CN216434018U - Ozone gas phase titration standard device - Google Patents

Ozone gas phase titration standard device Download PDF

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CN216434018U
CN216434018U CN202121549014.0U CN202121549014U CN216434018U CN 216434018 U CN216434018 U CN 216434018U CN 202121549014 U CN202121549014 U CN 202121549014U CN 216434018 U CN216434018 U CN 216434018U
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gas
ozone
standard
phase titration
nitrogen dioxide
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刘沂玲
王德发
郝静坤
刘春宇
蔡春洪
曾武
李紫晗
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National Institute of Metrology
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National Institute of Metrology
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Abstract

The utility model provides an ozone gas phase titration standard device, and belongs to the technical field of accurate ozone concentration measurement standards. The method comprises the following steps: the nitric oxide standard gas high-pressure gas cylinder is respectively connected with the gas-phase titration cavity and the four-way valve; the nitrogen dioxide standard gas high-pressure gas cylinder is respectively connected with the gas phase titration cavity and the four-way valve, the gas phase titration cavity is connected with the four-way valve, and the four-way valve is also respectively connected with a nitric oxide gas analyzer and a nitrogen dioxide gas analyzer; and the ozone generator is respectively connected with the gas-phase titration cavity, the standard ozone gas analyzer and the detected ozone gas analyzer. According to the utility model, the ozone gas concentration is measured by measuring the reduction amount of nitric oxide and the increase amount of nitrogen dioxide, so that the influence of system deviation of a nitrogen dioxide gas analyzer and a nitric oxide gas analyzer on the ozone gas concentration measurement is avoided; the initial value of the nitrogen dioxide gas analyzer is improved by introducing the nitrogen dioxide standard gas, and the measurement accuracy can be obviously improved.

Description

Ozone gas phase titration standard device
Technical Field
The utility model belongs to the technical field of accurate ozone concentration measurement standards, and particularly relates to an ozone gas phase titration standard device.
Background
The existing ozone concentration measurement standard tracing mode is divided into two categories, one category is based on the Lambert-beer law, the accurate measurement of the ozone concentration is related to each physical parameter and spectral absorption coefficient in the Lambert-beer law, such as an ozone standard photometer (SRP) measurement reference device adopted globally, and the measuring range of the device is not more than 1 mu mol/mol; the other type is that the ozone and nitric oxide are quantitatively and rapidly reacted, gas phase titration is carried out, the concentration of the ozone is traced to the concentration of nitric oxide standard gas, the range of the existing device is not more than 1 mu mol/mol, and the nitrogen dioxide concentration generated by the device is measured only by a nitrogen dioxide analyzer, and the uncertainty value of the measurement is larger because the nitrogen dioxide has strong adsorbability and poor stability and is influenced by various factors during measurement.
SUMMERY OF THE UTILITY MODEL
The utility model aims to solve the problems in the prior art, provides an ozone gas phase titration standard device, is an ozone gas phase titration standard device from low concentration (ppb level) to high concentration (ppm level), and particularly has a self-verification function for accurately and quantitatively measuring ozone gas with concentration higher than 1 mu mol/mol.
The utility model is realized by the following technical scheme:
in one aspect of the present invention, there is provided an ozone gas phase titration standard apparatus, comprising:
the nitric oxide standard gas high-pressure gas cylinder is respectively connected with the gas-phase titration cavity and the four-way valve;
the nitrogen dioxide standard gas high-pressure gas cylinder is respectively connected with the gas phase titration cavity and the four-way valve, the gas phase titration cavity is connected with the four-way valve, and the four-way valve is also respectively connected with a nitric oxide gas analyzer and a nitrogen dioxide gas analyzer;
and the ozone generator is respectively connected with the gas-phase titration cavity, the standard ozone gas analyzer and the detected ozone gas analyzer.
The utility model is further improved in that:
the nitric oxide standard gas high-pressure gas cylinder is connected with a first three-way joint, and the first three-way joint is respectively connected with the gas phase titration cavity and the four-way valve through a gas pipeline;
the nitrogen dioxide standard gas high-pressure gas cylinder is connected with a second three-way joint, and the second three-way joint is respectively connected with the gas phase titration cavity and the four-way valve through gas pipelines;
the ozone generator is connected with a four-way joint, and the four-way joint is respectively connected with the gas phase titration cavity, the standard ozone gas analyzer and the detected ozone gas analyzer through gas pipelines;
the gas phase titration cavity is also connected with a third three-way joint, and the third three-way joint is respectively connected with the back pressure valve and the four-way valve through a gas pipeline; and the four-way valve is also connected with a fourth three-way joint, and the fourth three-way joint is respectively connected with a nitric oxide gas analyzer and a nitrogen dioxide gas analyzer through gas pipelines.
The utility model is further improved in that:
the four-way valve is provided with four interfaces which are respectively a first interface, a second interface, a third interface and a fourth interface, and only one of the first interface, the second interface and the fourth interface is communicated with the third interface during working.
The utility model is further improved in that:
and after being connected with the first three-way joint, the nitric oxide standard gas high-pressure gas cylinder is respectively connected with the gas phase titration cavity and the second interface of the four-way valve through gas pipelines.
The utility model is further improved in that:
and after being connected with the second three-way joint, the nitrogen dioxide standard gas high-pressure gas cylinder is respectively connected with the gas phase titration cavity and a fourth interface of the four-way valve through a gas pipeline.
The utility model is further improved in that:
and after the gas phase titration cavity is connected with a third three-way joint through a gas pipeline, one path is connected with a back pressure valve through the gas pipeline and then is emptied through the gas pipeline, and the other path is connected with a first interface of the four-way valve through the gas pipeline.
The utility model is further improved in that:
and a third interface of the four-way valve is connected with a fourth three-way joint through a gas pipeline and then respectively connected with a nitrogen dioxide gas analyzer and a nitric oxide gas analyzer through gas pipelines.
Compared with the prior art, the utility model has the beneficial effects that:
(1) the ozone gas phase titration standard device enables the concentration of ozone gas to trace the source to the time, the flow and the molar quantity of substances, and the tracing chain is complete and clear;
(2) the ozone gas phase titration standard device has a self-verification function, so that the measured ozone gas concentration is accurate and reliable, and the influence of the self measurement errors of a nitrogen dioxide gas analyzer and a nitrogen monoxide gas analyzer on the measurement result is avoided;
(3) because the ozone gas concentration is measured by measuring the reduction amount of the nitric oxide and the increase amount of the nitrogen dioxide, the influence of the system deviation of a nitrogen dioxide gas analyzer and a nitric oxide gas analyzer on the ozone gas concentration measurement is avoided;
(4) because the nitrogen dioxide standard gas is introduced, the initial value of the nitrogen dioxide gas analyzer is improved, and the problems of poor sensitivity and poor accuracy in the process of analyzing the low-concentration nitrogen dioxide gas are avoided.
(5) The device of the utility model can not only trace the source and analyze the fixed value of the ozone concentration, but also detect and calibrate the detected ozone analyzer.
Drawings
FIG. 1 is a schematic diagram of the construction of an ozone gas phase titration standard apparatus according to the present invention.
In the figure, 1, a nitric oxide standard gas high-pressure gas cylinder, 2, a nitrogen dioxide standard gas high-pressure gas cylinder, 3, a first three-way joint, 4, a gas-phase titration cavity, 5, a second three-way joint, 6, a third three-way joint, 7, a back pressure valve, 8, a four-way valve, 801, a first interface, 802, a second interface, 803, a third interface, 804, a fourth interface, 9, a fourth three-way joint, 10, a nitrogen dioxide gas analyzer, 11, a nitric oxide gas analyzer, 12, an ozone generator, 13, a four-way joint, 14, a standard ozone gas analyzer, 15 and a detected ozone gas analyzer.
Detailed Description
The utility model is described in further detail below with reference to the accompanying drawings:
[ example 1 ]
The utility model provides an ozone gas phase titration standard device, as shown in figure 1, comprising: the device comprises a nitric oxide standard gas high-pressure gas cylinder 1, a nitrogen dioxide standard gas high-pressure gas cylinder 2, a first three-way joint 3, a gas phase titration chamber 4, a second three-way joint 5, a third three-way joint 6, a back pressure valve 7, a four-way valve 8, a fourth three-way joint 9, a nitrogen dioxide gas analyzer 10, a nitric oxide gas analyzer 11, an ozone generator 12, a four-way joint 13 and a standard ozone gas analyzer 14;
the nitric oxide standard gas high-pressure gas cylinder 1 is connected with a first three-way joint 3, and the first three-way joint 3 is respectively connected with a gas phase titration chamber 4 and a four-way valve 8 through a gas pipeline;
the nitrogen dioxide standard gas high-pressure gas cylinder 2 is connected with a second three-way joint 5, and the second three-way joint 5 is respectively connected with the gas phase titration chamber 4 and the four-way valve 8 through gas pipelines;
the ozone generator 12 is connected with a four-way joint 13, the four-way joint 13 is respectively connected with the gas phase titration cavity 4, the standard ozone gas analyzer 14 and the detected ozone gas analyzer 15 through gas pipelines, and the detected ozone gas analyzer 15 is used for detecting the ozone concentration;
the gas phase titration cavity 4 is also connected with a third three-way joint 6, and the third three-way joint 6 is respectively connected with a back pressure valve 7 and a four-way valve 8 through a gas pipeline; the four-way valve 8 is also connected with a fourth three-way joint 9, and the fourth three-way joint 9 is respectively connected with a nitric oxide gas analyzer 11 and a nitrogen dioxide gas analyzer 10 through gas pipelines.
The four-way valve 8 has four ports, which are a first port 801, a second port 802, a third port 803 and a fourth port 804, respectively, and only one of the first port 801, the second port 802 and the fourth port 804 is communicated with the third port 803 when in operation.
After being connected with the first three-way joint 3, the nitric oxide standard gas high-pressure gas cylinder 1 is respectively connected with the gas phase titration chamber 4 and the second interface 802 of the four-way valve 8 through gas pipelines.
After being connected with the second three-way joint 5, the nitrogen dioxide standard gas high-pressure gas cylinder 2 is respectively connected with the gas phase titration chamber 4 and the fourth interface 804 of the four-way valve 8 through gas pipelines.
After the gas phase titration cavity 4 is connected with the third three-way joint 6 through a gas pipeline, one path is connected with the back pressure valve 7 through the gas pipeline and then is emptied through the gas pipeline, and the other path is connected with the first interface 801 of the four-way valve 8 through the gas pipeline.
The third port 803 of the four-way valve 8 is connected to the fourth three-way joint 9 through a gas line, and then is connected to the nitrogen dioxide gas analyzer 10 and the nitric oxide gas analyzer 11 through gas lines, respectively.
The ozone generator 12 is connected with the four-way joint 13 through a gas pipeline, and then is respectively connected with the gas phase titration cavity 4, the standard ozone gas analyzer 14 and the detected ozone gas analyzer 15 through gas pipelines.
The gas flow path direction in the ozone gas phase titration standard device is as follows:
after nitric oxide standard gas in a nitric oxide standard gas high-pressure gas cylinder 1 passes through a first three-way joint 3, one path of nitric oxide standard gas enters a gas phase titration chamber 4; after passing through a second three-way joint 5, one path of the nitrogen dioxide standard gas in the nitrogen dioxide standard gas high-pressure gas cylinder 2 enters a gas phase titration chamber 4; ozone gas generated by the ozone generator 12 passes through the four-way joint 13, and then enters the gas phase titration cavity 4; after passing through the third three-way joint 6, one path of gas from the gas phase titration chamber 4 enters the first interface 801 of the four-way valve 8, and when the first interface 801 is communicated with the third interface 803, the gas passes through the fourth three-way joint 9 and then enters the nitrogen dioxide gas analyzer 10 and the nitric oxide gas analyzer 11 respectively; the gas from the gas phase titration chamber 4 can also be exhausted after passing through a back pressure valve 7;
after passing through the first three-way joint 3, the nitric oxide standard gas in the nitric oxide standard gas high-pressure gas cylinder 1 enters the second interface 802 of the four-way valve 8 through the other path, and when the second interface 802 is communicated with the third interface 803, the gas passes through the fourth three-way joint 9 and then enters the nitrogen dioxide gas analyzer 10 and the nitric oxide gas analyzer 11 respectively;
after passing through the second three-way joint 5, the nitrogen dioxide standard gas in the nitrogen dioxide standard gas high-pressure gas cylinder 2 enters the fourth interface 804 of the four-way valve 8 through the other path, and when the fourth interface 804 is communicated with the third interface 803, the gas passes through the fourth three-way joint 9 and then respectively enters the nitrogen dioxide gas analyzer 10 and the nitric oxide gas analyzer 11;
ozone gas generated by the ozone generator 12 passes through the four-way joint 13, and then enters the standard ozone gas analyzer 14 through the other path; and the other path enters a detected ozone gas analyzer 15.
[ example 2 ]
The method for tracing the ozone gas concentration by utilizing the ozone gas phase titration standard device comprises the following steps of:
step 1, carrying out gas-phase titration on nitric oxide standard gas and ozone generated by an ozone generator 12 in a gas-phase titration chamber 4:
NO+O3→NO2+O2 (1)
controlling the ozone amount entering the gas phase titration cavity 4 to be not higher than the nitric oxide standard gas amount entering the gas phase titration cavity 4;
and 2, communicating the second interface 802 with the third interface 803 by controlling the four-way valve 8, so that the concentration of the nitric oxide standard gas can be measured by the nitric oxide gas analyzer 11, and the nitric oxide standard gas is used for calibrating the nitric oxide gas analyzer 11 to ensure that the measured value is accurate (calibration of the nitric oxide gas analyzer 11, namely, a nitric oxide mark is communicated with the nitric oxide gas analyzerA quasi-gas, which adjusts and calibrates the indicating value of the instrument according to the concentration value of the nitric oxide standard gas); and recording the concentration value of the nitric oxide standard gas, and recording the concentration value as CNO.0
Step 3, the fourth interface 804 is communicated with the third interface 803 by controlling the four-way valve 8, so that the concentration of the nitrogen dioxide standard gas can be measured by the nitrogen dioxide gas analyzer 10, and the nitrogen dioxide gas analyzer 10 is calibrated to ensure that the measured value is accurate (calibration of the nitrogen dioxide gas analyzer 10, namely, the nitrogen dioxide standard gas is introduced into the nitrogen dioxide gas analyzer, and the indication value of the instrument is adjusted and calibrated according to the concentration value of the nitrogen dioxide standard gas); and recording the concentration value of the nitrogen dioxide standard gas as CNO2.0
Step 4, the first interface 801 and the third interface 803 are communicated by controlling the four-way valve 8, the concentration of the nitric oxide gas in the gas (at this time, the gas is a mixed gas of nitric oxide, nitrogen dioxide, ozone and oxygen) after the gas phase titration is finished by the gas phase titration chamber 4 is measured by the nitric oxide gas analyzer 11, and the concentration value of the nitric oxide gas is recorded as CNO.1(ii) a The concentration of the nitrogen dioxide gas in the channel gas is measured by a nitrogen dioxide gas analyzer 10, and the concentration value of the nitrogen dioxide gas is recorded as CNO2.1
Step 5, as can be seen from formula (1),
CO3.1=CNO.0-CNO.1 (2)
CO3.2=CNO2.1-CNO2.0 (3)
CO3.D=CO3.1-CO3.2 (4)
wherein, CO3.1And CO3.2Is the ozone concentration; cO3.DIs the difference between the two ozone concentration values.
The calculated ozone concentration C of the theoretical formula (4)O3.DShould be 0, i.e. the reduction in the nitric oxide gas concentration should be equal to the increase in the nitrogen dioxide gas concentration, and these two values are equal to the measured ozone concentration. In practice, the linear range of measurement is limited by the nitrogen dioxide gas analyzer 10 and the nitric oxide gas analyzer 11Accuracy, stability, resolution, response time, etc., the values obtained by equations (2) and (3) may be different, i.e., C obtained by equation (4)O3.DIs not 0.
Step 6, when C obtained in formula (4)O3.DWhen 0, then C is selectedO3.1Is the ozone gas concentration value generated by the ozone generator 12, CO3.1The values are used as standard values for calibrating the standard ozone gas analyzer 14, and also as standard values for calibrating the ozone gas analyzer 15 to be tested.
It can be easily seen that the ozone gas concentration value is traced back to the nitric oxide standard gas by the nitric oxide gas analyzer 11. The total amount of the nitric oxide standard gas is traced to time, flow and molar concentration, so that the tracing chain is complete and clear; similarly, the ozone gas concentration value is traced to the nitrogen dioxide standard gas by the nitrogen dioxide gas analyzer 10. The quality of the nitrogen dioxide standard gas is traced to time, flow and molar concentration, so that the tracing chain is complete and clear; and the ozone gas concentration value is mutually verified by the nitric oxide standard gas and the nitrogen dioxide standard gas, so that the self-verification function is realized, and the measurement errors caused by factors such as measurement linearity, accuracy, stability, resolution, response time and the like of the nitrogen dioxide gas analyzer 10 and the nitrogen dioxide gas analyzer 11 are avoided.
Step 7, when C obtained in formula (4)O3.DIf not 0, C is calculated by the following equations (5), (6) and (7)O3.E1And CO3.E2
CO3.M=(CO3.1+CO3.2)/2 (5)
CO3.E1=(CO3.1-CO3.M)/CO3.M (6)
CO3.E2=(CO3.2-CO3.M)/CO3.M (7)
If CO3.E1Value and CO3.E2The values are all within the measurement error range (when the ozone concentration is within the range of 0-1000ppb, the maximum allowable error MPE is + -5 ppb or + -5%; when the ozone concentration is within the range of 0-1000ppm, the maximum allowable error MPE is + -2% FS), then C is takenO3.MOzone gas concentration value generated for ozone generatorC of theO3.MThe values are used as standard values for calibrating the standard ozone gas analyzer 14, and also as standard values for calibrating the ozone gas analyzer 15 to be tested.
It is easy to see that, as in step 6, the ozone gas concentration values are respectively traced to time, flow and molar quantity of substances, so that the tracing chain is clear and complete; and has the function of self-verification, thereby avoiding the measurement errors caused by the factors of linearity, accuracy, stability, resolution, response time and the like of the measurement of the nitrogen dioxide gas analyzer 10 and the nitric oxide gas analyzer 11.
If CO3.E1Value and CO3.E2And if any one of the values exceeds the allowable measurement error range, checking the nitrogen dioxide gas analyzer 10 and the nitric oxide gas analyzer 11, and testing according to the step 6 and the step 7 after the measurement faults are eliminated.
In the description of the present invention, it is to be noted that, unless otherwise explicitly specified or limited, the terms "connected" and "connected" are to be interpreted broadly, e.g., as being fixed or detachable or integrally connected; can be mechanically or electrically connected; may be directly connected or indirectly connected through an intermediate. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
Finally, it should be noted that the above-mentioned technical solution is only one embodiment of the present invention, and it will be apparent to those skilled in the art that various modifications and variations can be easily made based on the application method and principle of the present invention disclosed, and the method is not limited to the above-mentioned specific embodiment of the present invention, so that the above-mentioned embodiment is only preferred, and not restrictive.

Claims (7)

1. An ozone gas phase titration standard device, wherein the ozone gas phase titration standard device comprises:
the nitric oxide standard gas high-pressure gas cylinder is respectively connected with the gas-phase titration cavity and the four-way valve;
the nitrogen dioxide standard gas high-pressure gas cylinder is respectively connected with the gas phase titration cavity and the four-way valve, the gas phase titration cavity is connected with the four-way valve, and the four-way valve is also respectively connected with a nitric oxide gas analyzer and a nitrogen dioxide gas analyzer;
and the ozone generator is respectively connected with the gas-phase titration cavity, the standard ozone gas analyzer and the detected ozone gas analyzer.
2. The ozone gas phase titration standard device according to claim 1, wherein a first three-way joint is connected to the nitric oxide standard gas high pressure gas cylinder, and the first three-way joint is respectively connected with the gas phase titration chamber and the four-way valve through gas pipelines;
the nitrogen dioxide standard gas high-pressure gas cylinder is connected with a second three-way joint, and the second three-way joint is respectively connected with the gas phase titration cavity and the four-way valve through gas pipelines;
the ozone generator is connected with a four-way joint, and the four-way joint is respectively connected with the gas-phase titration cavity, the standard ozone gas analyzer and the detected ozone gas analyzer through gas pipelines;
the gas phase titration cavity is also connected with a third three-way joint, and the third three-way joint is respectively connected with the back pressure valve and the four-way valve through a gas pipeline; and the four-way valve is also connected with a fourth three-way joint, and the fourth three-way joint is respectively connected with the nitric oxide gas analyzer and the nitrogen dioxide gas analyzer through gas pipelines.
3. The ozone gas phase titration standard according to claim 2, wherein the four-way valve has four ports, a first port, a second port, a third port and a fourth port, and only one of the first port, the second port and the fourth port is in communication with the third port during operation.
4. The ozone gas phase titration standard device according to claim 3, wherein the nitric oxide standard gas high pressure gas cylinder is connected with the first three-way joint and then respectively connected with the gas phase titration chamber and the second interface of the four-way valve through gas pipelines.
5. The ozone gas phase titration standard device according to claim 3, wherein the nitrogen dioxide standard gas high pressure gas cylinder is connected with the second three-way joint and then respectively connected with the gas phase titration chamber and the fourth port of the four-way valve through gas pipelines.
6. The ozone gas phase titration standard device according to claim 3, wherein after the gas phase titration chamber is connected with the third three-way joint through a gas pipeline, one path is connected with a back pressure valve through a gas pipeline and then is evacuated through a gas pipeline, and the other path is connected with the first interface of the four-way valve through a gas pipeline.
7. The ozone gas phase titration standard device according to claim 3, wherein a third port of the four-way valve is connected with the fourth three-way joint through a gas pipeline, and then is respectively connected with the nitrogen dioxide gas analyzer and the nitric oxide gas analyzer through gas pipelines.
CN202121549014.0U 2021-07-08 2021-07-08 Ozone gas phase titration standard device Active CN216434018U (en)

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