CN112098365B - Multi-spectral line gas absorption spectrum line type fitting measurement method based on orthogonal decomposition - Google Patents
Multi-spectral line gas absorption spectrum line type fitting measurement method based on orthogonal decomposition Download PDFInfo
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- G01N21/39—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using tunable lasers
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Abstract
The invention discloses a multispectral gas absorption spectrum linear fitting measurement method based on orthogonal decomposition, which comprises the steps of firstly selecting a characteristic spectral line range of target gas, and measuring to obtain an absorption linear range; secondly, the measured absorption line type is subjected to orthogonal decomposition, and a low-order term below n-order (n is usually more than 2) is removed to obtain a line type phi related to the optical wave frequency v M (v); screening and removing spectral lines with weaker line intensity in the range of the selected characteristic spectral line from the spectral database; initial values of gas concentration Xabs and temperature T are given, theoretical line shapes of the screened spectral lines are calculated, and the same orthogonal decomposition processing is carried out to obtain a line shape phi S (v); using Xabs and T as variables and a theoretical absorption line phi' S (v) gas-absorbing Linear Φ' M And (v) carrying out least square fitting, and iteratively updating Xabs and T until a convergence condition is met, and outputting concentration and temperature. The invention reduces the spectral line screening standard, accelerates the calculation speed of multispectral fitting, and increases the application range of the TDLAS measurement method.
Description
The technical field is as follows:
the invention relates to a multispectral gas absorption spectrum line type fitting measurement method based on orthogonal decomposition.
Background art:
the tunable diode laser can generate laser with narrow line width, and the output wavelength and the power of the tunable diode laser linearly change along with the injection current. When the injection current of the diode laser is in sawtooth wave tuning, the laser power of the laser wavelength output in sawtooth wave can be obtained. The laser wavelength is repetitively scanned over a selected absorption line range of the target gas to obtain an absorption profile of the absorption line.
The TDLAS temperature measurement is based on selecting proper absorption molecules and absorption spectrum line pairs. Under different application environments, spectral lines need to be selected for actual measured objects, the traditional TDLAS temperature measurement line selection criterion is strict, and the basic line selection experience criterion has the following points:
(1) The two spectral lines need to be sufficiently absorbed within a selected temperature range;
(2) Both lines should not be disturbed by absorption of neighboring lines;
(3) The comprehensive absorption area ratio of the two spectral lines is a monotonous function related to the temperature, the intensities of the two spectral lines are similar, and the two spectral lines have different variation trends along with the change of the temperature T;
(4) The two spectral lines have enough energy difference of low-state energy level to ensure enough good temperature sensitivity;
the traditional double-spectral-line TDLAS measuring method leads the ratio of the line intensity to be a sensitive function of the temperature through two absorption spectral lines of target gas, and the temperature calculation formula is as follows
Where h is Planck's constant, k is Boltzmann's constant, c is the speed of light, E 1 And E 2 Low state energy levels, S, of two spectral lines, respectively 1 And S 2 Strong lines, T, of two spectral lines respectively 0 For reference temperature, R = a 1 /A 2 Integral absorption area A for two lines 1 And A 2 After obtaining the temperature T, the gas concentration is calculated according to the following formula
Wherein, P is pressure intensity, L is measuring path length, and v is optical wave frequency. In actual line selection, it is often difficult to select a spectral line that completely meets the above line selection standard because of the existence of interference spectral lines, and the interference spectral lines affect the calculation of the gas integral absorbance ratio R (T), thereby causing measurement errors and limiting the development and popularization of the TDLAS technology.
In order to solve the problem of interference spectral line, the measured absorption line can be iteratively fitted by using a theoretical absorption line to obtain the temperature and the concentration of the gas. However, when fitting a multispectral line, the line shape of each spectral line needs to be recalculated in each iterative parameter updating process, the calculated amount is large, and the real-time performance cannot be guaranteed. During fitting, the calculation speed can be improved by removing the interference peak of the calculated theoretical line type, but too much interference peak is removed, so that the residual error between the theoretical line type and the actually measured line type is too large, and the fitting precision is reduced.
The invention content is as follows:
the invention provides a multispectral gas absorption spectrum line type fitting measurement method based on orthogonal decomposition, which is used for solving the problems of narrow application range and low calculation speed of a gas detection method based on the traditional double-spectral-line TDLAS technology, expanding the application range of TDLAS and accelerating the calculation speed.
The technical scheme adopted by the invention is as follows:
the multispectral gas absorption spectrum line type fitting measurement method based on orthogonal decomposition comprises the following steps:
1) Selecting a plurality of characteristic absorption spectral lines of the target gas and combining the characteristic absorption spectral lines into two groups of spectral line clusters, wherein the total number of the selected spectral lines is N;
2) Measurement of absorption line type Φ 'of selected line Range target gas with TDLAS method' M (v), obtaining parameters of each characteristic absorption spectral line in the two groups of spectral line clusters through a HITEMP spectral database;
3) Removing the spectral lines with the line intensity lower than the strongest spectral line intensity by one order of magnitude from the N selected spectral lines, wherein the number of the remaining spectral lines is Q;
4) Giving an initial value T of the target gas temperature guess Initial value of concentration Xabs guess Inquiring a HITEMP spectral database and calculating theoretical absorption line type phi of Q spectral lines' S (ν)；
5) Orthogonal decomposition is respectively carried out on the gas absorption line type obtained in the step 2) and the theoretical absorption line type obtained in the step 4), and low order terms with the same order are removed to obtain a corrected measurement line type phi M (v) and the modified theoretical Linear form Φ S (ν)；
6) Using the modified theoretical absorption line form phi S (v) for the corrected measurement line form phi M (v) iterative fittingAnd synthesizing to obtain the concentration and the temperature of the target gas.
Furthermore, a spectral line cluster consisting of a plurality of spectral lines is used as a characteristic spectral line, and high-precision measurement can be performed when more interference spectral lines exist near the main characteristic spectral line, so that the line selection standard can be reduced, and the application range of the TDLAS technology is expanded.
Further, the integrated absorption area a of the main spectral lines in the two sets of spectral line clusters used for temperature measurement have different correlations with the gas temperature T.
Furthermore, spectral lines with weak partial lines are removed from the theoretical line for fitting the measurement line, so as to improve the fitting speed, and the number of removed weak spectral lines is appropriate, so that the requirement on measurement accuracy can be met.
Further, orthogonal decomposition is carried out on the measurement absorption line type and the theoretical absorption line type of the gas, and low-order terms with the same order are removed, so that residual errors between the theoretical line type and the measurement line type caused by the fact that the strong and weak spectral lines are removed are reduced, and parameter measurement accuracy is guaranteed.
Further, obtaining parameters of each characteristic absorption spectrum line in two groups of spectrum line clusters through the HITEMP spectrum database comprises the following steps: the method comprises the steps of line intensity at a reference temperature, low-state energy level, line intensity, self broadening, air broadening and temperature dependence coefficient at various temperatures and concentrations, and the line type of a spectral line can be obtained by combining measurement path length according to database parameters.
The invention has the following beneficial effects:
1) The measuring method for the multi-spectral line gas absorption spectrum line type fast fitting based on the orthogonal decomposition can reduce the spectral line selection standard and enlarge the application range of the TDLAS technology;
2) The measuring method based on the orthogonal decomposition for the linear fast fitting of the multi-spectral-line gas absorption spectrum eliminates absorption spectral lines with weak line intensity, and improves the calculation efficiency;
3) The measuring method for the multispectral gas absorption spectrum line type fast fitting based on the orthogonal decomposition adopts the orthogonal decomposition treatment, reduces the residual error between a theoretical line type and a measuring line type caused by the fact that absorption lines with weak line intensity are removed, improves the calculation efficiency and ensures the measuring precision.
Description of the drawings:
FIG. 1 is a diagram of a measurement system architecture of the present invention;
in the figure, 1-industrial personal computer, 2-DA card, 3-laser controller, 4-laser, 5-laser, 6-laser controller, 7-wavelength division multiplexer, 8-single mode fiber, 9-transmitting end, 10-gas to be measured, 11-receiving end, 12-multimode fiber, 13-photoelectric detector and 14-AD card;
FIG. 2 is a graph of absorption profiles within selected ranges of the present invention;
FIG. 3 is a graph of integrated absorption area ratio versus temperature for a spectral line cluster used to measure temperature in accordance with the present invention;
FIG. 4 is a flow chart of the algorithm of the present invention;
FIG. 5 is an absorption line fit without orthogonal decomposition processing;
FIG. 6 shows the fitting of the absorption line by the orthogonal decomposition process in the present invention.
The specific implementation mode is as follows:
the invention will be further described with reference to the accompanying drawings.
In order to achieve the technical purpose, the invention provides a multiline gas absorption spectrum line-type fitting measurement method based on orthogonal decomposition, which comprises the following steps:
1) The absorption line of the selected gas is a combination of a plurality of lines;
2) Orthogonal decomposition is carried out on the gas absorption line type, and low-order terms are removed;
3) Spectral lines with line intensities one order of magnitude lower than the line intensity of the strongest spectral line are removed before least squares fitting of the absorption line profile.
The present invention will be described in detail with reference to specific embodiments.
1) Determining an environment to be tested: determining the gas to be detected, and determining the optical path length L, the variation range of the gas concentration X and the variation range of the gas temperature T. For example, H2O is used as a target gas, the optical path length L =650cm, the volume concentration of the gas is 8% -12%, and the gas temperature variation range is 800K-2000K;
2) A measurement system is built, as shown in figure 1, an industrial personal computer 1 generates a modulation signal, an analog signal is output to laser controllers 3 and 6 through a dual-channel DA card 2, tunable semiconductor lasers 4 and 5 are driven to emit light, the ranges of 1544nm +/-0.1 nm and 1556nm +/-0.1 nm are scanned alternately, two spectral ranges are combined by a wavelength division multiplexer 7, the combined beam is transmitted to a transmitting end 9 through a single-mode optical fiber 8, penetrates through gas to be measured 10 to be received by a receiving end 11, is transmitted to a photoelectric detector 13 through a multimode optical fiber 12 to be converted into an electric signal, the electric signal is collected by an AD board card 14 to be a digital signal, the digital signal is processed by the industrial personal computer 1, and the spectral absorption line type is calculated.
3) Selecting a characteristic spectrum line cluster: according to the HITEMP spectral database, two clusters of characteristic spectra of H2O at 6476.4cm-1 (1544 nm) and 6423.5cm-1 (1556 nm), respectively, were selected, and their absorption profiles at 1300K and 11% concentration are shown in FIG. 2a and FIG. 2b, respectively. There are a number of H2O absorption lines within the spectrum, 6515 lines in fig. 2a and 9554 lines in fig. 2 b.
4) Relationship of absorbance ratio of spectral line cluster to temperature: for the spectral line clusters used for temperature measurement, the comprehensive absorption area ratio or peak ratio of the two spectral line clusters should be a monotonic function with respect to temperature and the absorption intensities of the two spectral lines in the environment to be measured should be similar and have different relationships with temperature changes (the ratio value has a monotonic relationship with temperature). FIG. 3 shows the trend of the integrated absorption area ratio of two spectral line clusters with temperature, and the absorbance ratio is monotonous with temperature.
5) And (5) orthogonal decomposition processing. For the measured absorption line type Φ' M (v) performing Gram-Schmidt orthogonal decomposition, and removing low-order terms.
The absorption line profile obtained by measurement is represented by the absorption line profile phi of a plurality of spectral lines' M,j Composition of
In the above formula, j represents the j-th spectral line, N is the total number of spectral lines, and ν is the optical wave frequency.
To be measuredAbsorbing linear Φ' M (v) based on orthogonal basis
Subscript i corresponds to the ith sample point. Wherein D k Is an orthogonal radical, a k Is an expansion coefficient of order k, defined as
Where I is the total number of sampling points, orthogonal basis D k The first and second construction methods of (1) are as follows
D 0 ＝1
D 1 ＝ν i -α 0 ；
The orthogonal base of k order is obtained by the following recursion formula
D k+1 ＝(ν-α k )D k -β k D k-1 ；
Wherein the recurrence coefficient alpha k And beta k Is defined as
The absorption line after the low-order term is removed is expressed as
Where n represents the highest order to be removed.
6) Non-linear least squares fit of the absorption line. The method comprises the following steps:
(a) Initial values of gas concentration Xabs and temperature T of iterative fitting are given;
(b) Querying a HITEMP database to obtain parameters of each spectral line in a spectral line cluster;
(c) Within respective pair of rangesTwo spectral line clusters are screened, and the extraction line intensity is 10 -24 calculating theoretical absorption line types of spectral lines above cm & lt-1 & gt/(mol & ltcm & gt & lt-2 & gt), (1544 nm band is reduced from 9554 spectral lines to 17 spectral lines, and 1556nm band is reduced from 6515 spectral lines to 1 spectral line);
(d) Performing orthogonal decomposition treatment on the theoretical absorption line type as the measurement line type;
(e) And finally, performing iterative fitting on the measurement line type by using the line type to obtain the concentration and the temperature value of the gas.
The linear fitting algorithm flow is shown in fig. 4.
To illustrate the necessity of orthogonal decomposition after discarding a part of the weaker spectral lines to improve the calculation efficiency, the fitting results without orthogonal decomposition and after orthogonal decomposition are compared as follows. The results of screening for strong dominant lines but performing iterative fitting without performing step (d) schmitt orthogonal decomposition are shown in fig. 5. The fit yielded a temperature of 1367K with a relative error of 5.1%, a concentration of 12.5% and a relative error of 13.6%. The fitting situation after the high-order schmitt orthogonal decomposition processing of the present invention is shown in fig. 6. The fitting residual error after the orthogonal decomposition correction becomes small, the temperature obtained by fitting is 1305K, the relative error is 0.38%, the concentration is 10.4%, the relative error is 5.5%, the relative error of temperature measurement is one order of magnitude smaller than that of uncorrected measurement, and the error of concentration measurement is 40% of that of uncorrected measurement.
Therefore, the measurement method based on the orthogonal decomposition multiline gas absorption spectrum line type fast fitting is feasible. Compared with the traditional method for detecting gas by using the TDLAS technology, the method has the advantages that the spectral line selection standard is low, the applicable spectral line range is widened, the difficulty in building the TDLAS measuring system is reduced, different application environments can be flexibly handled, the measuring timeliness is improved, and the application range of the TDLAS technology is effectively expanded.
The above-described embodiments should not be construed as limiting the scope of the invention. The key to the invention is the gas temperature, concentration based on a line fit of the multiline absorption spectra, and the technical details involved therein. Any modification made to the present invention is within the scope of the present invention without departing from the spirit or scope of the present invention.
The foregoing is illustrative of the preferred embodiments of the present invention and it will be appreciated by those skilled in the art that changes may be made in this embodiment without departing from the principles of the invention, the scope of which is defined by the appended claims.
Claims (4)
1. The multispectral gas absorption spectrum line type fitting measurement method based on orthogonal decomposition is characterized by comprising the following steps of: the method comprises the following steps:
1) Selecting a plurality of characteristic absorption spectral lines of the target gas and combining the characteristic absorption spectral lines into two groups of spectral line clusters, wherein the total number of the selected spectral lines is N;
2) Measuring absorption line type phi 'of target gas with TDLAS method' M (v), obtaining parameters of each characteristic absorption spectral line in the two groups of spectral line clusters through a HITEMP spectral database;
3) Removing the spectral lines with the line intensity lower than the strongest spectral line intensity by one order of magnitude from the N selected spectral lines, wherein the number of the remaining spectral lines is Q;
4) Giving an initial value T of the target gas temperature guess Initial value of concentration Xabs guess Inquiring a HITEMP spectral database and calculating theoretical absorption line type phi of Q spectral lines' S (ν)；
5) Respectively carrying out orthogonal decomposition on the gas absorption line type obtained in the step 2) and the theoretical absorption line type obtained in the step 4), and removing low-order terms with the same order number to obtain a corrected measurement line type phi M (v) and the modified theoretical line form Φ S (ν)；
6) Using the modified theoretical absorption line form phi S (v) for the corrected measurement line form phi M And (v) carrying out iterative fitting to obtain the concentration and the temperature of the target gas.
2. The method of line-fitting measurement of an orthogonal decomposition based multiline gas absorption spectrum as claimed in claim 1, wherein: to the measured absorption line type Φ' M (v) as Gram-SPerforming orthogonal decomposition on chmidt, and removing low-order terms;
the obtained absorption line type is measured as an absorption line type phi 'consisting of a plurality of lines' M,j Consists of the following components:
in the formula, j represents the j spectral line, N is the total number of spectral lines, and v is the light wave frequency;
measured absorption line type Φ' M (v) based on orthogonal basis the following expansion is made:
the index i corresponds to the ith sample point, where D k Is an orthogonal radical, a k Is an expansion coefficient of order k, and is defined as:
where I is the total number of sampling points, orthogonal basis D k The first and second construction methods of (1) are as follows:
D 0 ＝1
D 1 ＝ν i -α 0 ；
the orthogonal base of k order is obtained by the following recursion formula:
D k+1 ＝(ν-α k )D k -β k D k-1 ；
wherein the recurrence coefficient alpha k And beta k Is defined as:
the absorption line after the lower order terms are removed is expressed as:
wherein n represents the highest order to be removed;
to theoretical absorption line type phi' S (v) carrying out the same Gram-Schmidt orthogonal decomposition, and removing low-order terms to obtain the modified theoretical absorption line type phi S (ν)。
3. The method of claim 1, wherein the method comprises: integral absorption area A of two selected groups of spectral line clusters 1 、A 2 The ratio R of (A) to (B) is a monotonic function of the gas temperature T.
4. The method of claim 1, wherein the method comprises: obtaining parameters of each characteristic absorption spectral line in two groups of spectral line clusters through a HITEMP spectral database comprises the following steps: line intensity at reference temperature, low-state energy level at various temperatures and concentrations, line intensity, self-broadening, air broadening and temperature dependence coefficient.
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