CN102183468A - 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 as the production equipment or the production place of 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 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, influence global climate.The concentration of measuring various ingredients gas in the flue gas effectively is the precondition of control pollution sources toxic emission.
Non-dispersion infrared (NDIR) spectroscopic methodology has the ability that multicomponent pollutant is monitored simultaneously, this quasi-instrument is simple in structure usually, cost is low, measuring accuracy is high, good stability, can carry out man-machine interaction easily, be the desirable monitoring equipment of continuous blow-down monitoring system (CEMS) on power station and the incinerator.Infrared-gas absorption bands during yet the non-disperse infrared spectrum method is selected all exists certain absorption to disturb between a lot of gases, and the interference that comprises other gas in the instrument environment for use is (as H
2O) and the cross interference between the object gas to be measured.In addition, non-dispersion infrared multicomponent analysis instrument also faces problems such as light source ages, mains ripple, particle scattering, and all these can be referred to as interference, if do not revised, will influence the accuracy in detection and the sensitivity of instrument greatly.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 accurate measurement 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 reduce 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 to sample cell to sample cell by a plurality of target filtering channels 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) wherein a kind of object gas component of multicomponent gas of feeding variable concentrations in sample cell, the detection light signal that receives by photo-detector obtains the response function of wherein a kind of object gas component of multicomponent gas in each target filtering channel, 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, feed 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 the total absorbance of each object gas component in the multicomponent gas respectively;
(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) total absorbance of each object gas component is revised to eliminate the system drifting error in the multicomponent gas that respectively step (2) obtained of the system drifting correction measured value that obtains by step (2), 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 except that steam the total absorbance of each object gas component revise, disturb to eliminate steam, the interference function of multicomponent gas each the object gas component except that steam that obtains by step (3) offsets in the multicomponent gas after steam disturbs except that steam the total absorbance of each object gas component and revises, to eliminate the cross interference between each object gas component, obtain the pure absorbance of each target components gas in the multicomponent gas at last;
(5) the response function inverting in each comfortable each target filtering channel of the pure absorbance of each object gas component in the multicomponent gas that obtains according to step (4), and each object gas component of multicomponent gas obtains each object gas component concentrations 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 magnitude of voltage respectively 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 cross interference between each object gas component, set up the pure absorbance that to eliminate the object gas component of cross interference, the object gas component of palpus elimination cross interference is eliminated the total absorbance after steam disturbs, equation except that steam between the interference function of other object gas components: the object gas component that must eliminate cross interference is eliminated the pure absorbance+interference function of other object gas components except that steam of the object gas component of the total absorbance=palpus elimination cross interference after steam disturbs, with the different equations simultaneousnesses that must eliminate the object gas component of the cross interference disturbance equation group that comes from different backgrounds and possess different abilities, by finding the solution the pure absorbance that polynary disturbance equation group obtains each object gas component in the multicomponent gas.
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 the interference of steam to steam in the interference function correction testing environment of other filtering channel; Utilize the interference function of multicomponent gas each object gas component except that steam,, can obtain the pure absorbance of all types of target gas composition in the multicomponent gas, the cross interference between the revise goal gas composition by setting up and finding the solution polynary disturbance equation group.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 gas during polycomponent is measured, and have improved measuring accuracy.Use a plurality of filtering channels to be respectively applied for the analysis of multiple gases; Introduce a reference filtering passage, can eliminate the system drifting that extraneous factor causes well; In the steam filtering channel, do not exist the absorption of any other gas or absorption to ignore, the interference of steam in the environment for use of correction analysis instrument well can normally be operated in the environment of humidity or vapour concentration variation analyser; The cross correlation function that calculating is obtained, the size of cross interference is utilized cross correlation function between can the quantitative test object gas, 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 cross interference between revise goal gas.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
3Or the like.
Description of drawings
Fig. 1 flows out block diagram for the present invention.
Fig. 2 is for using example steam interference eliminated of the present invention front and back Changing Pattern figure, wherein:
Fig. 2 (a) is for feeding 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 preceding 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.
Fig. 3 eliminates front and back Changing Pattern figure for using example cross interference of the present invention, wherein:
Fig. 3 (a) is for feeding 2.50%, 7.50%, 12.50%, 17.50%, the CO of 22.50% concentration respectively in sample cell
2The time, the absorbance Changing Pattern figure of each filtering channel before the cross interference correction; Fig. 3 (b) is the absorbance Changing Pattern figure of each filtering channel after the cross interference correction.
Embodiment
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 or the like) 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, and for example: seeing through wavelength with the center is the filtering channel inverting CH of 3.26 μ m
4Concentration; Seeing through wavelength with the center is the concentration of the filtering channel inverting CO of 4.63 μ m; Seeing through wavelength with the center is the concentration of the filtering channel inverting NO of 5.21 μ m; Seeing through wavelength with the center is the filtering channel inverting NO of 6.25 μ m
2Concentration; Seeing through wavelength with the center is the filtering channel inverting CO of 4.84 μ m
2Concentration, or the like.
The present invention utilizes the interference of steam filtering channel correction steam to 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 the steam interference function to other object gas component, revises the interference of steam to multicomponent gas to be measured, improves the detection sensitivity and the accuracy of system.
The present invention can simulate the response function of object gas component X at each target filtering channel by feed a certain object gas component X of variable concentrations in sample cell.
The present invention is by feeding 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) or the like.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 or the like.
The present invention can simulate the response function of object gas component X at each target filtering channel by feed a certain object gas component X of variable concentrations in sample cell.For example: the SO that feeds 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) or the like.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 cross interference size of filtering channel; A
20(X) can quantitative test SO
2To NO
2The cross interference size of filtering channel; A
30(X) can quantitative test SO
2Cross interference size to the NO filtering channel; A
40(X) can quantitative test SO
2To cross interference size of CO filtering channel or the like.In like manner can quantitatively obtain other object gas 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
Or the like.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
Or the like.
Among the present invention, because the cross interference more complicated between the object gas component, may all there be interference between any two, 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 three component object gas cross interference, 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 three kinds of object gas SO respectively
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
2Cross interference correction during the on-line analysis simultaneously of component gas such as O.
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) cross interference between revise goal gas; (4) concentration of inverting object gas.
With object gas NO is 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 or the like, finish this step and obtain the drift correction measured value.
Second step [formula (2)]: the FZ here is producer's correction term, is in absolute zero gas (dry and do not contain infrared absorption pollutant) the bar value of acquisition down.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, the object gas difference, UZ is also different, and different occasion, the different measuring time, all might be different, promptly UZ is affected by environment very big, carry out scene zero calibration all might be different at every turn, finish this step and can revise the influence 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, finish the cross interference between this step energy revise goal gas, obtain disturbing correction measured value, the i.e. pure absorbance of each object gas.
The 4th step [formula (4)]: utilize NO will disturb the concentration of revised pure absorbance inverting for gas at the response function of NO filtering channel.
Claims (4)
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 to sample cell to sample cell by a plurality of target filtering channels 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) wherein a kind of object gas component of multicomponent gas of feeding variable concentrations in sample cell, the detection light signal that receives by photo-detector obtains the response function of wherein a kind of object gas component of multicomponent gas in each target filtering channel, 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, feed 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 the total absorbance of each object gas component in the multicomponent gas respectively;
(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) total absorbance of each object gas component is revised to eliminate the system drifting error in the multicomponent gas that respectively step (2) obtained of the system drifting correction measured value that obtains by step (2), 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 except that steam the total absorbance of each object gas component revise, disturb to eliminate steam, the interference function of multicomponent gas each the object gas component except that steam that obtains by step (3) offsets in the multicomponent gas after steam disturbs except that steam the total absorbance of each object gas component and revises, to eliminate the cross interference between each object gas component, obtain the pure absorbance of each target components gas in the multicomponent gas at last;
(5) the response function inverting in each comfortable each target filtering channel of the pure absorbance of each object gas component in the multicomponent gas that obtains according to step (4), and each object gas component of multicomponent gas obtains each object gas component concentrations in the multicomponent gas.
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 magnitude of voltage respectively to.
4. the interference correction of Multi-Component Gas Analyzing according to claim 1 and retrieving concentration method, it is characterized in that: in the described step (3), when eliminating the cross interference between each object gas component, set up the pure absorbance that to eliminate the object gas component of cross interference, the object gas component of palpus elimination cross interference is eliminated the total absorbance after steam disturbs, equation except that steam between the interference function of other object gas components: the object gas component that must eliminate cross interference is eliminated the pure absorbance+interference function of other object gas components except that steam of the object gas component of the total absorbance=palpus elimination cross interference after steam disturbs, with the different equations simultaneousnesses that must eliminate the object gas component of the cross interference disturbance equation group that comes from different backgrounds and possess different abilities, by finding the solution the pure absorbance that polynary disturbance equation group obtains each object gas component in the multicomponent gas.
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