Detector Suitable for Measurements from Light Aircraft", JOURNAL OF ATMOSPHERIC AND OCEANIC TECHNOLOGY, vol. 09, no. 02, 1 April 1992 (1992-04-01), pages 142 - 148 * |
| 王会祥等: "化学发光法检测10~(-12)(体积比)臭氧", 现代科学仪器, no. 05, 25 October 2004 (2004-10-25), pages 42 - 45 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111308025A (en) * | 2020-04-20 | 2020-06-19 | 淄博青禾检测科技有限公司 | Wide-range nitric oxide sensor system |
| EP4089401A1 (en) * | 2021-05-10 | 2022-11-16 | Siemens Aktiengesellschaft | Measuring device and method for measuring at least two different components of a fluid using raman scattering and chemiluminescence |
| CN114136898A (en) * | 2021-11-05 | 2022-03-04 | 中国科学院合肥物质科学研究院 | System and method for measuring photochemical net generation rate of high-precision cavity ozone |
| CN114264646A (en) * | 2021-12-13 | 2022-04-01 | 中国科学院大连化学物理研究所 | Device and method for detecting NO by photodiode with temperature compensation |
| CN114264646B (en) * | 2021-12-13 | 2024-05-07 | 中国科学院大连化学物理研究所 | Device and method for detecting NO by using photodiode with temperature compensation |
| CN117191706A (en) * | 2023-09-15 | 2023-12-08 | 小仙炖霸州食品有限公司 | Azometer |
| CN117191706B (en) * | 2023-09-15 | 2024-02-13 | 小仙炖霸州食品有限公司 | Azometer |
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