CN108827949B - Nitrogen dioxide and ozone combined online detection device and method - Google Patents
Nitrogen dioxide and ozone combined online detection device and method Download PDFInfo
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Abstract
The invention discloses a combined online detection device and method for nitrogen dioxide and ozone. The invention utilizes the gas-liquid phase chemiluminescence principle with high detection sensitivity, simultaneously realizes the combined online detection of two conventional polluted gases of nitrogen dioxide and ozone in the atmosphere, is convenient for eliminating the mutual interference between the two gases, improves the accuracy of the detection result, reduces the detection cost, has simple structure, small volume, light weight and convenient carrying, and can be conveniently applied to the field of field emergency detection.
Description
Technical Field
The invention relates to the technical field of gas detection, in particular to a nitrogen dioxide and ozone combined on-line detection device and method.
Background
Ozone is a photochemical pollution gas, has strong oxidizing property, and has great harm to human bodies and plants. Nitrogen dioxide is also an important atmospheric pollutant gas and is the only chemical source of ozone in the tropospheric atmosphere. Nitrogen dioxide and ozone are currently used as main detection indexes for environmental monitoring in various countries in the world.
In the field of fixed-point monitoring, a gas-phase chemiluminescence method is generally adopted for detecting nitrogen dioxide, and an ultraviolet absorption photometry method is generally adopted for detecting ozone. Therefore, the detection method and the detection apparatus are completely different for the detection of two gases. This results in higher equipment costs and higher detection and maintenance costs. Meanwhile, the gas phase chemiluminescence method converts nitrogen dioxide into nitric oxide for detection, and interference of other nitrogen-containing gases is introduced in the reduction conversion process; the sensitivity of the ultraviolet absorption photometry is not high and is easy to be interfered. Although the gas-liquid phase chemiluminescence method is reported in the literature to be used for measuring nitrogen dioxide and ozone, certain interference exists between the gas-liquid phase chemiluminescence method and the measurement is difficult to completely eliminate the influence of the interference when the gas-liquid phase chemiluminescence method is independently used for measuring.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a nitrogen dioxide and ozone combined online detection device and method, which utilize the same detection system and detection method to carry out real-time online synchronous detection on nitrogen dioxide and ozone gas in the atmosphere.
The invention provides a nitrogen dioxide and ozone combined online detection device, which comprises a detection system, a liquid path system, a gas path system and a main control system, wherein the detection system is connected with the liquid path system;
the detection system comprises a first detector for detecting nitrogen dioxide and a second detector for detecting ozone, wherein the first detector and the second detector are respectively provided with a liquid inlet, a liquid outlet, an air inlet and an air outlet;
the liquid path system comprises a first liquid inlet unit connected with the liquid inlet of the first detector, a first liquid outlet unit connected with the liquid outlet of the first detector, a second liquid inlet unit connected with the liquid inlet of the second detector and a second liquid outlet unit connected with the liquid outlet of the second detector;
the gas path system comprises a gas inlet unit connected with the gas inlet of the first detector and the gas inlet of the second detector and a gas outlet unit connected with the gas outlet of the first detector and the gas outlet of the second detector;
the main control system is electrically connected with the detection system, the liquid path system and the air path system.
According to one embodiment of the nitrogen dioxide and ozone combined online detection device, the first liquid inlet unit comprises a first reagent flow path and a first cleaning agent flow path which are arranged in parallel, the first reagent flow path comprises a first reagent storage container and a first peristaltic pump, and the first cleaning agent flow path comprises a cleaning agent storage container and a second peristaltic pump; the first liquid outlet unit comprises a third peristaltic pump and a waste liquid collecting container.
According to one embodiment of the nitrogen dioxide and ozone combined online detection device, the second liquid inlet unit comprises a second reagent flow path and a second cleaning agent flow path which are arranged in parallel, the second reagent flow path comprises a second reagent storage container and a fourth peristaltic pump, and the second cleaning agent flow path comprises a cleaning agent storage container and a fifth peristaltic pump; the second liquid outlet unit comprises a sixth peristaltic pump and a waste liquid collecting container.
According to one embodiment of the combined nitrogen dioxide and ozone online detection device, the first detector and the second detector share a cleaning agent storage container and a waste liquid collection container; the peristaltic pumps are all ultra-miniature ball peristaltic pumps.
According to one embodiment of the nitrogen dioxide and ozone combined online detection device, the air inlet unit comprises an air filter, and the air outlet unit comprises a flowmeter, a gas purifying column and a vacuum pump which are sequentially connected.
According to one embodiment of the combined nitrogen dioxide and ozone online detection device, the flow meter comprises a first flow meter connected with the air outlet of the first detector and a second flow meter connected with the air outlet of the second detector, and the flow meters are laminar flow type gas mass flow meters.
According to one embodiment of the combined nitrogen dioxide and ozone online detection device of the invention, the first reagent for detecting nitrogen dioxide in the first liquid inlet unit is luminol, potassium hydroxide, sodium sulfite and Na 2 A mixed solution of EDTA and potassium iodide, a secondThe second reagent for ozone detection in the liquid inlet unit is a mixed solution of luminol, potassium hydroxide and ethylene glycol, and a gas purifying column in the gas outlet unit is filled with a mixture of activated carbon and potassium permanganate activated alumina particles.
The invention further provides a combined online detection method for nitrogen dioxide and ozone, which utilizes the combined online detection device for nitrogen dioxide and ozone to carry out combined online detection for nitrogen dioxide and ozone.
According to one embodiment of the combined nitrogen dioxide and ozone online detection method of the present invention, the method comprises the steps of:
A. calibrating the nitrogen dioxide and ozone combined online detection device to obtain a function model between the actual concentration of the two gases and detection signals of the first detector and the second detector when the nitrogen dioxide and the ozone coexist;
B. the first liquid inlet unit, the first liquid outlet unit, the second liquid inlet unit and the second liquid outlet unit are controlled to respectively send a first detection reagent and a second detection reagent to the first detector and the second detector, and the air inlet unit and the air outlet unit are controlled to simultaneously send gas to be detected to the first detector and the second detector;
C. c, recording chemiluminescence signals of the first detector and the second detector through a main control system, and calculating in real time according to the function model obtained in the step A to obtain the actual concentration of nitrogen dioxide and ozone in the gas to be detected;
D. after detection, the first liquid inlet unit and the first liquid outlet unit and the second liquid inlet unit and the second liquid outlet unit are controlled to respectively send cleaning reagents to the first detector and the second detector, and after cleaning is finished, the cleaning reagents are reserved.
According to one embodiment of the combined nitrogen dioxide and ozone online detection method of the present invention, calibrating the combined nitrogen dioxide and ozone online detection device in step a specifically includes the following sub-steps:
step 1: sequentially introducing 50ppbv and 100ppbv nitrogen dioxide gas into the detection system, respectively recording chemiluminescent signals detected by the first detector and the second detector, and listing two according to the detection resultLinear regression model equations between the nitrogen oxide gas concentration and the chemiluminescent signals detected by the first and second detectors, respectively, are written as I NO2 ＝C NO2 m 1 +a 1 And J NO2 ＝C NO2 m 2 +a 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein I is NO2 A chemiluminescent signal J for the nitrogen dioxide gas detected by the first detector NO2 C is the chemiluminescent signal of the nitrogen dioxide gas detected by the second detector NO2 Is the concentration of nitrogen dioxide gas;
step 2: sequentially introducing 50ppbv and 100ppbv of ozone gas into a detection system, respectively recording chemiluminescence signals detected by a first detector and a second detector, listing a linear regression model equation between the concentration of the ozone gas and the chemiluminescence signals detected by the first detector and the second detector according to detection results, and respectively recording I O3 ＝C O3 n 2 +b 2 ，J O3 ＝C O3 n 1 +b 1 The method comprises the steps of carrying out a first treatment on the surface of the Wherein I is O3 A chemiluminescent signal J for the ozone gas detected by the first detector O3 C is the chemiluminescent signal of the ozone gas detected by the second detector O3 Is the concentration of ozone gas;
step 3: deducing a function model between the actual concentration of the two gases and detection signals of the first detector and the second detector when the nitrogen dioxide and the ozone coexist according to a linear regression model equation of the first detector and the second detector for the nitrogen dioxide and the ozone respectively, wherein the function model is as follows:
wherein I is 1 For chemiluminescent signal detected by the first detector, J O3 A chemiluminescent signal detected by the second detector.
Compared with the prior art, the nitrogen dioxide and ozone combined online detection device and method provided by the invention utilize the gas-liquid phase chemiluminescence principle with high detection sensitivity, realize the combined online detection of two conventional polluted gases of nitrogen dioxide and ozone in the atmosphere, facilitate the elimination of mutual interference between the two gases, improve the accuracy of detection results, reduce the detection cost, and have the advantages of simple structure, small volume, light weight and convenience in carrying, and can be conveniently applied to the field of field emergency detection.
Drawings
Fig. 1 illustrates a schematic structure of a combined nitrogen dioxide and ozone online detection device according to an exemplary embodiment of the present invention.
Reference numerals illustrate:
1-liquid path system, 111-first reagent storage container, 112-second reagent storage container, 113-cleaning agent storage container, 114-waste liquid collection container, 121-first peristaltic pump, 122-second peristaltic pump, 123-third peristaltic pump, 124-fourth peristaltic pump, 125-fifth peristaltic pump, 126-sixth peristaltic pump;
2-detection system, 21-first detector, 22-second detector;
3-gas circuit system, 31-air filter, 32-first flowmeter, 33-second flowmeter, 34-gas purifying column, 35-vacuum pump;
4-master control system.
Detailed Description
All of the features disclosed in this specification, or all of the steps in a method or process disclosed, may be combined in any combination, except for mutually exclusive features and/or steps.
Any feature disclosed in this specification may be replaced by alternative features serving the same or equivalent purpose, unless expressly stated otherwise. That is, each feature is one example only of a generic series of equivalent or similar features, unless expressly stated otherwise.
The structure and principle of the nitrogen dioxide and ozone combined on-line detection device of the invention will be described in detail.
Fig. 1 illustrates a schematic structure of a combined nitrogen dioxide and ozone online detection device according to an exemplary embodiment of the present invention.
As shown in fig. 1, according to an exemplary embodiment of the present invention, the combined online detection device for nitrogen dioxide and ozone includes a detection system 2, a liquid path system 1, a gas path system 3, and a main control system 4, where the detection system 2 is a device for performing a detection reaction, the liquid path system 1 implements liquid path control on the detection system 2, the gas path system implements gas path control on the detection system 2, and the main control system 4 is used for controlling each component to implement combined online detection.
Specifically, the detection system 2 includes a first detector 21 for nitrogen dioxide detection and a second detector 22 for ozone detection, and the first detector 21 and the second detector 22 are each provided with a liquid inlet, a liquid outlet, an air inlet, and an air outlet. Wherein the first detector 21 and the second detector 22 are gas-liquid phase chemiluminescent detectors.
The liquid path system 1 comprises a first liquid inlet unit connected with the liquid inlet of the first detector 21, a first liquid outlet unit connected with the liquid outlet of the first detector 21, a second liquid inlet unit connected with the liquid inlet of the second detector 22 and a second liquid outlet unit connected with the liquid outlet of the second detector 22.
The first liquid inlet unit comprises a first reagent flow path and a first cleaning agent flow path which are arranged in parallel, the first reagent flow path comprises a first reagent storage container 111 and a first peristaltic pump 121, and the first cleaning agent flow path comprises a cleaning agent storage container 113 and a second peristaltic pump 122; the first liquid outlet unit comprises a third peristaltic pump 123 and a waste liquid collection container 114. Wherein the first reagent for detecting nitrogen dioxide in the first liquid inlet unit is luminol, potassium hydroxide, sodium sulfite and Na 2 Mixed solution of EDTA and potassium iodide, sodium sulfite and Na 2 EDTA for sensitization of nitrogen dioxide, na 2 EDTA, potassium iodide are used for attenuation of ozone interference.
Similarly, the second liquid inlet unit includes a second reagent flow path and a second cleaning agent flow path disposed in parallel, the second reagent flow path including a second reagent storage container 112 and a fourth peristaltic pump 124, the second cleaning agent flow path including a cleaning agent storage container 113 and a fifth peristaltic pump 125; the second liquid outlet unit comprises a sixth peristaltic pump 126 and a waste liquid collection container 114. The second reagent used for ozone detection in the second liquid inlet unit is a mixed solution of luminol, potassium hydroxide and glycol, and the glycol is used for sensitization of ozone and attenuation of nitrogen dioxide.
Wherein the first detector 21 and the second detector 22 share the cleaning agent storage container 113 and the waste liquid collection container 114, simplifying the structure of the device, and facilitating the use and maintenance. The peristaltic pump is an ultra-miniature ball peristaltic pump, has low energy consumption and small volume, hardly generates abrasion to a pump pipe, and can reduce maintenance cost and maintenance times.
Because the reagent flow paths and the cleaning agent flow paths of the first detector 21 and the second detector 22 are driven by different peristaltic pumps respectively, the cleaning speed and the cleaning effect can be effectively improved due to the large flow rate of the cleaning channel. Compared with the structure that the electromagnetic valve is adopted before to switch between the detection reagent and the cleaning reagent, the liquid path pipeline between the liquid reagent storage device and the detector is shorter, high energy consumption devices such as the electromagnetic valve are not needed, the pipeline switching times are few, the liquid inlet speed of liquid is improved, the preheating time of the instrument after the instrument is started is shortened, and the working efficiency is improved.
And the gas circuit system 3 comprises a gas inlet unit connected to the gas inlet of the first detector 21 and the gas inlet of the second detector 22 and a gas outlet unit connected to the gas outlet of the first detector 21 and the gas outlet of the second detector 22.
Specifically, the air intake unit includes an air filter, and the air inlet of the first detector 21 and the air inlet of the second detector 22 are connected to the outside air through the air filter; the gas outlet unit comprises a flowmeter, a gas purifying column 34 and a vacuum pump 35 which are sequentially connected, wherein the flowmeter comprises a first flowmeter 32 connected with the gas outlet of the first detector 21 and a second flowmeter 33 connected with the gas outlet of the second detector 22, and the flowmeters are laminar flow type gas mass flowmeters, so that the power consumption is reduced, and the control precision and the control speed are improved. In addition, the gas purifying column 34 in the gas outlet unit is filled with a mixture of activated carbon and potassium permanganate activated alumina particles for absorbing the detection gas, particularly the polluted gas in the exhaust gas in the calibration process, and preventing secondary pollution.
The main control system 4 is electrically connected with the detection system 2, the liquid path system 1 and the gas path system 3, so that the combined online detection of nitrogen dioxide and ozone is realized through the respective actions of the modules.
According to the nitrogen dioxide and ozone combined online detection method, the nitrogen dioxide and ozone combined online detection device is specifically utilized to carry out combined online detection of the nitrogen dioxide and the ozone.
Specifically, the detection method includes the following steps.
Step A:
and calibrating the nitrogen dioxide and ozone combined online detection device to obtain a functional model between the actual concentration of the two gases and detection signals of the first detector and the second detector when the nitrogen dioxide and the ozone coexist.
Through the pre-calibration and the function model, the concentration of the two gases can be directly combined and detected on line in the subsequent detection process.
The calibrating the nitrogen dioxide and ozone combined online detection device specifically comprises the following substeps:
step 1: sequentially introducing 50ppbv and 100ppbv of nitrogen dioxide gas into the detection system, respectively recording chemiluminescence signals detected by the first detector and the second detector, listing a linear regression model equation between the concentration of the nitrogen dioxide gas and the chemiluminescence signals detected by the first detector and the second detector according to detection results, and respectively recording I NO2 ＝C NO2 m 1 +a 1 And J NO2 ＝C NO2 m 2 +a 2 。
Wherein I is NO2 A chemiluminescent signal J for the nitrogen dioxide gas detected by the first detector NO2 C is the chemiluminescent signal of the nitrogen dioxide gas detected by the second detector NO2 Is the concentration of nitrogen dioxide gas;
step 2: sequentially introducing ozone gas of 50ppbv and 100ppbv into the detection system, and respectively recording a first detector and a second detectorThe detected chemiluminescent signals are listed according to the detection result, and the linear regression model equation between the concentration of ozone gas and the chemiluminescent signals detected by the first detector and the second detector is respectively recorded as I O3 ＝C O3 n 2 +b 2 ，J O3 ＝C O3 n 1 +b 1 。
Wherein I is O3 A chemiluminescent signal J for the ozone gas detected by the first detector O3 C is the chemiluminescent signal of the ozone gas detected by the second detector O3 Is the concentration of ozone gas;
step 3: deducing a function model between the actual concentration of the two gases and detection signals of the first detector and the second detector when the nitrogen dioxide and the ozone coexist according to a linear regression model equation of the first detector and the second detector for the nitrogen dioxide and the ozone respectively, wherein the function model is as follows:
wherein I is 1 For chemiluminescent signals detected by the first detector, I 2 A chemiluminescent signal detected by the second detector.
Thus, the actual concentration of the two gases can be calculated in the actual detection process by the function model comprising the obtained calibration parameters.
And (B) step (B):
the first liquid inlet unit, the first liquid outlet unit, the second liquid inlet unit and the second liquid outlet unit are controlled to respectively send the first detection reagent and the second detection reagent to the first detector and the second detector, and the air inlet unit and the air outlet unit are controlled to simultaneously send the gas to be detected to the first detector and the second detector.
Step C:
and C, recording chemiluminescence signals of the first detector and the second detector through a main control system, and calculating in real time according to the function model obtained in the step A to obtain the actual concentration of nitrogen dioxide and ozone in the gas to be detected.
Step D:
after detection, the first liquid inlet unit and the first liquid outlet unit and the second liquid inlet unit and the second liquid outlet unit are controlled to respectively send cleaning reagents to the first detector and the second detector, and after cleaning is finished, the cleaning reagents are reserved.
Preferably, the liquid inlet speed during cleaning is greater than the liquid inlet speed during detection, so as to improve the cleaning speed and the cleaning effect; and the liquid inlet speed is slightly less than the liquid outlet speed, so that the liquid accumulation in the detector is prevented.
The invention will be further illustrated with reference to specific examples.
First, the nitrogen dioxide and ozone combined on-line detection device with the structure shown in fig. 1 is assembled.
Next, nitrogen dioxide and ozone standard gases of the required concentrations are generated in the laboratory on site, wherein the nitrogen dioxide standard gas is generated from a nitrogen dioxide standard gas generator based on a permeation tube technology, and the ozone standard gas is generated from an ozone generator based on an ultraviolet photolysis technology. The concentration of the generated standard gas is 2, 50ppbv and 100ppbv, the standard gas is introduced into the assembled detection device, the average value of detection data of 1 minute is recorded, wherein the response values of the first detector to the nitrogen dioxide standard gas and the ozone standard gas are respectively as follows: (2307, 4601) and (23, 42); the response values of the second detector to the nitrogen dioxide standard gas and the ozone standard gas are respectively as follows: (13, 21) and (1782, 3573).
The functional model between the actual concentration of the two gases and the detection signals of the first detector and the second detector when the nitrogen dioxide and the ozone coexist is obtained according to the calibration method, and is as follows:
I NO2 ＝C NO2 m 1 +a 1
J NO2 ＝C NO2 m 2 +a 2
I O3 ＝C O3 n 2 +b 2
J O3 ＝C O3 n 1 +b 1
fitting the formula according to the calibration data to obtain:
I N02 ＝C NO2 *45.88+13
J NO2 ＝C NO2 *0.16+5
I O3 ＝C O3 *0.38+4
J O3 ＝C O3 *35.82-9，
the gas to be detected is led into the detectors, and the chemiluminescent signals detected by the first and second detectors are respectively I 1 、I 2 At this time I 1 、I 2 Which are the sum of the nitrogen dioxide and ozone chemiluminescent signals detected by the two detectors, respectively.
Thus:
I 1 ＝I NO2 +I O3 ＝C NO2 m 1 +a 1 +C O3 n 2 +b 2
I 2 ＝J NO2 +J O3 ＝C NO2 m 2 +a 2 +C O3 n 1 +b 1
according to a calibration formula, the following can be obtained:
I 1 ＝C NO2 *45.88+C O3 *0.38+17
I 2 ＝C NO2 *0.16+C O3 *35.82-4
the two are combined to form a linear equation set, wherein m 1 、m 2 、n 1 、n 2 、a 1 、a 2 、b 1 、b 2 For calibrating the parameters of the obtained linear regression model. Solving the equation set can obtain:
and then, the device is used for carrying out combined online detection of nitrogen dioxide and ozone.
The method comprises the following specific steps:
1) The first peristaltic pump, the third peristaltic pump, the fourth peristaltic pump and the sixth peristaltic pump are controlled to work, the second peristaltic pump and the fifth peristaltic pump are stopped, the detection reagent enters the corresponding detector under the driving of the corresponding peristaltic pump to perform chemiluminescent reaction with the gas to be detected entering the detector, and the reaction waste liquid can be discharged to the waste liquid collecting container under the driving of the peristaltic pump
2) The vacuum pump is controlled to be opened, gas to be detected is filtered by the air filter under the action of the vacuum pump and then enters the corresponding detector to participate in the reaction, and the reacted gas is discharged from the gas outlet of the detector and is purified by the gas purifying column and then is discharged.
3) The main control system records the chemiluminescent signals of the first detector and the second detector, and directly calculates the actual concentration of nitrogen dioxide and ozone according to the function model. Detecting the gas in the laboratory, wherein the chemiluminescent signals of the first detector and the second detector are as follows: 1443 and 598, taking the data and the parameters of the calibration model into a regression equation set, and calculating to obtain the concentrations of the indoor nitrogen dioxide and the indoor ozone, wherein the concentrations are respectively as follows: 30.9ppbv and 16.4ppbv.
And cleaning the detection system after the detection is finished. Specifically, the second peristaltic pump, the third peristaltic pump, the fifth peristaltic pump and the sixth peristaltic pump are controlled to work, the first peristaltic pump and the fourth peristaltic pump are stopped, the cleaning reagent enters the corresponding detector under the driving of the corresponding peristaltic pump to complete the cleaning of the detector, and the cleaning waste liquid is discharged through the liquid outlet.
In summary, the nitrogen dioxide and ozone combined online detection device and method provided by the invention utilize the gas-liquid phase chemiluminescence principle with high detection sensitivity, realize the combined online detection of two conventional polluted gases of nitrogen dioxide and ozone in the atmosphere, facilitate the elimination of the mutual interference between the two gases, improve the accuracy of the detection result, reduce the detection cost, and have the advantages of simple structure, small volume, light weight and portability, and can be conveniently applied to the field of on-site emergency detection.
The invention is not limited to the specific embodiments described above. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification, as well as to any novel one, or any novel combination, of the steps of the method or process disclosed.
Claims (7)
1. The combined online detection method for the nitrogen dioxide and the ozone is characterized in that the combined online detection device for the nitrogen dioxide and the ozone is used for carrying out combined online detection on the nitrogen dioxide and the ozone; the device comprises a detection system, a liquid path system, a gas path system and a main control system;
the detection system comprises a first detector for detecting nitrogen dioxide and a second detector for detecting ozone, wherein the first detector and the second detector are respectively provided with a liquid inlet, a liquid outlet, an air inlet and an air outlet;
the liquid path system comprises a first liquid inlet unit connected with the liquid inlet of the first detector, a first liquid outlet unit connected with the liquid outlet of the first detector, a second liquid inlet unit connected with the liquid inlet of the second detector and a second liquid outlet unit connected with the liquid outlet of the second detector;
the gas path system comprises a gas inlet unit connected with the gas inlet of the first detector and the gas inlet of the second detector and a gas outlet unit connected with the gas outlet of the first detector and the gas outlet of the second detector;
the main control system is electrically connected with the detection system, the liquid path system and the air path system;
the method comprises the following steps:
A. calibrating the nitrogen dioxide and ozone combined online detection device to obtain a function model between the actual concentration of the two gases and detection signals of the first detector and the second detector when the nitrogen dioxide and the ozone coexist;
B. the first liquid inlet unit, the first liquid outlet unit, the second liquid inlet unit and the second liquid outlet unit are controlled to respectively send a first detection reagent and a second detection reagent to the first detector and the second detector, and the air inlet unit and the air outlet unit are controlled to simultaneously send gas to be detected to the first detector and the second detector;
C. c, recording chemiluminescence signals of the first detector and the second detector through a main control system, and calculating in real time according to the function model obtained in the step A to obtain the actual concentration of nitrogen dioxide and ozone in the gas to be detected;
D. after detection, the first liquid inlet unit and the first liquid outlet unit as well as the second liquid inlet unit and the second liquid outlet unit are controlled to respectively send cleaning reagents to the first detector and the second detector, and the cleaning is finished for later use;
calibrating the nitrogen dioxide and ozone combined online detection device in the step A specifically comprises the following substeps:
step 1: sequentially introducing 50ppbv and 100ppbv of nitrogen dioxide gas into the detection system, respectively recording chemiluminescence signals detected by the first detector and the second detector, listing a linear regression model equation between the concentration of the nitrogen dioxide gas and the chemiluminescence signals detected by the first detector and the second detector according to detection results, and respectively recording I NO2 ＝C NO2 m 1 +a 1 And J NO2 ＝C NO2 m 2 +a 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein I is NO2 A chemiluminescent signal J for the nitrogen dioxide gas detected by the first detector NO2 C is the chemiluminescent signal of the nitrogen dioxide gas detected by the second detector NO2 Is the concentration of nitrogen dioxide gas;
step 2: sequentially introducing 50ppbv and 100ppbv of ozone gas into a detection system, respectively recording chemiluminescence signals detected by a first detector and a second detector, listing a linear regression model equation between the concentration of the ozone gas and the chemiluminescence signals detected by the first detector and the second detector according to detection results, and respectively recording I O3 ＝C O3 n 2 +b 2 ，J o3 ＝C o3 n 1 +b 1 The method comprises the steps of carrying out a first treatment on the surface of the Wherein I is O3 A chemiluminescent signal J for the ozone gas detected by the first detector O3 C is the chemiluminescent signal of the ozone gas detected by the second detector O3 Is the concentration of ozone gas;
step 3: the function model between the actual concentration of the two gases when the nitrogen dioxide and the ozone coexist and the chemiluminescent signals detected by the first detector and the second detector is deduced according to the linear regression model equation of the nitrogen dioxide and the ozone by the first detector and the second detector respectively, wherein the function model is as follows:
wherein I is 1 For chemiluminescent signals detected by the first detector, I 2 A chemiluminescent signal detected by the second detector.
2. The combined online detection method of nitrogen dioxide and ozone according to claim 1, wherein the first liquid inlet unit comprises a first reagent flow path and a first cleaning agent flow path which are arranged in parallel, the first reagent flow path comprises a first reagent storage container and a first peristaltic pump, and the first cleaning agent flow path comprises a cleaning agent storage container and a second peristaltic pump; the first liquid outlet unit comprises a third peristaltic pump and a waste liquid collecting container.
3. The combined online detection method of nitrogen dioxide and ozone according to claim 2, wherein the second liquid inlet unit comprises a second reagent flow path and a second cleaning agent flow path which are arranged in parallel, the second reagent flow path comprises a second reagent storage container and a fourth peristaltic pump, and the second cleaning agent flow path comprises a cleaning agent storage container and a fifth peristaltic pump; the second liquid outlet unit comprises a sixth peristaltic pump and a waste liquid collecting container.
4. A combined online detection method of nitrogen dioxide and ozone according to claim 3, wherein the first detector and the second detector share a cleaning agent storage container and a waste liquid collection container; the peristaltic pumps are all ultra-miniature ball peristaltic pumps.
5. The method for combined online detection of nitrogen dioxide and ozone according to claim 1, wherein the air inlet unit comprises an air filter, and the air outlet unit comprises a flowmeter, a gas purifying column and a vacuum pump which are sequentially connected.
6. The method of claim 5, wherein the flow meter comprises a first flow meter connected to the gas outlet of the first detector and a second flow meter connected to the gas outlet of the second detector, and the flow meters are laminar flow gas mass flow meters.
7. The method for combined online detection of nitrogen dioxide and ozone according to claim 1, wherein the first reagent for detecting nitrogen dioxide in the first liquid inlet unit is luminol, potassium hydroxide, sodium sulfite, na 2 The second reagent used for ozone detection in the second liquid inlet unit is a mixed solution of luminol, potassium hydroxide and ethylene glycol, and a gas purifying column in the gas outlet unit is filled with a mixture of activated carbon and potassium permanganate activated alumina particles.
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| CN111693514B (en) * | 2020-05-07 | 2022-07-05 | 四川轻化工大学 | Online detection device and method utilizing online liquid-gas conversion |
| CN113189089B (en) * | 2021-03-19 | 2022-05-17 | 四川轻化工大学 | Ozone detection reagent and preparation device and preparation method thereof |
| CN114152653B (en) * | 2021-10-14 | 2023-08-08 | 中国计量科学研究院 | Method and device for decoupling and high-precision measurement of nitrogen dioxide and ozone concentration in atmosphere |
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