CN102183468B - Interference correction and concentration inversion method of multi-component gas analysis - Google Patents
Interference correction and concentration inversion method of multi-component gas analysis Download PDFInfo
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Abstract
The invention discloses an interference correction and concentration inversion method of multi-component gas analysis, which comprises the following steps: a reference filter channel is used for eliminating the system drifting because of external factors; the water vapor is utilized to correct the interference of the water vapor of an analysis meter in the service environment on the interference functions of the other filter channels; the cross-correlation functions are utilized to obtain the pure absorbance of various target gases in the mixed gas by establishing and solving a multivariable interference equation set, and the cross interference among the target gas is corrected; and after the interference is corrected, the response functions of each filter channel are utilized to inverse the concentration of the target gas. After a simple non-dispersion infrared analysis meter utilizes the interference correction and concentration inversion method provided by the invention, a detector is used for simultaneously and accurately detecting the concentration of various polluted gases such as CO2, CO, NO, NO2, SO2, CH4, N2O, HC, H2O, NH3, H2S and the like.
Description
Technical field
The present invention relates to multicomponent gas concentration optical measurement field, is specially a kind of interference correction and retrieving concentration method of Multi-Component Gas Analyzing.
Background technology
Some links in the commercial production all may become industrial pollution source such as production equipment or the Workplace of the uses such as raw material production, process, combustion process, heating and cooling process, Product organization process.SO
2, NO
2, NO, CO and CO
2Deng the important component part as fume emission, not only can destroy atmospheric environment, harm humans health, also be one of important origin cause of formation of city haze, reduce city visibility, destroy radiation balance of earth, affect global climate.The concentration of effectively measuring various ingredients gas in the flue gas is the precondition of control waste gas of pollutant discharging.
Non-dispersion infrared (NDIR) spectroscopic methodology has the ability that multicomponent pollutant is monitored simultaneously, this quasi-instrument usually simple in structure, cost is low, measuring accuracy is high, good stability, can carry out easily man-machine interaction, be the desirable monitoring equipment of Continuous emission monitoring system on power station and the incinerator (CEMS).Yet the selected middle infrared-gas absorption bands of non-disperse infrared spectrum method all exists certain absorption to disturb between a lot of gases, comprises that the interference of other gas in the instrument environment for use is (such as H
2O) and the intersection between the object gas to be measured disturb.In addition, non-dispersion infrared multicomponent analysis instrument also faces the problems such as light source ages, mains ripple, particle scattering, and all these can be referred to as interference, if do not revised, will greatly affect accuracy in detection and the sensitivity of instrument.Therefore, be necessary to work out a kind of interference correction and retrieving concentration method that is applicable to the non-dispersion infrared Multi-Component Gas Analyzing, to guarantee the Measurement accuracy of industrial pollution source polycomponent dusty gas.
Summary of the invention
The interference correction and the retrieving concentration method that the purpose of this invention is to provide a kind of Multi-Component Gas Analyzing are vulnerable to disturb the problem that causes accuracy in detection and sensitivity to solve prior art.
In order to achieve the above object, the technical solution adopted in the present invention is:
The interference correction of Multi-Component Gas Analyzing and retrieving concentration method, described multicomponent gas is placed in the sample cell, set up the reference filtering passage, comprise a plurality of target filtering channels of steam filtering channel, adopt light source to send reference light, send a plurality of detection light by a plurality of target filtering channels to sample cell to sample cell by the reference filtering passage, adopt photo-detector as receiving end, each object gas component is corresponding one by one in described target filtering channel and the multicomponent gas, it is characterized in that: may further comprise the steps:
(1) multicomponent gas that passes into variable concentrations in the sample cell is a kind of object gas component wherein, the detection light signal that receives by photo-detector obtains the wherein response function of a kind of object gas component in each target filtering channel of multicomponent gas, according to above-mentioned steps and then obtain response function in each comfortable each target filtering channel of each object gas component of multicomponent gas;
(2) in sample cell, pass into multicomponent gas to be measured, the reference optical signal that receives according to photo-detector obtains system drifting correction measured value, and the detection light signal of a plurality of target filtering channels that receive according to photo-detector obtains respectively the total absorbance of each object gas component in the multicomponent gas;
(3) according to the response function in each comfortable each target filtering channel of each object gas component in the multicomponent gas, by finding the solution response function and the cross correlation function of each object gas component between the response function of other target filtering channels that obtains each object gas component each self-corresponding target filtering channel at it, described cross correlation function disturbs the interference function of size to other target filtering channels as each object gas component of expression;
(4) the total absorbance correction of each object gas component is eliminated the system drifting error in the multicomponent gas that the system drifting correction measured value that obtains by step (2) obtains step (2) respectively, each the object gas component of multicomponent gas that obtains by step (3) wherein in the multicomponent gas that respectively step (2) obtained of the interference function of steam the total absorbance of outer each the object gas component of vapor-removing revise, disturb to eliminate steam, the interference function of outer each the object gas component of the multicomponent gas vapor-removing that obtains by step (3) offsets the total absorbance of outer each the object gas component of vapor-removing in the multicomponent gas after vapor-removing disturbs and revises, disturb with the intersection of eliminating between each object gas component, obtain at last the pure absorbance of each target components gas in the multicomponent gas;
(5) the pure absorbance of each object gas component in the multicomponent gas that obtains according to step (4), and the response function inverting in each comfortable each target filtering channel of each object gas component of multicomponent gas obtains the concentration of each object gas component in the multicomponent gas.
The interference correction of described Multi-Component Gas Analyzing and retrieving concentration method is characterized in that: described reference filtering passage, a plurality of target filtering channel are made of optical filter respectively.
The interference correction of described Multi-Component Gas Analyzing and retrieving concentration method is characterized in that: calculate after the detection light signal of a plurality of target filtering channels that each object gas component total absorbance separately receives by photo-detector in the described multicomponent gas converts respectively magnitude of voltage to.
The interference correction of described Multi-Component Gas Analyzing and retrieving concentration method, it is characterized in that: in the described step (3), when eliminating the intersection interference between each object gas component, set up the pure absorbance of the object gas component that must eliminate the intersection interference, the object gas component that palpus elimination intersection is disturbed is eliminated the total absorbance after the steam interference, equation outside the vapor-removing between the interference function of other object gas components: the interference function of other object gas components outside the pure absorbance+vapor-removing of the total absorbance after the object gas component elimination steam interference that palpus elimination intersection is disturbed=object gas component that palpus elimination intersection is disturbed, different must the elimination intersected the equations simultaneousness of the object gas component the disturbed disturbance equation group that comes from different backgrounds and possess different abilities, obtain the pure absorbance of each object gas component in the multicomponent gas by finding the solution polynary disturbance equation group.
The present invention is a kind of interference correction and retrieving concentration method of the Multi-Component Gas Analyzing based on the non-disperse infrared spectrum absorption process.Use the reference filtering passage to eliminate the system drifting that extraneous factor causes; Utilize steam to the interference of steam in the interference function correction testing environment of other filtering channel; Utilize the interference function of outer each the object gas component of multicomponent gas vapor-removing, by setting up and finding the solution polynary disturbance equation group, can obtain the pure absorbance of all types of target gas composition in the multicomponent gas, the intersection between the revise goal gas composition is disturbed.After disturb revising, utilize the response function in each comfortable each target filtering channel of each object gas component of multicomponent gas, with the pure absorbance inverting concentration that is object gas.
The acquisition methods of cross correlation function is as follows between object gas component of the present invention:
Object gas component A can use cross correlation function (or claiming interference function) quantitative description to the interference size of object gas B component:
A (τ): in the A filtering channel, the function corresponding relation formula of the absorbance of object gas component A and its concentration τ, B (τ): in the B filtering channel, the function corresponding relation formula of the absorbance of object gas component A and its concentration τ, C
MinBe the minimum detectable level of object gas component A in the analyser, C
MaxFull scale concentration value for object gas component A.
The present invention compared with prior art has the following advantages:
The interference correction of the Multi-Component Gas Analyzing that the present invention relates to and retrieving concentration method have solved the mutual interference problem of the gas in the measurement of multi-components, have improved measuring accuracy.Use a plurality of filtering channels to be respectively applied to the analysis of multiple gases; Introduce a reference filtering passage, can eliminate well the system drifting that extraneous factor causes; In the steam filtering channel, do not exist the absorption of any other gas or absorption to ignore, the well interference of steam in the environment for use of correction analysis instrument can normally be operated in the environment of humidity or vapour concentration variation analyser; The cross correlation function that calculating is obtained, intersect the size of disturbing between can the quantitative test object gas, utilize cross correlation function, by setting up and find the solution the method for polynary disturbance equation group, can obtain the pure absorbance of all types of target gas in the mixed gas, the intersection between revise goal gas is disturbed.A simple NDIR non dispersive infrared analyzer, use this patent related interference correction and retrieving concentration method after, use a detector just can accurately detect the concentration of multiple dusty gas the while, for example, CO
2, CO, NO, NO
2, SO
2, CH
4, N
2O, HC, H
2O, NH
3Etc..
Description of drawings
Fig. 1 is that block diagram is flowed out in the present invention.
Fig. 2 disturbs elimination front and back Changing Pattern figure for using example steam of the present invention, wherein:
Fig. 2 (a) is for passing into 0.5%, 1.5%, 2.5%, 3.5%, the H of 4.5% concentration respectively in sample cell
2During O, disturb the absorbance Changing Pattern figure of front each filtering channel of steam correction; Fig. 2 (b) is the absorbance Changing Pattern figure of each filtering channel after the correction of interference steam.
Changing Pattern figure before and after Fig. 3 disturbs for application example of the present invention intersects and eliminates, wherein:
Fig. 3 (a) is for passing into 2.50%, 7.50%, 12.50%, 17.50%, the CO of 22.50% concentration respectively in sample cell
2The time, intersect and disturb the absorbance Changing Pattern figure that revises front each filtering channel; Fig. 3 (b) disturbs the absorbance Changing Pattern figure that revises rear each filtering channel for intersecting.
Embodiment
Such as Fig. 1～shown in Figure 3.Among the present invention, there is not any gas absorption in the optical filter bandwidth of reference filtering passage or absorbs and to ignore, any time signal fluctuation (as: the light source ages that causes of external interference, voltage fluctuation, dust scattering etc.) amplitude is identical with the object gas filtering channel, utilizes the extraneous interference of fluctuating and bringing of signal correction of reference filtering passage.
The present invention utilizes the concentration of the absorbance inverting gas with various of different frequency bands, for example: see through wavelength take the center and be the filtering channel inverting CH of 3.26 μ m
4Concentration; See through wavelength take the center and be the concentration of the filtering channel inverting CO of 4.63 μ m; See through wavelength take the center and be the concentration of the filtering channel inverting NO of 5.21 μ m; See through wavelength take the center and be the filtering channel inverting NO of 6.25 μ m
2Concentration; See through wavelength take the center and be the filtering channel inverting CO of 4.84 μ m
2Concentration, etc.
The present invention utilizes steam filtering channel correction steam to the interference of object gas, and the light signal of this filtering channel only reflects H in the testing environment
2The variation of O utilizes steam absorbance and steam to the interference function of other object gas component, revises steam to the interference of multicomponent gas to be measured, improves detection sensitivity and the accuracy of system.
The present invention can simulate object gas component X at the response function of each target filtering channel by pass into a certain object gas component X of variable concentrations in sample cell.
The present invention is by passing into the H of variable concentrations in sample cell
2O can simulate H
2O is at the response function of each filtering channel.For example: H
2O is at H
2The response function F of O filtering channel
0(X); H
2O is at SO
2The response function F of filtering channel
1(X); H
2O is at CO
2The response function F of filtering channel
2(X); H
2O is at NO
2The response function F of filtering channel
3(X); H
2O is at the response function F of NO filtering channel
4(X) etc.By finding the solution F
i(X) (i=1,2,3,4 ...) and F
0(X) related function F
I0(X) can quantitative test H
2O is to the interference size of each target filtering channel, for example: F
10(X) can quantitative test H
2O is to SO
2The interference size of filtering channel; F
20(X) can quantitative test H
2O is to CO
2The interference size of filtering channel; F
30(X) can quantitative test H
2O is to NO
2The interference size of filtering channel; F
40(X) can quantitative test H
2O is to interference size of NO filtering channel etc.
The present invention can simulate object gas component X at the response function of each target filtering channel by pass into a certain object gas component X of variable concentrations in sample cell.For example: the SO that passes into variable concentrations
2, can draw SO
2At SO
2The response function A of filtering channel
0(X); SO
2At CO
2The response function A of filtering channel
1(X); SO
2At NO
2The response function A of filtering channel
2(X); SO
2Response function A at the NO filtering channel
3(X); SO
2Response function A at the CO filtering channel
4(X) etc.By finding the solution A
i(X) (i=1,2,3,4 ...) and A
0(X) related function A
I0(X) can quantitative test SO
2To the interference size of each target filtering channel, for example: A
10(X) can quantitative test SO
2To CO
2The intersection of filtering channel is disturbed size; A
20(X) can quantitative test SO
2To NO
2The intersection of filtering channel is disturbed size; A
30(X) can quantitative test SO
2Intersection to the NO filtering channel is disturbed size; A
40(X) can quantitative test SO
2Intersection to the CO filtering channel is disturbed size etc.In like manner can quantitatively obtain other object gas such as CO
2, NO
2, NO, CO, CH
4, N
2O, HC are to the interference size of each target filtering channel.
The present invention surveys the total absorbance that magnitude of voltage after the conversion can at first calculate each object gas component by photo-detector, for example: H when having the object gas component of multiple variable concentrations in the sample cell
2The O total absorbance
SO
2Total absorbance
CO
2Total absorbance
NO
2Total absorbance
The NO total absorbance
Etc..According to H
2The O total absorbance
With interference function F
I0(X) can obtain total absorbance after steam is disturbed in each object gas component correction, for example: SO
2The total absorbance behind the steam is disturbed in correction
CO
2The total absorbance behind the steam is disturbed in correction
NO
2The total absorbance behind the steam is disturbed in correction
NO revises the total absorbance behind the interference steam
Etc..
Among the present invention, because the intersection between the object gas component is disturbed more complicated, may all there be between any two interference, can be revised by the method for setting up polynary disturbance equation group, utilize each object gas component correction to disturb total absorbance and a series of interference function behind steam can reach above purpose.Be modified to example with the interference of three component object gas intersection, if SO
2Correction disturbs the total absorbance behind the steam to be
CO
2Correction disturbs the total absorbance behind the steam to be
NO
2Correction disturbs the total absorbance behind the steam to be
A
10(X) expression SO
2To CO
2The interference function of filtering channel; A
20(X) expression SO
2To NO
2The interference function of filtering channel; B
01(X) expression CO
2To SO
2The interference function of filtering channel; B
21(X) expression CO
2To NO
2The interference function of filtering channel; C
02(X) expression NO
2To SO
2The interference function of filtering channel; C
12(X) expression NO
2To CO
2The interference function of filtering channel, SO
2Pure absorbance use
Expression, CO
2Pure absorbance use
Expression, NO
2Pure absorbance use
Expression, so SO
2, CO
2, NO
2Three target filtering channels can be set up following ternary disturbance equation group:
Find the solution this system of equations and can obtain respectively three kinds of object gas SO
2, CO
2, NO
2Pure absorbance
Disturb revised absorbance can be directly used in the gas concentration inverting.Making uses the same method can also resolve CO
2, CO, NO, NO
2, SO
2, CH
4, N
2O, HC, NH
3, H
2Intersection during the simultaneously on-line analysis of the component gas such as O is disturbed and is revised.
During Multi-Component Gas Analyzing of the present invention, the retrieving concentration of each component gas all will be finished following step:
(1) eliminates hardware fluctuation or system drifting; (2) realize zero-compensation and revise steam and disturb; (3) intersection between revise goal gas is disturbed; (4) concentration of inverting object gas.
Take object gas NO as example, in inverting gas concentration process, consider following some correction:
Drift correction measured value: A
N0=ln (V
Ref'/V
N0') ... ... ... ... (1)
Zero-compensation measured value: A
N0(1)-FZ-UZ........................ (2)
Interference gas: CO
2, NO
2, SO
2
Disturb and revise measured value: A
N0=(2)-distracter (CO
2, NO
2, SO
2) ... (3)
NO retrieving concentration: (3) → NO concentration ... ... ... ... ... (4)
The first step [formula (1)]: introduce a reference filtering passage, measured value is converted into absorbance, eliminate the system drifting that any outside cause causes: the scattering of particle, the sedimental extinction effect of analyser window, aging or light signal Strength Changes that voltage fluctuation causes etc., finish this step and obtain the drift correction measured value.
Second step [formula (2)]: the FZ here is producer's correction term, is the value that obtains under absolute zero gas (dry and do not contain infrared absorption pollutant) bar.For NO, FZ=ln (V
Ref/ V
NO).It should be noted that different target gas, the FZ value is different, as to CO
2, FZ=ln (V
Ref/ V
CO2); To SO
2, FZ=ln (V
Ref/ V
SO2), and so on.UZ is user's calibration item, and the offset of introducing during on-the-spot zero calibration is the value that obtains under on-the-spot zero gas (contain part steam but the do not contain the infrared absorption pollutant) condition, and UZ is exactly the difference of ' on-the-spot zero point ' and ' actual zero point ' in fact.Equally, object gas is different, and UZ is also different, and different occasion, the different measuring time, all might be different, namely UZ is affected by environment very large, carry out scene zero calibration all might be different at every turn, finish this step and can revise the impact that steam disturbs, and obtain the zero-compensation measured value.
The 3rd step [formula (3)]: the foundation of equation with many unknowns group and solution procedure, the intersection of finishing between this step energy revise goal gas is disturbed, and obtains disturbing correction measured value, the i.e. pure absorbance of each object gas.
The 4th step [formula (4)]: utilize NO will disturb revised pure absorbance inverting to be the concentration of gas at the response function of NO filtering channel.
Claims (3)
1. the interference correction of Multi-Component Gas Analyzing and retrieving concentration method, described multicomponent gas is placed in the sample cell, set up the reference filtering passage, comprise a plurality of target filtering channels of steam filtering channel, adopt light source to send reference light, send a plurality of detection light by a plurality of target filtering channels to sample cell to sample cell by the reference filtering passage, adopt photo-detector as receiving end, each object gas component is corresponding one by one in described target filtering channel and the multicomponent gas, it is characterized in that: may further comprise the steps:
(1) passes into a kind of object gas component in the multicomponent gas of variable concentrations in the sample cell, the detection light signal that receives by photo-detector obtains the response function of a kind of object gas component in each target filtering channel in the multicomponent gas, according to above-mentioned steps and then obtain the response function in each comfortable each target filtering channel of each object gas component in the multicomponent gas;
(2) in sample cell, pass into multicomponent gas to be measured, the reference optical signal that receives according to photo-detector obtains system drifting correction measured value, and the detection light signal of a plurality of target filtering channels that receive according to photo-detector obtains respectively the total absorbance of each object gas component in the multicomponent gas;
(3) by in sample cell, passing into a certain object gas component of variable concentrations, simulate the object gas component at the response function of each target filtering channel, obtain the cross correlation function of each object gas component between the response function of other target filtering channels by finding the solution, described cross correlation function disturbs the interference function of size to other target filtering channels as each object gas component of expression;
(4) the total absorbance correction of each object gas component is eliminated the system drifting error in the multicomponent gas that the system drifting correction measured value that obtains by step (2) obtains step (2) respectively, the total absorbance of outer each the object gas component of vapor-removing is revised in the multicomponent gas that the interference function of the steam in each the object gas component of multicomponent gas that obtains by step (3) obtains step (2) respectively, disturb to eliminate steam, the interference function of outer each the object gas component of the multicomponent gas vapor-removing that obtains by step (3) offsets the total absorbance of outer each the object gas component of vapor-removing in the multicomponent gas after vapor-removing disturbs and revises, disturb with the intersection of eliminating between each object gas component, obtain at last the pure absorbance of each target components gas in the multicomponent gas;
(5) response function in the multicomponent gas that obtains according to step (4) in each comfortable each target filtering channel of the pure absorbance of each object gas component and each object gas component of multicomponent gas, inverting obtains the concentration of each object gas component in the multicomponent gas;
In the described step (3), when eliminating the intersection interference between each object gas component, set up the pure absorbance of the object gas component that must eliminate the intersection interference, the object gas component that palpus elimination intersection is disturbed is eliminated the total absorbance after the steam interference, equation outside the vapor-removing between the interference function of other object gas components: the interference function of other object gas components outside the pure absorbance+vapor-removing of the total absorbance after the object gas component elimination steam interference that palpus elimination intersection is disturbed=object gas component that palpus elimination intersection is disturbed, different must the elimination intersected the equations simultaneousness of the object gas component the disturbed disturbance equation group that comes from different backgrounds and possess different abilities, obtain the pure absorbance of each object gas component in the multicomponent gas by finding the solution polynary disturbance equation group.
2. the interference correction of Multi-Component Gas Analyzing according to claim 1 and retrieving concentration method, it is characterized in that: described reference filtering passage, a plurality of target filtering channel are made of optical filter respectively.
3. the interference correction of Multi-Component Gas Analyzing according to claim 1 and retrieving concentration method is characterized in that: calculate after the detection light signal of a plurality of target filtering channels that each object gas component total absorbance separately receives by photo-detector in the described multicomponent gas converts respectively magnitude of voltage to.
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| CN103592415B (en) * | 2013-10-25 | 2015-09-09 | 上海申瑞继保电气有限公司 | Single-component gas concentration correction process in transformer oil |
| CN103760125B (en) * | 2014-01-22 | 2017-02-08 | 中国科学院合肥物质科学研究院 | Method for improving inversion accuracy of high greenhouse gas concentration |
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| CN104819958B (en) * | 2015-05-19 | 2017-03-29 | 清华大学 | Automatically the method and apparatus of steam interference is eliminated in Fourier transform infrared spectroscopy gas detecting |
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| CN111929269B (en) * | 2020-09-23 | 2021-01-15 | 上海翼捷工业安全设备股份有限公司 | Three-channel infrared methane detector resistant to water vapor interference |
| CN113758891B (en) * | 2021-08-18 | 2022-06-03 | 清华大学 | Method, device and equipment for calculating component concentration of mixed gas and storage medium |
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| CN114965616A (en) * | 2022-06-01 | 2022-08-30 | 国网湖北省电力有限公司超高压公司 | SF6 decomposition gas detection method |
| CN115639168B (en) * | 2022-12-21 | 2023-04-07 | 杭州泽天春来科技有限公司 | Gas detection method, system and medium for gas analyzer |
| CN117288711B (en) * | 2023-11-24 | 2024-03-19 | 四方光电股份有限公司 | Leakage monitoring device and monitoring method for power battery |
| CN117388204B (en) * | 2023-12-13 | 2024-04-12 | 杭州泽天春来科技股份有限公司 | Nitric oxide gas analysis system, method and computer readable storage medium |
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| CN101281125A (en) * | 2008-05-19 | 2008-10-08 | 安徽敏测光电科技有限公司 | Method and apparatus for monitoring intelligent infrared multi-component harmful gas |
| CN101587068A (en) * | 2009-05-27 | 2009-11-25 | 陈小英 | Multi-sensor gas analyzer |
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