JP2003035662A - Quantitative analysis calibration method - Google Patents

Abstract

(57) [Problem] To quantify a predetermined substance in a mixed substance by calibrating a noise component. SOLUTION: This is a quantitative analysis calibration method for calculating a noise component amount in a calibration step and calculating a concentration of a predetermined substance in a mixed substance, wherein the calibration step collects a zero spectrum and a standard spectrum, and Calculate the transmittance based on the predetermined concentration and the ideal extinction coefficient to obtain the noise component amount, change the predetermined wavelength to another predetermined wavelength, repeat the same process, accumulate the noise component amount of each wavelength, In the normal measurement step, the measurement spectrum of the mixed substance is collected, the amount of noise component is subtracted from the measurement spectrum and the zero spectrum, the absorbance is calculated, the same processing is repeated by changing the predetermined wavelength to another predetermined wavelength, and the other processing is repeated. The absorbance at a predetermined wavelength is calculated, the absorbance at each wavelength is integrated, and the concentration of the predetermined substance in the mixed substance is calculated based on a previously determined calibration curve.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a quantitative analysis and calibration method for quantifying a predetermined substance in a mixed substance.

[0002]

2. Description of the Related Art Generally, when quantitatively analyzing a substance using an absorption spectrum, the concentration and the absorbance are proportional to each other according to Lambert-Beer's law. Is measured to obtain each absorbance, a calibration curve is created from each predetermined concentration and each absorbance, and in the case of a substance whose concentration is unknown, the absorbance is measured and applied to the calibration curve for quantification.

The wavelength 210 in actual gas absorption analysis
19 shows an example of a calibration curve of SO ₂ in nm, the calibration curve is shown in FIG.
As shown in, the slope of the calibration curve is saturated in the high-concentration portion in the horizontal direction, and the Lambert-Beer law is not obeyed.

It is considered that one of the causes of not complying with the Lambert-Beer's law is due to a noise component. There is stray light noise in which unwanted stray light enters the detector in the noise component, and as shown in FIG. In the case of a spectroscopic analysis example that does not use a detector, the stray light 1 is generated by the light source 2 such as reflected light from the housing, scattered light, etc., and enters the detector 4 without passing through the sample 3 to affect the measurement. I'm giving. Further, as shown in FIG. 21, when the spectroscope 7 is provided on the rear side of the sample 6, the stray light 8 is generated by the scattering in the spectroscope 7 from the light source 9, and the stray light 8 is detected separately from the light of the target wavelength. 10
It gets in and affects the measurement. Here, FIG.
In FIG. 0, in FIG. 21, 5 and 11 are optical paths, and 12 is a diffraction grating.

Therefore, when a calibration curve is used in quantitative analysis, only a narrow portion on a straight line is used or various methods of dividing the calibration curve range are adopted.

[0006]

However, in a mixed substance such as a mixed gas, a noise component is also present, and the absorption spectrum of another substance overlaps with the absorption spectrum of the predetermined substance. There is a problem that it is not possible to measure only the spectrum, and it is not possible to measure the concentration of the predetermined substance contained in the mixed substance.

The present invention has been made in view of the above-mentioned circumstances, and an object thereof is to provide a quantitative analysis calibration method for calibrating a noise component to quantify a predetermined substance in a mixed substance.

[0008]

According to a first aspect of the present invention, a noise component amount Pm (d) which changes with the passage of time is calculated in a calibration step, and a predetermined substance is selected from a mixed substance whose composition ratio is unknown. A quantitative analysis calibration method for calculating a concentration by a normal measurement step, wherein the calibration step collects a zero spectrum Pz (d) of zero concentration of a standard substance and a standard spectrum Pr (d) of a predetermined concentration for calibration. As the wavelength setting step, the processing wavelength of each of the received light spectra Pz (d) and Pr (d) is set to a predetermined wavelength, and the standard spectrum Pr is set.
The transmittance Trs (d) is calculated from the predetermined concentration of (d) and an ideal extinction coefficient without a noise component, which is obtained in advance, and the noise component amount Pm (d) is calculated.

## EQU00004 ## Pm (d) = (Pr (d) -Trs (d) .P
z (d)) / (1-Trs (d)), and the same process is repeated by changing the predetermined wavelength to another predetermined wavelength and returning the processing procedure to the calibration wavelength setting step, thereby repeating another predetermined wavelength. The noise component amount Pm (d) is calculated and the noise component amounts of the respective wavelengths are integrated. In the normal measurement step, a measurement spectrum is collected from a mixed substance whose composition ratio is unknown, and each measurement wavelength setting step is performed. The processing wavelength of the received spectrum is set to a predetermined wavelength, and the noise component amount Pm is calculated from the measurement spectrum and the zero spectrum Pz (d).
(D) is subtracted to calculate the absorbance, and the same procedure is repeated by changing the predetermined wavelength to another predetermined wavelength and returning the processing procedure to the measurement wavelength setting step to calculate the absorbance of another predetermined wavelength. Then, the absorbance of each wavelength is accumulated, and the concentration of the predetermined substance in the mixed substance is calculated from the calibration curve obtained from the mixed substance in advance.

According to a second aspect of the present invention, when the concentration of a predetermined substance is calculated from a mixed substance whose composition ratio is unknown and the concentration of the next predetermined substance is continuously calculated, the concentration of the previous predetermined substance is calculated. If the time interval from the calculation to the calculation of the concentration of the next predetermined substance has passed the predetermined time, the processing procedure is returned to the calibration step, and if the time interval is before the predetermined time has passed, The quantitative analysis calibration method according to claim 1, wherein the processing procedure is returned to the normal measurement stage.

According to a third aspect of the present invention, each received spectrum from zero concentration of a single substance to each predetermined concentration is sampled, and a processing wavelength of each received spectrum is set to a predetermined wavelength as a wavelength setting step for a single substance. As a noise component amount setting step, the noise component is temporarily set to a light-receiving spectrum of zero density or an arbitrary temporary noise component amount smaller than a light-receiving spectrum of a predetermined density, and the temporary noise component amount is set to a light-receiving spectrum of zero density and a predetermined density. It is assumed that the absorbance at each specified concentration is calculated by subtracting it from the received light spectrum, and that the relationship between each specified concentration and the absorption follows a straight line.

## EQU00005 ## Y = aX + b a: Slope b: From the intercept, the concentration is substituted for X and the absorbance is substituted for Y to obtain the correlation coefficient by the linear regression method, and then the temporary noise component amount is changed to another temporary noise component amount. The same procedure is repeated by returning the processing procedure to the noise component amount setting step to obtain another correlation coefficient, and by selecting the largest one from the plurality of correlation coefficients in each temporary noise component amount, the selection is performed. The slope corresponding to the correlation coefficient determined is determined as the absorption coefficient of the predetermined wavelength and the amount of noise component is determined, and the predetermined wavelength is changed to another predetermined wavelength to change the processing procedure to the single substance wavelength setting step. By returning, the same processing is repeated to determine the extinction coefficient and the noise component amount of other predetermined wavelengths respectively, and the extinction coefficient of each wavelength and the noise component amount of each wavelength included in the received spectrum of a single substance are integrated. Claim The present invention relates to the quantitative analysis calibration method described in 1 or 2.

According to a fourth aspect of the present invention, each received light spectrum from zero concentration of a single substance to each predetermined concentration is sampled, and a processing wavelength of each received light spectrum is set to a predetermined wavelength as a wavelength setting step for a single substance. As a noise component amount setting step, the noise component is temporarily set to a light-receiving spectrum of zero density or an arbitrary temporary noise component amount smaller than a light-receiving spectrum of a predetermined density, and the temporary noise component amount is set to a light-receiving spectrum of zero density and a predetermined density. It is assumed that the absorbance at each specified concentration is calculated by subtracting it from the received light spectrum, and that the relationship between each specified concentration and the absorption follows a straight line.

[Formula 6] Y = aX + b a: Slope b: From the intercept, the concentration is substituted for X and the absorbance is substituted for Y to obtain the intercept by the linear regression method, and then the temporary noise component amount is changed to another temporary noise component amount for processing. The same processing is repeated by returning the procedure to the noise component amount setting step to obtain another intercept, and by selecting the intercept closest to zero from the plurality of intercepts in each provisional noise component amount, the selected intercept is obtained. Similar processing is performed by determining the corresponding slope as the absorption coefficient of a predetermined wavelength and determining the amount of noise component, and further changing the predetermined wavelength to another predetermined wavelength and returning the processing procedure to the wavelength setting step for the single substance. 3. The absorption coefficient of another predetermined wavelength and the amount of noise component are respectively determined by repeating the above, and the absorption coefficient of each wavelength and the amount of noise component of each wavelength contained in the received spectrum of a single substance are integrated. Quantitative analysis calibration method of
It is related to.

According to a fifth aspect of the present invention, a light-receiving spectrum of a mixed substance having a zero concentration and a plurality of light-receiving spectra having different composition ratios are sampled, and a processing wavelength of each light-receiving spectrum is set to a predetermined wavelength as a wavelength setting step for the mixed substance. Calculate the absorbance of the predetermined wavelength at each composition ratio by subtracting the noise component amount of the predetermined wavelength calculated in advance from a single substance from the reception spectrum of zero concentration and the reception spectrum of each composition ratio. Is changed to another predetermined wavelength and the same procedure is repeated by returning the treatment procedure to the wavelength setting step for the mixed substance to calculate the absorbance at each other predetermined wavelength at each composition ratio, and the absorbance at each wavelength and The calibration curve for quantitative analysis according to claim 1, 2, 3 or 4, wherein a calibration curve of a predetermined substance in a mixed substance is created by performing a multivariate analysis using data of each composition ratio. , It is those related to.

As described above, according to the first aspect, the composition ratio is unknown by calibrating the noise component amount which changes with the passage of time in the calibration stage and using the calibrated noise component amount and the calibration curve prepared in advance. Since the concentration of the predetermined substance is calculated from the mixed substance, it is possible to easily calculate the concentration of the predetermined substance in the mixed substance without recreating a calibration curve even when the amount of noise components changes. .

According to the second aspect, in continuously calculating the concentration of the predetermined substance in the mixed substance, from the time when the concentration of the previous predetermined substance is calculated to the time when the concentration of the next predetermined substance is calculated. Since the processing procedure is changed according to the passage of time, the amount of noise components that changes with the passage of time is calibrated according to the passage of time, and as a result, continuous analysis for continuously measuring the concentration of a substance can be performed reliably and accurately. It can be carried out.

According to the third or fourth aspect, the optimum one is selected from a plurality of correlation coefficients or a plurality of intercepts calculated by the linear regression method via the amount of the temporary noise component, and the optimum wavelength of a single substance is selected. Since the absorption coefficient and the noise component amount are obtained, and the same processing is performed by changing the predetermined wavelength, the absorption coefficient and the noise component amount at other predetermined wavelengths are obtained, and the absorption coefficient and the noise component amount at each wavelength are integrated. It is possible to accurately obtain the absorption coefficient and the amount of noise component of each wavelength in one substance.

According to the present invention, the absorbance at each composition ratio is calculated by removing the noise component amount from the mixed substance by using the noise component amount of each wavelength calculated from a single substance, and using each data. Since the data such as the absorbance of the predetermined substance in the mixed substance is calculated by performing the multivariate analysis by using the multivariate analysis, it is possible to create a plurality of calibration curves for the predetermined substance at each wavelength. Further, since the amount of noise components is removed from the received light spectrum, it is possible to correct a calibration curve saturated at high concentration and create a highly accurate calibration curve with high reproducibility.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the drawings.

1 to 4 show a flow of an embodiment for carrying out the quantitative analysis / calibration method of the present invention, and A, B, C and D show connection points of the respective flows.

When carrying out the quantitative analysis calibration method of the present invention, there are a step of obtaining a noise component amount and an extinction coefficient, a stage of creating a calibration curve, and a calibration stage of calibrating a noise component amount which changes with the passage of time. , The step of calculating the concentration of a predetermined substance from a mixed substance whose mixture composition ratio is unknown.

The step of obtaining an ideal extinction coefficient free from noise components will be described. First, as in the case of creating a general calibration curve, when the concentration of a single substance (single gas) is zero,
And the concentrations are n1, n2, n3 ... (at least 3 or more)
The light-receiving spectrum P (d) (light-receiving intensity, light-receiving area) when the value is changed to is measured.

Next, after measuring a plurality of received light spectra P (d), the initial wavelength d is set as a single substance wavelength processing step so as to select a wavelength for processing each received light spectrum.

Here, the measured light reception spectrum of each wavelength contains stray light noise of a noise component,

(7) P (d) = Ps (d) + Pm (d) P (d): Measured received light spectrum (measured spectrum) Ps (d): received light spectrum of substance Pm (d): Stray light noise received spectrum Becomes

Therefore, in general, an expression for obtaining the absorbance at each wavelength,

## EQU8 ## A (d) = log (Pz (d) / P (d)) A (d): Absorbance Pz (d): Zero spectrum (reception spectrum when the concentration of the substance is zero) P (d): From the measured received spectrum (measured spectrum), subtract the received spectrum of stray light noise,

## EQU9 ## As (d) = log ((Pz (d) -nPm
(D)) / (P (d) -nPm (d))) As (d): corrected absorbance Pz (d): zero spectrum (light-receiving spectrum when the concentration of the substance is zero) P (d): measured Light reception spectrum (measurement spectrum) nPm (d): Temporary stray light noise is set as a noise component amount setting step so as to quantify the noise component of stray light noise by transforming it into a light reception spectrum of temporary stray light noise (temporary noise component amount). A noise component amount (temporary stray light) nPm (d) is provisionally set.

Subsequently, the temporary noise component amount nPm (d) is
It is confirmed that the received light spectrum Pz (d) of zero density is smaller than the received light spectrum P (d) of a predetermined density, and the temporary noise component amount nPm (d) is temporarily set to zero with respect to [Equation 9]. Value, each predetermined concentration at the initial wavelength d (n
1, n2, n3 ...) and the measured value of the zero spectrum (received spectrum) Pz (d) at zero density at the initial wavelength d are substituted,
The absorbance As (d) corresponding to each predetermined concentration is calculated.

The relationship between each calculated absorbance and each predetermined concentration is represented by the Lambert-Beer equation.

(10) A = αn A: Absorbance α: extinction coefficient n: concentration According to, a linear calibration curve is obtained, so

[Formula 11] Y = aX + b a: slope b: in the equation of intercept, X is a value of each predetermined concentration (n1, n2, n3 ...),
The calculated value of each absorbance As (d) is substituted for Y and processed by a linear regression method such as the least square method to obtain the correlation coefficient r (R ² ), the intercept b, and the slope a.

Here, the processing by the linear regression method is shown in [Table 1].
In the linear regression method, a plurality of sets (at least three sets or more) of the collected and calculated concentration X and absorbance Y are considered as K.

[0027]

[Table 1]

The covariance Sxy of X and Y is

[Equation 12] Sxy = (1 / k) Σxy−avg_x × avg_y At this time,

(13) a = Sxy / Sxx

B = avg_y−Sxy × avg_y / Sxx

Further, the square R ² of the correlation coefficient r is

[Equation 15] R ² = Sxy ² / (Sxx · Syy), and when the calculated value of r (R ² ) is the largest (close to 1), a plurality of pairs of concentration X and absorbance Y are obtained. Judge that it is located on a straight line. Further, when r (R ² ) becomes the largest, b = 0 (closest to zero), so b may be used as a reference. In the linear regression method, when nPm that minimizes the sum of squares of the errors is obtained, R ² does not always become the maximum, and b = 0 does not hold, so that it cannot be applied.

After obtaining the correlation coefficient r, the intercept b, and the slope a when the provisional noise component amount nPm is zero by such a linear regression method, after the slope a, at least the correlation coefficient r and the intercept b are obtained. One is temporarily stored.

Next, the zero temporary noise component amount nPm (d)
To the noise component amount setting step, the noise component is temporarily set to another temporary noise component amount nPm (d) by adding a predetermined increase amount ΔnPm to It is confirmed that the component amount nPm (d) is smaller than the light-receiving spectrum (zero spectrum) Pz (d) of zero concentration or the light-receiving spectrum (measurement spectrum) P (d) of a predetermined concentration.

After confirmation, firstly the absorbance As (d)
In the same manner as the processing for obtaining the above, for [Equation 9], a temporary setting value of other temporary noise component amount nPm (d) and a received light spectrum of each predetermined density (n1, n2, n3 ...) At the initial wavelength d. The absorbance As (d) corresponding to each predetermined concentration at the initial wavelength d is calculated by substituting the measured value of P (d) and the measured value of the zero spectrum Pz of zero concentration at the initial wavelength d, respectively, and Similar to the above-described process of calculating the correlation coefficient and the like by the linear regression method, another correlation coefficient r, another intercept b, and another slope a in another temporary noise component amount nPm (d) are obtained, and similarly. Temporarily store.

Next, another temporary noise component amount nPm (d)
To the noise component amount setting step by adding a predetermined increase amount ΔnPm to
Pm (d) is temporarily set and the same process is repeated to obtain another correlation coefficient r, another intercept b, and another slope a for another temporary noise component amount nPm (d), and similarly temporarily store them. .

As described above, in the process of gradually increasing the increase amount ΔnPm to the temporary noise component amount nPm (d), a plurality of slopes a at the initial wavelength d, a plurality of correlation coefficients r and the intercept b at the initial wavelength d are obtained. It is what is accumulated.

Further, the increasing amount of temporary noise component nPm
The process is stopped when (d) exceeds the received light spectrum (zero spectrum) Pz (d) of zero concentration or the received light spectrum (measured spectrum) P (d) of a predetermined concentration. Here, the processing may be stopped when the accumulated number of the correlation coefficient r or the accumulated number of the intercept b exceeds a predetermined value.

After the processing is stopped, each temporary noise component amount nP
Correlation coefficient r from among a plurality of correlation coefficients r in m (d)
Is selected, the one having the largest (closest to 1) is selected, and the one having the intercept b closest to zero is selected from the plurality of intercepts b in each temporary noise component amount nPm (d). Here, when selecting the correlation coefficient r and the intercept b, either the correlation coefficient r or the intercept b may be processed. Further, when the one having the largest correlation coefficient r is selected, the maximum value of R ² is obtained, and it can be obtained by the differential method or the hill climbing method. In addition, ΔnP is set only for the section near the maximum value so that the point that becomes the maximum is searched in detail.
You may make m small. Furthermore, the correlation coefficient r and the intercept b
In the case of selecting, the correlation coefficient r and the intercept b in the predetermined temporary noise component amount nPm (d) are calculated without accumulating a large number of the correlation coefficient r and the intercept b, and are temporarily stored before. It is also possible to compare the correlation coefficient r and the intercept b, and always leave the one having the largest correlation coefficient r and the one having the intercept b closest to zero.

Next, from the information of at least one of the selected correlation coefficient r and intercept b, the actual noise component amount Pm (d)
And the corresponding slope a calculated by the linear regression method are determined, and the determined slope a is used as the absolute absorption coefficient α at the initial wavelength d.

Actual noise component amount Pm at initial wavelength d
After obtaining (d), a predetermined wavelength width Δd is added to the initial wavelength d.
Is set to another predetermined wavelength d, and another predetermined wavelength d is set.
Is within the specified range, and as shown in Fig. 1,
By returning the processing procedure to the single substance wavelength setting stage,
Below, the stray light noise is calculated as the temporary noise component amount (temporary stray light) nPm.
Similar processing such as provisional setting in (d) is performed, and the correlation coefficient r
And the intercept b, the actual noise component amount Pm (d) at another predetermined wavelength d is determined, and the corresponding slope a calculated by the linear regression method is determined. The absolute absorption coefficient α at the predetermined wavelength d is set.

In this way, by gradually adding the predetermined wavelength width Δd to the predetermined wavelength d and performing the same processing, the actual noise component amount Pm (d) and the absolute absorption coefficient α at each wavelength are integrated. When the increasing predetermined wavelength d exceeds a predetermined range, the processing is stopped and the absolute absorption coefficient spectrum at each wavelength is obtained.

Actual noise component amount Pm at each wavelength
After the determination of (d), the process proceeds to the step of creating a calibration curve, and the step of creating the calibration curve is as shown in FIG. 2 when the concentration of the mixed substance (mixed gas) Pz (d) is zero, and A plurality of light receiving spectra (light receiving intensity, light receiving area) P (d) when the composition ratio (concentration ratio) of each component is changed is measured.
Here, the mixed substance (mixed gas) to be measured may or may not contain a single substance (single gas).

Next, each received spectrum Pz (d), P
The initial wavelength d is set as the wavelength processing step for the mixed substance so as to select the wavelength for processing (d), and it is confirmed that the initial wavelength d is within the predetermined range. Subsequently, the noise component amount Pm (d) in the case of the initial wavelength d is selected and prepared from the actual noise component amount Pm (d) at each wavelength obtained in the previous step, and the following [Formula 16] is satisfied. The value of the noise component amount Pm (d) at the initial wavelength d, the measured value of the received light spectrum P (d) of each composition ratio at the initial wavelength d, and the zero spectrum (received light spectrum) P at zero concentration at the initial wavelength d.
The absorbance As (d) of the mixed substance at each composition ratio (concentration) is calculated by substituting the measured values of z (d).

[0042]

## EQU16 ## As (d) = log ((Pz (d) -Pm
(D)) / (P (d) -Pm (d))) As (d): modified absorbance Pz (d) of the mixed substance: zero spectrum of the mixed substance (light-receiving spectrum when the concentration of the substance is zero) P (D): Measured light-receiving spectrum of the mixed substance (measurement spectrum) Pm (d): Actual light-receiving spectrum of stray light noise calculated from a single substance (actual noise component amount)

Here, the measurement of a single substance and a mixed substance is
By using the same measuring device, the noise component amount of each wavelength contained in the single substance and the noise component amount of each wavelength contained in the mixed substance are substantially the same. The measurement interval between the measurement of the absorption spectrum of a single substance and the measurement of the absorption spectrum of a mixed substance is the time during which the amount of noise components does not change.

After calculating the absorbance As (d) at the initial wavelength d, a predetermined wavelength width Δd is added to the initial wavelength d to set another predetermined wavelength d, and the processing procedure is mixed as shown in FIG. After returning to the wavelength setting step for the substance, the same process is performed thereafter, and the absorbance As (d) at another predetermined wavelength d at each composition ratio is obtained.
Ask for.

As described above, by gradually adding the predetermined wavelength width Δd to the predetermined wavelength d and performing the same process, the absorbance As (d) of each composition ratio at each wavelength is accumulated, and the increasing predetermined wavelength d is increased. Processing is stopped when the specified range is exceeded,
Multivariate analysis is performed using the data such as the absorbance As (d) and each composition ratio.

The multivariate analysis will be described below.
Multivariate analysis includes multiple regression analysis, principal component regression analysis, PLS,
There are CLS, neural network, etc.
(Partial Least Squares) An example of using the calculation theory of the model will be described.

(PLS model calculation theory) X is an explanatory variable and y is an objective variable.

[0048]

[Equation 17]

In the case of the concentration estimation model based on the absorbance spectrum waveform analysis, x (n, d) in [Equation 17] is
Absorbance at wavelength d and measurement number n, y (n)
Is the concentration when the measurement number is n. N is the number of measurements (the number of samples), and D is the number of wavelength divisions (the number of explanatory variables).

In the PLS method, the explanatory variable X and the objective variable y are obtained by the two basic equations [Equation 18] and [Equation 19].

[0051]

X = TP ^T + E T: Latent variable P: Loading E: Residual of explanatory variable X Superscript T: Transposed matrix

[0052]

Y = Tq + f q: coefficient f: residual of the objective variable y

Further, the latent variable T, the loading P and the coefficient q are shown as [Equation 20], [Equation 21] and [Equation 22].

[0054]

[Equation 20] t (n, a): a component th measurement number n of latent variables A: Number of component (a range of 1~N selectable) t _a: latent variable vector of a component th latent variables T

[0055]

[Equation 21] p (a, d): Loading of the wavelength d of the a-component A: Number of components (selectable within the range of 1 to N) p _a : Loading vector of the a-component of the loading P

[0056]

[Equation 22] q = (q (1), q (2), q (3), ...,
q (a), ... Q (A)) q _a = q (a) q (a): Coefficient of the a-th component.

Here, the features of the model are represented by the top 6
It is a component for the second time, and more than that reduces the prediction error. The optimum number of components A is determined by performing cross variation.

Next, in the PLS method, the information of the explanatory variable X is not directly used for modeling the objective variable y, but a part of the information of the explanatory variable X is converted into a latent constant t and the latent constant t.
Is used to model the objective variable y.

[0059] (potential constant t) t _a, if a is a linear combination of the explanatory variables X, represented by [Expression 23].

[0060]

[Mathematical formula-see original document] t _a = Xw _a w _a is a weight vector, which is expressed as [Equation 24].

[0061]

[Equation 24] w (d, a): Weighting coefficient of the wavelength d of the a-th component

(Calculation of the First Component) Next, the case where there is one component (a = 1) will be described. When there is one component a, [Equation 18] and [Equation 19] are converted into [Equation 25] ], [Equation 2
6].

[0063]

[Expression 25] X = t ₁ p ₁ ^T + E

[0064]

Y = t ₁ q ₁ + f From [Equation 23], the latent constant t is transformed into [Equation 27].

[0065]

[Equation 27] If the norm of w is set to 1, [Equation 28] is obtained.

[0066]

[Equation 28]

Further, the PLS model is to increase the correlation between the objective variable y and the latent constant t and at the same time increase the variance of t. The condition that satisfies this is that the objective variable y of [Equation 29] and the latent constant t This is the point where the covariance S of the constant t is maximized.

[0068]

(29) S = y ^T t

Here, the condition that maximizes S under the constraint condition that the norm of w is 1 is obtained as shown in [Equation 30] using Lagrange's undetermined multiplier method.

[0070]

[Equation 30]

Since the function G is a function of the variable w, G is replaced by w
Partial differentiation is performed on (d, 1) to obtain [Formula 31] and [Formula 3].
2] is obtained.

[0072]

[Equation 31]

[0073]

[Equation 32] Multiplying both sides of this [Equation 32] by w (d, 1), [Equation 3]
3].

[0074]

[Expression 33] Further, the sum of d is obtained as [Equation 34].

[0075]

[Equation 34]

Here, from the constraint condition of ‖w ₁ ‖ = 0, [Equation 35] is obtained.

[0077]

[Equation 35]

The left side of [Equation 31] is S = y in [Equation 29].
Since it is the definition of ^T t, 2μ is the value of y ^T t. Therefore, the maximum value of w that maximizes S = y ^T t is [Equation 36]
Given in.

[0079]

[Equation 36] Since the norm of w ₁ is 1, w is [Equation 37].

[0080]

W ₁ = X ^T y / ‖X ^T y‖ where the latent variable t is obtained by [Formula 38].

[0081]

(38) t ₁ = Xw ₁

The loading vector p of [Equation 25]
₁ is obtained by [Equation 39] so that the sum of squares of the elements of the residual E of the explanatory variable X is minimized.

[0083]

P ₁ = X ^T t ₁ / t ₁ ^T t ₁

The coefficient q _a of [Equation 26] is calculated by [Equation 40] from the condition so that the sum of squares of the elements of the residual vector f of the objective variable y is minimized.

[0085]

Q ₁ = y ^T t ₁ / t ₁ ^T t ₁

(Calculation after Second Component) The model formula of the second component is expressed by [Formula 41] and [Formula 42].

[0087]

X = t ₁ p ₁ ^T + t ₂ p ₂ ^T + E

[0088]

Y = t ₁ q ₁ + t ₂ q ₂ + f

Here, in modeling with one component, t ₁ p ₁ ^{T of} [Formula 41] of X is used, and t ₁ q _{1 of} y is used.
Was used for the explanation, the remaining information is [Numerical equation 43],
It can be replaced with [Equation 44].

[0090]

X _new = X−t ₁ p ₁ ^T

[0091]

Y _new = y−t ₁ q ₁

Using X _new and y _new , [Formula 41],
[Formula 42] becomes [Formula 45] and [Formula 46].

[0093]

X _new = t ₂ p ₂ ^T + E

[0094]

Y _new = t ₂ q ₂ + f

This is except that the component number is increased by one.
This is the same formula as [Formula 25] and [Formula 26].

Therefore, similarly to the first component, t ₂ , p ₂ , q
You can ask for ₂ .

By repeating this loop, the third and subsequent components can be calculated.

(Calculation of Regression Vector) The model formula in which the necessary number of components is repeated A times is [Equation 47], [Equation 48]
Can be written as

[0099]

X = TP ^T = t ₁ p ₁ ^T + ... + t _a p _a ^T + ... + t _A p _A ^T

[0100]

Y = Tq = t ₁ q ₁ + ... + t _a q _a + ... + t _a q _a

The latent variable t in [Equation 48] is t in [Equation 23].
Substituting ₁ = Xw ₁ , the model equation estimated is
9].

[0102]

Y = Xw ₁ q ₁ + (X−t ₁ p ₁ ^T ) w ₂ q ₂ + ...

Y = Xw ₁ q ₁ + Xw ₂ q ₂ −t ₁ p ₁ ^T w ₂ q ₂ + ...

In this [Equation 50], t ₁ = Xw in [Equation 23]
Substituting ₁ and putting together in X gives [Equation 51].

[0104]

[Number 51] _{y = X (w 1 q 1} + w 2 q 2 -w 1 p 1 T w 2 q 2 ...)

Here, a certain vector to be explained, as in [Equation 52]

[Outer 1] For the objective variable

[Outside 2] Is converted into a model formula for estimating.

[0106]

[Equation 52]

In [Equation 52], b is called a regression vector and is represented by [Equation 53].

[0108]

[Equation 53]

The regression vector b is calculated from [Equation 51] to [Equation 5]
4] is required.

[0110]

B = W (P ^T W) ^-1

The above PLS algorithm is summarized in FIG.

From the beginning of the calculation by the PLS method,
The minute is set to a = 1 to obtain the first component, and then [Formula 37]
The weight vector w of the first component described in_aTo calculate w_a
The latent variable t of [Equation 37] is calculated based on
Loading vector P_aAnd calculate the value of [Equation 40]
Number q_aIs calculated to obtain the loading vector P_aClerk
Number q_aTo the second component described in [Formula 43] and [Formula 44]
The model is set and the component a is incremented as a = a + 1
And whether or not it is necessary to calculate the next component in step 1.
Judge, and if necessary (Yes), that is, the second component
Weight vector w _aReturn to and repeat the same operation
After that, set the next component and increment
However, in step 1, the required number of components are calculated and not required.
When (No), the regression vector b described in [Equation 54] is
Calculate and finish.

When the multivariate analysis is completed, data such as the absorbance and composition ratio (concentration) of the predetermined substance contained in the mixed substance can be calculated, and a plurality of calibration curves at each wavelength of the predetermined substance can be prepared. .

Next, the calibration step for calibrating the noise component amount after starting the calibration curve after starting the calibration curve will be explained. As shown in FIG. 3, the calibration step is a zero spectrum Pz (d) of zero concentration. And a standard spectrum Pr (d) having a predetermined concentration nr of a standard single substance are sampled and measured. The standard single substance used here is the minimum requirement that the absorption spectrum does not overlap with the absorption spectrum of the predetermined substance for which the concentration is to be determined within a certain range, and that it is a stable substance.

Next, after measuring the zero spectrum Pz (d) and the standard spectrum Pr (d), as a calibration wavelength processing step, a wavelength for processing each of the received light spectra Pz (d) and Pr (d) is selected. The initial wavelength d is set, and the ideal absorption coefficient α (d) and the predetermined concentration nr of the standard spectrum Pr (d) at the initial wavelength d without the noise component obtained in the previous step are set.

[Mathematical formula-see original document] Trs (d) = 10- [ ^{alpha] (d) * nr} Trs (d): Substituted into the transmittance, the transmittance Trs does not include the noise component amount of stray light.
Calculate (d).

Here, the transmittance Trs (d) is the zero spectrum Pz (d) and the standard spectrum Pr at zero density.
By subtracting the unknown noise component amount Pm (d) from (d),

(56) Trs (d) = (Pr (d) -Pm (d))
Since the relational expression of / (Pz (d) -Pm (d)) is established,

(57) Trs (d) (Pz (d) -Pm (d)) =
Pr (d) -Pm (d)

(58) Pm (d) = (Pr (d) -Trs (d) ·
Pz (d)) / (1-Trs (d)), the calculated value of the transmittance Trs (d) that does not include the noise component amount of stray light and the zero spectrum Pz (0) of zero density with respect to [Equation 58]. d) Measured value and standard spectrum Pr
By substituting the measured values of (d) respectively, the noise component amount Pm (d) that has changed due to the passage of a predetermined time or the like is obtained,
Calibrate.

After the noise component amount Pm (d) at the initial wavelength d is calibrated, a predetermined wavelength width Δd is added to the initial wavelength d to set another predetermined wavelength d, and as shown in FIG. Is returned to the calibration wavelength setting stage, and the same processing is performed thereafter to calibrate the noise component amount Pm (d) at another predetermined wavelength d.

As described above, by gradually adding the predetermined wavelength width Δd to the predetermined wavelength d and performing the same processing, the calibrated noise component amount Pm (d) at each wavelength is integrated to increase the predetermined wavelength d. The processing is stopped at the time when the predetermined range is exceeded, and the process shifts to the normal measurement stage.

The normal measurement step will be described. As shown in FIG. 4, the measurement spectrum P of the mixed substance whose composition ratio is unknown is shown.
(D) is sampled and measured. Here, the composition of the mixed substance may be different in composition ratio, but it is necessary that the composition is substantially the same as the composition of the mixed substance for which the calibration curve is prepared.

After the measurement spectrum P (d) is measured, the initial wavelength d is set as the measurement wavelength processing step so that the wavelengths for processing the respective light reception spectra P (d) and Pz (d) are set, and the composition ratio is set. By subtracting the calibrated noise component amount Pm (d) from the measured spectrum P (d) and the zero spectrum Pz (d) of the mixed substance whose

As (d) = log ((Pz (d) −Pm
(D)) / (P-Pm (d))) As (d): A calibrated absorbance formula is created, and the calculated value of the calibrated noise component amount Pm (d) is zero with respect to [Equation 59]. The calibrated absorbance As (d) at the initial wavelength d is calculated by substituting the measured value of the spectrum Pz (d) and the measured value of the measured spectrum P, respectively.

Calibrated absorbance As (d) at initial wavelength d
After calculating, the predetermined wavelength width Δd is added to the initial wavelength d to set another predetermined wavelength d, and the processing procedure is returned to the measurement wavelength setting step as shown in FIG. Then, the calibrated absorbance As (d) at another predetermined wavelength d is calculated.

As described above, the calibrated absorbance As (d) at each wavelength is accumulated by gradually adding the predetermined wavelength width Δd to the predetermined wavelength d and performing the same process, and the increasing predetermined wavelength d is set to the predetermined value. When the concentration exceeds the range, the treatment is stopped, and the concentration curve of the predetermined substance is calculated from the mixed substance whose composition ratio is unknown by using the previously obtained calibration curve.

Here, the process of calculating the concentration n of the predetermined substance in the mixed substance by the calibration curve will be described. The concentration n of the predetermined substance is the regression vector b shown in [Equation 54] as a calibration curve.
Thus, the calibrated absorbance As (d) at each wavelength can be obtained by the following [Equation 60] as in [Equation 52].

[0124]

[Equation 60]

That is, as shown in the following [Equation 61], the absorption number of the wavelength division number D and the wavelength d corresponding thereto is calculated from the regression vector b and calculated to calculate a predetermined substance from the mixed substance whose composition ratio is unknown. The concentration n of can be calculated.

[0126]

[Equation 61]

After obtaining the concentration n of the predetermined substance from the measured spectrum P (d) of the mixed substance, a step of calculating a concentration of the predetermined substance by sampling a new mixed substance whose composition ratio is unknown as a continuous analysis By continuously monitoring the elapsed time from the time when the concentration of the previous predetermined substance is calculated to the time when the concentration of the next predetermined substance is calculated, as shown in FIGS. If a predetermined time that causes a change in the component amount Pm (d) has passed, the processing procedure is returned to the calibration stage,
If a predetermined time before the change in the noise component amount Pm (d) occurs, the processing procedure is returned to the normal measurement stage. Furthermore, the same processing procedure is repeated to calculate the concentration of the next measurement sample,
After that, the same processing is continued until there are no unknown measurement samples. Here, the predetermined time during which the noise component amount Pm (d) changes varies depending on the type of substance and the like, and is set appropriately.

Hereinafter, various processes in the process of calculating the concentration of a predetermined substance from a mixed substance of which the composition is unknown will be actually shown, and the temporary noise component amount nPm (d), the correlation coefficient R ² , the intercept b, etc. will be obtained. In the above example, by setting the predetermined wavelength d to 210 nm, the provisional noise component amount nPm (d) is nPm,
The noise component amount Pm (d) is Pm, and the zero spectrum Pz
(D) is Pz, and received light spectrum (measurement spectrum) P
(D) is shown as P, respectively.

(Embodiment 1) The case of changing the temporary noise component amount nPm of stray light in SO ₂ will be described with reference to a calibration curve. As shown in FIG. 6, when the temporary noise component amount nPm is changed, the calibration curve is changed. It is clear that the slope of rises and the calibration curve becomes substantially linear with a certain value of the temporary noise component amount nPm. Further, when the relationship between the temporary noise component amount nPm when the temporary noise component amount nPm at this time is changed and the square of the correlation coefficient R ² is shown, as shown in FIG. 7 and FIG. nPm has a maximum at a predetermined position (near 1560). Here, FIG. 8 is an enlarged view of the vicinity of the maximum value in FIG. Furthermore,
Intercept b when the temporary noise component amount nPm at this time is changed
As shown in FIG. 9, b is a predetermined position and b =
It becomes 0. Therefore, when the correlation coefficient R ² is the maximum value and b is zero, the provisional noise component amount nPm becomes the actual noise component amount Pm (actual stray light), and the actual noise component amount P
It is assumed that m is 1560 to 1570, and the slope a corresponding to the extinction coefficient α is 0.0149 at 210 nm. Furthermore, when it is shown how much the noise component amount Pm is included in the measured light receiving spectrum P, as shown in FIG. 10, the zero spectrum Pz and the light receiving spectrum P are obtained at each wavelength.
It is clear that there is a predetermined amount of noise component amount Pm under.

(Embodiment 2) The noise component amount Pm of the actual stray light is adjusted by intentionally adjusting the optical system in the same device.
Using an example in which the difference is changed, as shown in FIG. 11, the calibration curve including the noise component amount Pm shows the noise component amount P of stray light.
The curvature increases and the inclination changes with the size of m. Also, from the calibration curve of FIG. 11, the noise component amount Pm
Is removed, stray light is large (noise component is large) in FIG.
3 stray light (in noise component) and small stray light (small noise component) in FIG. 14, the calibration curve becomes a substantially straight line regardless of the size of stray light (noise component amount) It is clear that also becomes almost constant.

Example 3 A mixed substance (mixed gas) containing SO ₂ was actually processed from 200 nm to 350 nm by adding a predetermined wavelength width Δd to a predetermined wavelength d, and SO ₂ was subjected to multivariate analysis, SO _{2 in} mixed substances
Calculate the data such as absorbance. Here, [Table 2] shows three of each composition ratio (concentration 20 ppm, 60 pp
m, 100 ppm), and each composition ratio has three wavelengths (200.52 nm, 20.77 nm, 20).
1.02 nm) is shown.

[0132]

[Table 2]

As a result, FIG. 15 shows the zero spectrum Pz, the noise component amount Pm, and the received light spectrum (measurement spectrum) P at each wavelength, and FIG. 16 shows the absolute absorption coefficient spectrum at each wavelength. Further, the calibration curve created by the multivariate analysis exists for each wavelength, and the absorbance spectrum before correction shown in FIG. 17 is corrected to the absorbance spectrum after correction shown in FIG. 18 through the calibration step and the measurement step as appropriate. To do.

As described above, by calibrating the noise component amount which changes with the passage of time in the calibration stage and using the calibrated noise component amount and the calibration curve prepared in advance, a predetermined substance from a mixed substance whose composition ratio is unknown is calibrated. Since the concentration is calculated, it is possible to easily calculate the concentration of the predetermined substance in the mixed substance without creating a calibration curve again even when the amount of noise component changes.

In addition, when continuously calculating the concentration of a predetermined substance in a mixed substance, it corresponds to the passage of time from the time when the concentration of the previous predetermined substance is calculated to the time when the concentration of the next predetermined substance is calculated. Since the processing procedure is changed according to the passage of time, the amount of noise component that changes with the passage of time can be calibrated according to the passage of time, and as a result, continuous analysis for continuously measuring the concentration of the substance can be performed reliably and precisely.

Furthermore, an optimum one is selected from a plurality of correlation coefficients or a plurality of intercepts calculated from the linear regression method via the temporary noise component amount, and the absorption coefficient and the noise component amount of a predetermined wavelength in a single substance are selected. Obtain the absorption coefficient and the noise component amount of other predetermined wavelength by changing the predetermined wavelength and performing the same process, and accumulate the absorption coefficient and noise component amount of each wavelength. The coefficient and the amount of noise component can be accurately obtained.

Furthermore, by using the noise component amount of each wavelength calculated from a single substance, the absorbance at each composition ratio is calculated by removing the noise component amount from the mixed substance, and the multivariate analysis is performed using each data. By doing so, the data such as the absorbance of the predetermined substance in the mixed substance is calculated, so that it is possible to create a plurality of calibration curves for each wavelength of the predetermined substance. Here, by using the same measuring device for measuring the single substance and the mixed substance, the amount of noise components of each wavelength contained in the single substance and the amount of noise component of each wavelength contained in the mixed substance become substantially the same. Therefore, the noise component amount of the mixed substance can be removed by the noise component amount of the single substance. Further, since the amount of noise components is removed from the received light spectrum, it is possible to correct a calibration curve saturated at high concentration and create a highly accurate calibration curve with high reproducibility.

The quantitative analysis / calibration method of the present invention is not limited to the above-mentioned embodiment, and it goes without saying that various modifications can be made without departing from the scope of the present invention.

[0139]

As described above, according to the quantitative analysis / calibration method of the present invention, various excellent effects as described below can be obtained.

I) According to claim 1, the composition ratio is unknown by calibrating the noise component amount which changes with the passage of time in the calibration stage and using the calibrated noise component amount and the calibration curve prepared in advance. Since the concentration of the predetermined substance is calculated from the mixed substance, even if the amount of the noise component changes, the concentration of the predetermined substance in the mixed substance can be easily calculated without creating a calibration curve again.

II) According to claim 2, when continuously calculating the concentration of the predetermined substance in the mixed substance, when calculating the concentration of the next predetermined substance from the time when the concentration of the previous predetermined substance is calculated Since the processing procedure is changed according to the passage of time, the amount of noise component that changes with the passage of time is calibrated according to the passage of time, and as a result, continuous analysis that continuously measures the concentration of the substance is ensured. Can be done with precision.

III) According to claim 3 or 4, the optimum one is selected from a plurality of correlation coefficients or a plurality of intercepts calculated from the linear regression method via the amount of temporary noise components, and a predetermined value in a single substance is selected. Since the absorption coefficient and the noise component amount of the wavelength are obtained and the predetermined wavelength is changed and the same processing is performed, the absorption coefficient and the noise component amount of the other predetermined wavelength are obtained, and the absorption coefficient and the noise component amount of each wavelength are integrated. The absorption coefficient and the amount of noise components of each wavelength in a single substance can be accurately obtained.

IV) According to claim 5, the absorbance at each composition ratio is calculated by removing the noise component amount from the mixed substance by using the noise component amount at each wavelength calculated from a single substance, and Since the data such as the absorbance of the predetermined substance in the mixed substance is calculated by performing a multivariate analysis using, it is possible to create a plurality of calibration curves for each wavelength of the predetermined substance. Further, since the amount of noise components is removed from the received light spectrum, it is possible to correct a calibration curve saturated at high concentration and create a highly accurate calibration curve with high reproducibility.

[Brief description of drawings]

FIG. 1 is a flow showing an example of an embodiment for carrying out the quantitative analysis calibration method of the present invention.

FIG. 2 is a continuous flow from FIG.

FIG. 3 is a flowchart showing a calibration step continuously from FIG.

FIG. 4 is a flowchart showing a normal measurement stage continuously from FIG.

FIG. 5 is a diagram showing an algorithm based on multivariate analysis (PLS method).

FIG. 6 is a diagram showing a calibration curve when a temporary noise component amount of stray light is changed in SO ₂ .

7 is a diagram showing a relationship between the amount of temporary noise components and the square value of a correlation coefficient when the amount of temporary noise components is changed in FIG.

8 is an enlarged view showing the vicinity of the maximum value in FIG.

9 is a diagram showing a relation of intercepts when the amount of temporary noise components is changed in FIG.

FIG. 10 is a diagram showing to what extent a measured light reception spectrum includes a noise component amount.

FIG. 11 is a diagram showing an example of a calibration curve when the optical system is intentionally adjusted in the same device to change the actual noise component amount of stray light.

12 is a diagram showing a calibration curve obtained by removing the amount of each noise component from the calibration curve of large stray light (large noise component) in FIG. 11;

13 is a diagram showing a calibration curve when each noise component amount is removed from the calibration curve in stray light (in noise component) of FIG. 11;

14 is a diagram showing a calibration curve when each noise component amount is removed from the calibration curve for small stray light (small noise component) in FIG. 11;

FIG. 15 is a diagram showing a zero spectrum, a noise component amount, and a light reception spectrum (measurement spectrum) at each wavelength.

FIG. 16 is a diagram showing an absolute absorption coefficient spectrum at each wavelength.

FIG. 17 is a diagram showing an absorbance spectrum before correction at each wavelength.

FIG. 18 is a diagram showing an absorbance spectrum after correction at each wavelength.

FIG. 19 is a view showing a conventional calibration curve of SO _{2 having} a wavelength of 210 nm.

FIG. 20 is a schematic diagram showing stray light in the case of non-dispersive spectroscopic analysis.

FIG. 21 is a schematic diagram showing stray light in the case of spectroscopic analysis using a spectroscope.

[Explanation of symbols]

As (d) Absorbance P (d) Light receiving spectrum (measurement spectrum) Pm (d) Actual noise component amount nPm (d) Temporary noise component amount Pr (d) Standard spectrum Pz (d) Zero spectrum Trs (d) Transmittance α (d) extinction coefficient R ² correlation coefficient r correlation coefficient a slope b intercept d predetermined wavelength (initial wavelength) n concentration

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Ken Kobayashi             3-15 Toyosu, Koto-ku, Tokyo Ishikawajima             Harima Heavy Industries Tokyo Engineering Co., Ltd.             In the center (72) Inventor Takehito Yagi             3-15 Toyosu, Koto-ku, Tokyo Ishikawajima             Harima Heavy Industries Tokyo Engineering Co., Ltd.             In the center (72) Inventor Masataka Ohara             2-2-1 Otemachi, Chiyoda-ku, Tokyo Stone             Kawashima Harima Heavy Industries Co., Ltd. F term (reference) 2G059 AA01 BB01 CC06 EE01 FF08                       HH03

Claims (5)

[Claims] 1. A quantitative analysis calibration method for calculating a noise component amount Pm (d) that changes with the passage of time in a calibration step, and for calculating the concentration of a predetermined substance from a mixed substance whose composition ratio is unknown in a normal measurement step. In the calibration step, a zero spectrum Pz (d) of zero concentration of the standard substance and a standard spectrum Pr (d) of a predetermined concentration are sampled, and each received spectrum P is set as a calibration wavelength setting step.
Set the processing wavelengths of z (d) and Pr (d) to predetermined wavelengths,
The transmittance Trs (d) is calculated based on a predetermined concentration of the standard spectrum Pr (d) and an ideal extinction coefficient without a noise component obtained in advance, and the noise component amount Pm (d) is calculated as follows: (D) = (Pr (d) −Trs (d) · Pz (d)) / (1−Trs (d)), the predetermined wavelength is changed to another predetermined wavelength, and the processing procedure is set to the calibration wavelength. By repeating the same processing by returning to the stage, the noise component amount Pm (d) of another predetermined wavelength is calculated and the noise component amount of each wavelength is integrated, and in the normal measurement stage, the composition ratio is unknown. The measurement spectrum is sampled from the substance, the processing wavelength of each received spectrum is set to a predetermined wavelength as a measurement wavelength setting step, and the noise component amount Pm (d) is subtracted from the measurement spectrum and the zero spectrum Pz (d), respectively, to obtain the absorbance. And calculate By repeating the same process by changing the predetermined wavelength to another predetermined wavelength and returning the processing procedure to the measurement wavelength setting step, the absorbances of other predetermined wavelengths are calculated and the absorbances of the respective wavelengths are accumulated, and the mixed substance is prepared in advance. A calibration method for quantitative analysis, characterized in that the concentration of a predetermined substance in a mixed substance is calculated from a calibration curve obtained from. 2. When calculating the concentration of a predetermined substance from a mixed substance of which the composition ratio is unknown and continuously calculating the concentration of the next predetermined substance, after calculating the concentration of the previous predetermined substance, If the time interval until the concentration of the predetermined substance is calculated exceeds the predetermined time, the processing procedure is returned to the calibration step, and if the time interval is before the predetermined time has elapsed, the processing procedure is changed to the normal measurement step. The quantitative analysis calibration method according to claim 1. 3. A light reception spectrum from zero concentration of a single substance to each predetermined concentration is sampled, and a processing wavelength of each light reception spectrum is set to a predetermined wavelength as a wavelength setting step for a single substance, and a noise component amount setting step is performed. As the noise component is temporarily set to a light-receiving spectrum of zero density or an arbitrary temporary noise component amount smaller than the light-receiving spectrum of a predetermined density, and the temporary noise component amount is subtracted from the light-receiving spectrum of zero density and the light-receiving spectrum of a predetermined density, respectively. The absorbance at each given concentration is calculated, and assuming that the relationship between each given concentration and the absorbance follows a straight line, Y = aX + b a: slope b: From the intercept, the concentration is substituted for X and the absorbance is substituted for Y to obtain a phase by linear regression method. The similar process is repeated by obtaining the relation number, then changing the temporary noise component amount to another temporary noise component amount, and returning the processing procedure to the noise component amount setting step. The correlation coefficient of is determined, and by selecting the largest one from the plurality of correlation coefficients in each temporary noise component amount, the slope corresponding to the selected correlation coefficient is determined as the absorption coefficient of the predetermined wavelength and the noise component The amount is determined, the same procedure is repeated by changing the predetermined wavelength to another predetermined wavelength and returning the processing procedure to the wavelength setting step for the single substance, and the absorption coefficient and the noise component amount of the other predetermined wavelength are determined. The quantitative analysis calibration method according to claim 1 or 2, wherein the absorption coefficient of each wavelength and the amount of noise component of each wavelength included in the received light spectrum of a single substance are respectively determined and accumulated. 4. A light receiving spectrum from zero concentration of a single substance to each predetermined concentration is sampled, and a processing wavelength of each light receiving spectrum is set to a predetermined wavelength as a wavelength setting step for a single substance, and a noise component amount setting step is performed. As the noise component is temporarily set to a light-receiving spectrum of zero density or an arbitrary temporary noise component amount smaller than the light-receiving spectrum of a predetermined density, and the temporary noise component amount is subtracted from the light-receiving spectrum of zero density and the light-receiving spectrum of a predetermined density, respectively. The absorbance at each given concentration is calculated, and assuming that the relationship between each given concentration and the absorbance follows a straight line, Y = aX + b a: slope b: From the intercept, the concentration is substituted for X and the absorbance is substituted for Y Then, the temporary noise component amount is changed to another temporary noise component amount, and the processing procedure is returned to the noise component amount setting step to repeat the same processing, Obtain the piece, by selecting the one that is closest to zero from the plurality of intercepts in each temporary noise component amount, determine the slope corresponding to the selected intercept as the absorption coefficient of the predetermined wavelength and determine the noise component amount, Further, by changing the predetermined wavelength to another predetermined wavelength and returning the processing procedure to the single substance wavelength setting step, the same processing is repeated to determine the absorption coefficient and the noise component amount of the other predetermined wavelength, respectively. 3. The quantitative analysis calibration method according to claim 1, wherein the absorption coefficient of each wavelength and the amount of noise components of each wavelength included in the received light spectrum of one substance are integrated. 5. A light-receiving spectrum of a mixed substance having a zero concentration and a plurality of light-receiving spectra having different composition ratios are sampled, and a processing wavelength of each light-receiving spectrum is set to a predetermined wavelength as a wavelength setting step for the mixed substance, and a single wavelength is set beforehand. Calculate the absorbance of the predetermined wavelength at each composition ratio by subtracting the amount of the noise component of the predetermined wavelength calculated from the substance from the received spectrum of zero concentration and the received spectrum of each composition ratio, and the predetermined wavelength to other predetermined wavelength By repeating the same procedure by returning the treatment procedure to the wavelength setting step for the mixed substance, the absorbance at each other predetermined wavelength at each composition ratio is calculated, and the absorbance at each wavelength and the data of each composition ratio are calculated. 5. The quantitative analysis calibration method according to claim 1, 2, 3 or 4, wherein a calibration curve of a predetermined substance in the mixed substance is created by performing multivariate analysis.