CN109211884A - A kind of chemiluminescent analyzer NOx conversion efficiency rapid detection method - Google Patents
A kind of chemiluminescent analyzer NOx conversion efficiency rapid detection method Download PDFInfo
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Abstract
The present invention relates to engine exhaust measurement, especially a kind of chemiluminescent analyzer NOx conversion efficiency rapid detection method.The detection method, comprising the following steps: step 1: two o'clock calibration is carried out to CLD analyzer, with NO2And N2Hybrid standard gas as detection sample gas, record NO2Concentration nominal value A；Step 2: CLD analyzer is placed in NOxMeasurement channel makes detection sample gas pass through NOxConverter measures NOxConcentration value B；Step 3: NOx conversion efficiency is calculated by formula B/A*100%.The detection method step is simple, and time-consuming short, detection efficiency is high, will not compute repeatedly to error, and testing result accuracy is high, and detection device acquisition cost is low, eliminates the cost of detection device periodic calibration maintenance.
Description
Technical field
The present invention relates to engine exhaust measurement, especially a kind of chemiluminescent analyzer NOx conversion efficiency is quickly detected
Method.
Background technique
Measuring engine exhaust, there are two purposes, first is that certification test, examines whether exhaust meets what each department were implemented
Discharge statute of limitation；Second is that analysis combustion phenomena, research and improvement engine.The object of engine exhaust measurement includes CO2、
H2O、N2、CO、H2, the compositions such as HC, NOx.Wherein, CO, HC, NOx be to the harmful substance of environment and human body, especially to limit and
Measurement.Nitrogen (N under the condition of high temperature in cylinder, in air2) when being oxidized, can generate nitric oxide (NO) and
Nitrogen dioxide (NO2) etc. nitrogen oxides (NOx), under normal conditions exhaust in NO and NO2Volumetric concentration ratio be about 95:5.
Usually method used by measurement nitrogen oxides (NOx) concentration is called chemoluminescence method, i.e. CLD method, chemiluminescence
The testing principle of method is by the sample gas containing NO and excessive ozone (by pure oxygen O2O is generated by ozone generator3) while importing
When learning in luminescence analyzer in the reactor of NO detector (can only detect NO), NO therein can be by O3Oxidation generates NO2, and give birth to
At part NO2(about 10%) is in excitation state (NO2 *).As these NO2 *When being returned to ground state, excitation energy will be with photon
Form release, reaction equation NO+O3→NO2 *+O2；NO2 *→NO2+hv；Testing principle is as shown in Fig. 1.Due to luminous quantity and NO2
Production quantity, i.e., and O3The NO amount to react is directly proportional, so luminous intensity can be detected by photoelectric cell to measure sample gas
In NO concentration.
In order to further measure NOx (=NO+NO2) concentration, it is also necessary to using be filled with carbon compound converting means
(i.e. NOx conversion device) is first by NO contained in sample gas2It is reduced to NO.Reaction equation inside converter is as follows, restores NO2When
Need to consume carbon, reaction equation 2NO2→2NO+O2；NO2+C→NO+CO；2NO2+C→2NO+CO2；Converter working principle
As shown in Fig. 1.Since NO is not influenced by converter interior change, so according to nitrogen conservation, as long as sample gas is passed through
Converter can obtain NOx concentration, then subtract NO concentration with NOx concentration and can calculate NO2Concentration.Therefore NOx conversion device is by NO2
The efficiency for being converted into NO can impact measurement result.In order to guarantee that the accuracy of measurement result must be carried out periodically
The detection of NOx conversion efficiency, emission regulation demands NOx conversion device is by NO2The efficiency of NO is converted into not less than 95%.
Below with reference to conventional NOx conversion efficiency detection device and general flow chart (attached drawing 2) to NOx conversion efficiency detection side
Method and step are illustrated: the device for carrying out NOx conversion efficiency detection is the gas divider containing ozone generator, detection pair
Like the CLD analyzer containing NOx conversion device.There are two types of the calibrating gas used, and one is high pure oxygens, and one is main components
For the NOx and N of NO2Gaseous mixture.
The common detection methods of NOx conversion efficiency generally include following 4 steps:
Step 1: two o'clock calibration is carried out to CLD analyzer, is placed in NO Measurement channel, analyzer can only measure mixed at this time
Close the concentration of NO in gas.CLD analyzer ozone generator is opened, the ozone generator of gas divider is closed, it then will mixing
Gas continuously passes through gas divider, is passed through CLD analyzer and measures, and measures NO concentration value C, by adjusting the oxygen being passed through
Amount, makes C value be reduced to 80% or so of NO nominal concentration.
Step 2: CLD analyzer is still placed in NO Measurement channel, starts the ozone generator of gas divider, makes gaseous mixture
In a part of NO be oxidized to NO2, it is passed through CLD analyzer and measures, measure NO concentration value D, by adjusts O3Production rate makes D
Value is reduced to 10%~20% or so of NO nominal concentration.
Step 3: switching to NOx Measurement channel for CLD analyzer, gaseous mixture made to first pass through NOx conversion device, this step analysis
That instrument measures is NO and NO in gaseous mixture2Total concentration, i.e. NOx concentration value A.
Step 4: CLD analyzer is still placed in NOx Measurement channel, closes the ozone generator of gas divider, continues to make to mix
Closing gas, (NO in gaseous mixture will not be converted into NO at this time by NOx conversion device2), continue to measure NOx concentration value B.
(B-A) that acquire is the NO for not being reduced into NO when being passed through NOx conversion device2Concentration.(C-D) that acquires really exists
By O in gas divider3It is oxidized to NO2NO concentration, because of nitrogen conservation, this NO concentration is exactly to be passed through NOx conversion device
NO2Total concentration.
It thus can then derive the calculation formula of NOx conversion efficiency are as follows:
But there are following shortcoming and deficiency for above-mentioned tradition NOx conversion efficiency detection method: detecting step is cumbersome, time-consuming
Long, detection efficiency is low；Calibrating gas depletion rate is fast, and dosage is big, and testing cost is high；Error is big, and testing result is inaccurate or is difficult to
It meets the requirements, to further decrease detection efficiency；Detection method depends on expensive gas divider, detection device
Acquisition cost is high；Gas divider as detection device belongs to standard utensil, needs periodically to send state's external calibration, calibrates expense
Height, time-consuming for calibration, influences on pilot development huge.
Summary of the invention
The present invention is intended to provide a kind of chemiluminescent analyzer NOx conversion efficiency rapid detection method, detection method step
Rapid simple, time-consuming short, detection efficiency is high, will not compute repeatedly to error, and testing result accuracy is high, detection device acquisition cost
It is low, eliminate the cost of detection device periodic calibration maintenance.
To achieve the goals above, technical solution provided by the invention is such that a kind of chemiluminescent analyzer NOxTurn
Change efficiency rapid detection method, comprising the following steps:
Step 1: carrying out zero point and span gas to CLD analyzer expires site calibration, with NO2And N2Hybrid standard gas conduct
Sample gas is detected, NO is recorded2Concentration nominal value A；
Step 2: CLD analyzer is placed in NOxMeasurement channel makes detection sample gas pass through NOxConverter measures NOxConcentration value
B；
Step 3: NOx conversion efficiency is calculated by formula B/A*100%.
Wherein, NO can be used in the step 12Calibrating gas and N2Calibrating gas configures nominal NO according to experiment demand2With
N2Hybrid standard gas.
Wherein, it will test sample gas in the step 2 and pass through NOxGas flow when converter is 1200-1300mL/min.
Wherein, temperature when opening the ozone generator of CLD analyzer in the step 1 is 24-27 DEG C.
Wherein, relative humidity when opening the ozone generator of CLD analyzer in the step 1 is 65-70%.
The beneficial effects of the present invention are:
1. detection efficiency is high, counted according to practice, the NOx of a chemiluminescent analyzer is detected using existing conventional method
Transformation efficiency at least needs half an hour, and can shorten to 10 minutes with detection time of the present invention.
2. reducing or remitting the huge investment of detection device, the gas using the necessary purchasing price valuableness of existing conventional method is divided
Device, and purchase gas divider is not needed with the present invention, it is only necessary to by calibrating gas by NO and N2Gaseous mixture be changed to NO2
And N2Gaseous mixture, two kinds of calibrating gas prices are very nearly the same, to further eliminate detection device periodic calibration
Maintenance cost will not have any impact to pilot development
3. reducing or remitting the huge calibration maintenance cost of detection device, the influence to pilot development is greatly reduced.
4. greatly reducing the depletion rate and dosage of calibrating gas, testing cost is reduced, for emission test equipment
For a fairly large number of large and medium-sized laboratory, cost declining effect is just become apparent.
5. step of the present invention is simple, time-consuming short, error will not be computed repeatedly, testing result accuracy is high, detection device
Acquisition cost is extremely low, can substitute existing conventional detection side completely in addition to non-customer has the occasion of particular/special requirement to examining report
Method.
Detailed description of the invention
Fig. 1 is the detection principle diagram of chemoluminescence method；
Fig. 2 is NOx conversion efficiency detection device and general flow chart.
Specific embodiment
With reference to embodiment, claim of the invention is described in further detail, but do not constituted pair
Any restrictions of the invention, any limited times modification made in the claims in the present invention protection scope, are still weighed in the present invention
In the claimed range of benefit.
Same CLD analyzer used in following embodiment and comparative example.
Embodiment 1
Step 1: being the NO of 199ppm with nominal concentration2And N2Hybrid standard gas as detection sample gas, record NO2Concentration
Nominal value A is 199ppm.At 25.8 DEG C, when relative humidity is 69.2%, carrying out zero point and span gas to CLD analyzer expires site
Calibration.
Step 2: CLD analyzer is placed in NOxMeasurement channel makes detection sample gas pass through NOxConverter, gas flow are
1300mL/min measures NOxConcentration value B is 193.035ppm.
Step 3: calculating NOx conversion efficiency by formula B/A*100% is 97.0%.
Embodiment 2
Step 1: being the NO of 102ppm with nominal concentration2And N2Hybrid standard gas as detection sample gas, record NO2Concentration
Nominal value A is 102ppm.At 26.8 DEG C, when relative humidity is 65.2%, carrying out zero point and span gas to CLD analyzer expires site
Calibration.
Step 2: CLD analyzer is placed in NOxMeasurement channel makes detection sample gas pass through NOxConverter, gas flow are
1300mL/min measures NOxConcentration value B is 100.164ppm.
Step 3: calculating NOx conversion efficiency by formula B/A*100% is 98.2%.
Embodiment 3
Step 1: being the NO of 301ppm with nominal concentration2And N2Hybrid standard gas as detection sample gas, record NO2Concentration
Nominal value A is 301ppm.At 24.8 DEG C, when relative humidity is 67.3%, carrying out zero point and span gas to CLD analyzer expires site
Calibration.
Step 2: CLD analyzer is placed in NOxMeasurement channel makes detection sample gas pass through NOxConverter, gas flow are
1300mL/min measures NOxConcentration value B is 296.786ppm.
Step 3: calculating NOx conversion efficiency by formula B/A*100% is 98.6%.
Comparative example 1
Step 1: choosing the NO and N that nominal concentration is 182ppm2Gaseous mixture as detection sample gas, at 25.8 DEG C, relatively
When humidity is 69.2%, two o'clock (i.e. zero point and span gas expire site) calibration is carried out to CLD analyzer.CLD analyzer is placed in
NO Measurement channel opens CLD analyzer ozone generator, closes gas divider ozone generator, then continues gaseous mixture
By gas divider, it is passed through CLD analyzer, measures NO concentration value C, by adjusting the amount of oxygen being passed through, C value is made to be reduced to NO
80% or so of nominal concentration, measuring C value is 145.523ppm.
Step 2:CLD analyzer is still placed in NO Measurement channel, starts the ozone generator of gas divider, makes in gaseous mixture
A part of NO be oxidized to NO2, it is passed through CLD analyzer and measures, measure NO concentration value D, by adjusts O3Production rate makes D value
It is reduced to 10%~20% or so of NO nominal concentration.Measuring D value is 36.215ppm.
Step 3: CLD analyzer is switched into NOx Measurement channel, gaseous mixture is made to first pass through NOx conversion device, this step analyzer
That measure is NO and NO in gaseous mixture2Total concentration, i.e. NOx concentration value A.Measuring A value is 143.897ppm.
Step 4:CLD analyzer is still placed in NOx Measurement channel, closes the ozone generator of gas divider, continues to make to mix
Closing gas, (NO in gaseous mixture will not be converted into NO at this time by NOx conversion device2), continue to measure NOx concentration value B be
145.912ppm。
Step 5: calculating NOx conversion efficiency by formula 1- (B-A)/(C-D) is 98.2%.
Comparative example 2
Step 1: choosing the NO and N that nominal concentration is 260ppm2Gaseous mixture as detection sample gas, at 26.8 DEG C, relatively
When humidity is 65.2%, two o'clock (i.e. zero point and span gas expire site) calibration is carried out to CLD analyzer.CLD analyzer is placed in
NO Measurement channel opens CLD analyzer ozone generator, closes gas divider ozone generator, then continues gaseous mixture
By gas divider, it is passed through CLD analyzer, measures NO concentration value C, by adjusting the amount of oxygen being passed through, C value is made to be reduced to NO
80% or so of nominal concentration, measuring C value is 205.66ppm.
Step 2:CLD analyzer is still placed in NO Measurement channel, starts the ozone generator of gas divider, makes in gaseous mixture
A part of NO be oxidized to NO2, it is passed through CLD analyzer and measures, measure NO concentration value D, by adjusts O3Production rate makes D value
It is reduced to 10%~20% or so of NO nominal concentration.Measuring D value is 41.132ppm.
Step 3: CLD analyzer is switched into NOx Measurement channel, gaseous mixture is made to first pass through NOx conversion device, this step analyzer
That measure is NO and NO in gaseous mixture2Total concentration, i.e. NOx concentration value A.Measuring A value is 202.452ppm.
Step 4:CLD analyzer is still placed in NOx Measurement channel, closes the ozone generator of gas divider, continues to make to mix
Closing gas, (NO in gaseous mixture will not be converted into NO at this time by NOx conversion device2), continue to measure NOx concentration value B be
205.124ppm。
Step 5: calculating NOx conversion efficiency by formula 1- (B-A)/(C-D) is 98.4%.
Comparative example 3
Step 1: choosing the NO and N that nominal concentration is 320ppm2Gaseous mixture as detection sample gas, at 24.8 DEG C, relatively
When humidity is 67.3%, two o'clock (i.e. zero point and span gas expire site) calibration is carried out to CLD analyzer.CLD analyzer is placed in
NO Measurement channel opens CLD analyzer ozone generator, closes gas divider ozone generator, then continues gaseous mixture
By gas divider, it is passed through CLD analyzer, measures NO concentration value C, by adjusting the amount of oxygen being passed through, C value is made to be reduced to NO
80% or so of nominal concentration, measuring C value is 250.88ppm.
Step 2:CLD analyzer is still placed in NO Measurement channel, starts the ozone generator of gas divider, makes in gaseous mixture
A part of NO be oxidized to NO2, it is passed through CLD analyzer and measures, measure NO concentration value D, by adjusts O3Production rate makes D value
It is reduced to 10%~20% or so of NO nominal concentration.Measuring D value is 47.59ppm.
Step 3: CLD analyzer is switched into NOx Measurement channel, gaseous mixture is made to first pass through NOx conversion device, this step analyzer
That measure is NO and NO in gaseous mixture2Total concentration, i.e. NOx concentration value A.Measuring A value is 244.875ppm.
Step 4:CLD analyzer is still placed in NOx Measurement channel, closes the ozone generator of gas divider, continues to make to mix
Closing gas, (NO in gaseous mixture will not be converted into NO at this time by NOx conversion device2), continue to measure NOx concentration value B be
249.77ppm。
Step 5: calculating NOx conversion efficiency by formula 1- (B-A)/(C-D) is 97.6%.
According to testing principle it is found that the purpose of detection seeks to examine NOx conversion device by NO2Be converted into NO ability whether
Up to standard, regardless of how many process and conversion done using gas divider before for existing method, final purpose is all to generate
NO2, then again by NO2It is passed through NOx conversion device to be detected, i.e., test object is exactly NO2, so can directly take completely ready-made
NO2Standard Gases are detected, without NO Standard Gases are first generated NO by chemical reaction by other instruments equipment2.In addition
Because of nitrogen conservation, the practical B value measured is exactly the NO that NO is converted to after NOx conversion device2Concentration, therefore, according to
Method of the present invention it is time-consuming it is shorter, cost is lower, step is simpler under the premise of, reach identical or more with the prior art
The result of high accuracy.
Claims (4)
1. a kind of chemiluminescent analyzer NOxTransformation efficiency rapid detection method, which comprises the following steps:
Step 1: carrying out zero point and span gas to CLD analyzer expires site calibration, with NO2And N2Hybrid standard gas as detection
Sample gas records NO2Concentration nominal value A；
Step 2: CLD analyzer is placed in NOxMeasurement channel makes detection sample gas pass through NOxConverter measures NOxConcentration value B；
Step 3: NOx conversion efficiency is calculated by formula B/A*100%.
2. a kind of chemiluminescent analyzer NO according to claim 1xTransformation efficiency rapid detection method, which is characterized in that
It will test sample gas in the step 2 and pass through NOxGas flow when converter is 1200-1300mL/min.
3. a kind of chemiluminescent analyzer NO according to claim 1xTransformation efficiency rapid detection method, which is characterized in that
Temperature when opening the ozone generator of CLD analyzer in the step 1 is 24-27 DEG C.
4. a kind of chemiluminescent analyzer NO according to claim 1xTransformation efficiency rapid detection method, which is characterized in that
Relative humidity when opening the ozone generator of CLD analyzer in the step 1 is 65-70%.
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| CN110554028A (en) * | 2019-10-18 | 2019-12-10 | 合肥美钛健康产业有限公司 | Gas detection method and gas detection system based on same |
| CN111577435A (en) * | 2020-05-27 | 2020-08-25 | 河南绿泽环保科技有限公司 | Ozone generating device for detecting efficiency of tail gas converter of fuel oil motor vehicle |
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