CN110031413A - More concentration of metal ions detection methods in a kind of solution - Google Patents
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Abstract
It the invention discloses concentration of metal ions detection methods more in a kind of solution, executes as follows: calculating in solution to be measured the corresponding integral absorptivity of every kind of ion each wavelength in original wavelength section, and construct the target wavelength section of solution to be measured；The standard solution of ion M a kind of is carried out Ratio- derivative as extinction spectrum of the divisor factor to solution to be measured and handles to obtain the Ratio- derivative information of absorbance by the Ratio- derivative information for obtaining solution absorbance to be measured；Then, the concentration of residual ion in solution to be measured is calculated using kalman filter spectrophotometry in target wavelength section, then the densimeter based on residual ion calculates the ion concentration of the ion M as divisor factor.The present invention have speed it is fast, using simple, highly sensitive, do not need to carry out ion pre-separation can then to detect the concentration of more metal ions simultaneously, easily realize automation, detected simultaneously suitable for metal ions more in solution.
Description
Technical field
The invention belongs to the technical fields of quantitative spectrometric detection solution ion concentration, and in particular to more metals in a kind of solution
Ion concentration detection method.
Background technique
Wet zinc smelter industrial wastewater mainly includes a large amount of zinc (Zn) and trace metal ion, such as copper (Cu), cobalt (Co) and
Nickel (Ni), main zinc ion and components concentration are than up to 103, due to the intrinsic toxicity of heavy metal ion, excessive discharge
It can serious polluted water resources and influence human health.Therefore, real-time detection and strict control concentration of metal ions have important meaning
Justice.
At present, it has been proposed that a variety of methods are used for Simultaneous Determination metal ion, such as atomic absorption spectrum, voltammetry, height
Effect liquid phase chromatogram, uv-vis spectra and atomic fluorescence spectrophotometry etc..In these methods, uv-vis spectra is since it is in standard
Superiority in terms of true property, speed is fast and simplicity and cost-effectiveness and be widely used for a long time, become measurement heavy metal from
The important analysis method of one kind of son.
However, traditional uv-vis spectra detection is mainly used for single ion.When being applied to more metal ions, it is necessary to logical
It crosses chemical method and is pre-separated each component, complex steps, and real-time is poor.In order to avoid separating step, make extensively
Multicomponent analysis is carried out with several spectrophotometry.These methods include principal component regression (PCR), difference spectrophotometry, partially
Least square regression (PLSR), derivative spectrophotometry, kalman filter spectrophotometry and multi-wavelength linear regression analysis
(MLRA).But these methods are mainly used for multiple groups segregant similar in analytical concentration.It is molten for wet zinc smelter industrial wastewater
The concentration of main component zinc and trace metal ion is than up to 10 in liquid3, there are serious overlapping and interference in mixture.To mesh
Before until, since the sensitivity of components is lower, and interionic peak overlap seriously and interfere with each other, there are no a kind of detections
Method can synchronize the zinc and components in accurate measurement industrial wastewater.Therefore it urgently finds a kind of towards zinc hydrometallurgy industry
The method of the synchronous detection of more metal ions in waste water solution.
Summary of the invention
The object of the present invention is to provide concentration of metal ions detection methods more in a kind of solution, realize a variety of in solution
The method of the synchronous detection of concentration of metal ions, can accurately measure zinc and components concentration in industrial wastewater.
More concentration of metal ions detection methods, implementation procedure are as follows in a kind of solution provided by the invention:
The corresponding integral absorptivity of every kind of ion each wavelength in original wavelength section is calculated in solution to be measured, and is constructed
The target wavelength section of solution to be measured；
Wherein, the target wavelength section is made of the wavelength points that coefficient R is greater than threshold value, the coefficient R table
Show the ion characteristic information for including at wavelength points, coefficient R is bigger, bigger to the contribution of Kalman filter model；
Obtain the Ratio- derivative information of solution absorbance to be measured；
Wherein, the absorption spectrum of solution to be measured is obtained, and using the standard solution of ion M a kind of as divisor factor to be measured
The extinction spectrum of solution carries out Ratio- derivative and handles to obtain the Ratio- derivative information of absorbance, the absorbance ratio
Spectra Derivative is related to residual ion concentration, unrelated with ion M；
Then, the integral absorptivity of Ratio- derivative, ion based on solution absorbance to be measured and in target wavelength area
The interior concentration that residual ion in solution to be measured is calculated using kalman filter spectrophotometry, then based on the dense of residual ion
Degree is calculated as the ion concentration of the ion M of divisor factor.
The detection while present invention realizes different kinds of ions in solution using the above method, it is so-called while being detected as not needing
Ion is separated to the concentration that also can detecte out all ions.Wherein, the present invention is selected more by correlation coefficient threshold method
The with higher sensitivity range of wavelengths of metal ion, improves modeling accuracy；Secondly, the present invention is carried out using Ratio Spectrum counting backward technique
Overlap peak separation, is typically chosen the ion that is affected to other ions as divisor factor, for example wet zinc smelter industrial wastewater
In then select zinc ion, and then eliminate influence of the zinc ion to other ions, improve computational accuracy；Finally use Kalman
It filters spectrophotometry and eliminates interionic interference, can just check the concentration of different kinds of ions without isolation.
Further preferably, the process for calculating residual ion concentration using kalman filter spectrophotometry is as follows:
A1: initialization concentration vector X (λk), initialization concentration vector estimated valueValue is zero, concentration vector X
(λk) indicate residual ion concentration, λ indicate wavelength, λkIndicate the corresponding wavelength of k-th of wavelength points in target wavelength section；
A2: the ratio light of concentration vector sum concentration vector estimated value, solution absorbance to be measured based on previous wavelength points
Compose derivative, ion integral absorptivity calculate in target wavelength section current wavelength point concentration vector estimated value；
In formula,Indicate wavelength points λ in target wavelength sectionk, previous wavelength points λk-1It is corresponding dense
Spend vector estimated value, X (λk-1) indicate previous wavelength points λ in target wavelength sectionk-1Corresponding concentration vector, K (λk) indicate
Kalman gain, Z (λk) indicate wavelength points λkThe Ratio- derivative of corresponding solution absorbance to be measured, solution absorbance to be measured
Ratio- derivative indicate are as follows: It is solution to be measured in wavelength points λkThe absorbance at place, CM0
For the concentration of the standard solution of ion M,It is ion M in wavelength points λkIntegral absorptivity；HT(λk) it is residual ion in wave
Long point λkIntegral absorptivity derivative ratio matrix H (λk) transposed matrix, i-th of ion is in wavelength points λ in residual ionk's
Integral absorptivity derivative ratio indicates are as follows: It is i-th of ion in residual ion in wavelength points λk's
Integral absorptivity；
A3: the error of previous wavelength points and the concentration vector estimated value of current wavelength point in target wavelength section is calculated
Mean value exports the corresponding concentration vector estimated value of current wavelength point and obtains institute in solution to be measured if being less than default error threshold
State the concentration of residual ion.
Further preferably, any wavelength points λiLocate the Ratio- derivative and residual ion concentration of solution absorbance to be measured
Relational expression is as follows:
In formula, C1,C2...Cn-1Indicate in solution to be measured remaining n-1 ion concentration except deionization M,Indicate that remaining n-1 ion pair should be in wavelength points λ except deionization M in solution to be measurediThe absorbance system at place
Number, n are effects of ion species number to be measured.
From above-mentioned formula it is found that the Ratio- derivative of the absorbance of solution is related with residual ion concentration, but with work
It is unrelated for the ion concentration of divisor factor, and then eliminate the influence as other ions of the ion pair of divisor factor.
Further preferably, the corresponding default error threshold of the error mean of concentration vector estimated value is 10-4。
Further preferably, the process for constructing the target wavelength section of solution to be measured is as follows:
B1: the coefficient R of each wavelength points is calculated using correlation coefficient threshold method；
In formula, RiIndicate wavelength points λ in original wavelength sectioniThe related coefficient at place, yiIndicate by it is identical as solution to be measured from
Subconstiuent, the several groups solution of different ions concentration is in wavelength points λiThe absorbance vector of the absorbance composition at place, ymIndicate extinction
Spend vector yiMiddle absorbance mean value, siIndicate several groups solution described in the integral absorptivity linear fit based on ion in wavelength points
λiThe absorbance vector that the absorbance at place is constituted, wherein one group of solution is in wavelength points λiThe absorbance for locating linear fit is as follows:
In formula,Indicate one group of solution in wavelength points λiLocate the absorbance of linear fit,Indicate solution
Middle n class ion is in wavelength points λiThe integral absorptivity at place, C1,C2...CnRespectively indicate the dense of n class ion in one group of solution
Degree；
B2: the wavelength points building target wavelength section that coefficient R is greater than threshold value is extracted.
Further preferably, the corresponding threshold value of coefficient R is 0.95.
Further preferably, the corresponding absorbance of every kind of ion each wavelength in original wavelength section is calculated in solution to be measured
The process of coefficient is as follows:
D1: acquisition and solution same ion ingredient to be measured, the absorption spectrum of the several groups solution of different ions concentration；
Wherein, integral absorptivity of the same ion under the same wavelength points is unrelated with ion concentration；
D2: every kind of ion each wavelength in original wavelength section is calculated using linear regression method according to langbobier law
Corresponding integral absorptivity；
Wherein, in wavelength points λiLocate concentration, the relationship of integral absorptivity of each ion in the absorbance and solution of solution
It is as follows:
In formula,It indicates in wavelength points λiLocate the absorbance of solution,Indicate that n class ion is in wave in solution
Long point λiThe integral absorptivity at place, C1,C2...CnThe concentration of n class ion in one group of solution is respectively indicated, λ indicates wavelength.
Further preferably, the densimeter based on residual ion calculates the mistake of the ion concentration of the ion M as divisor factor
Journey is as follows:
The absorbance of solution to be measured and the relational expression of ion concentration are obtained according to langbobier law:
In formula,It indicates in wavelength points λiLocate the absorbance of solution,It indicates in solution except deionization M
N-1 class ion is in wavelength points λiThe integral absorptivity at place, C1...Cn-1Respectively indicate the n-1 class in one group of solution except deionization M
The concentration of ion, CMIndicate the concentration of ion M,Indicate ion M in wavelength points λiThe integral absorptivity at place, AdIndicate low frequency
Noise；
Absorption spectrum based on solution to be measured obtains the absorbance of solution, and by the concentration of residual ion and corresponds to absorbance
Coefficient substitutes into the ion concentration that relational expression calculates ion M.
Further preferably, the effects of ion includes zinc ion and trace metal ion, as divisor factor from
Son is zinc ion.
Beneficial effect
The present invention calculates every kind of ion by linear regression method according to the absorbance and concentration relationship of more metal mixed solution
Integral absorptivity；Overlap peak separation also is carried out using Ratio- derivative method, by the way that the standard of ion a kind of in solution is molten
Liquid does divisor factor, eliminates influence of the metal ion to other ions；Secondly, selection is mostly golden by correlation coefficient threshold method
Belong to the higher range of wavelengths of ion-sensitive degree, promotes modeling accuracy；Finally, being eliminated off using kalman filter spectrophotometry
Interference between son can detect the concentration of more metal ions without isolation.More metal ions that the present invention obtains while the side of detection
Method have speed it is fast, using simple, highly sensitive, do not need to carry out ion pre-separation, automation easily realized, suitable for molten
More metal ions detect simultaneously in liquid.
Detailed description of the invention
Fig. 1 is more concentration of metal ions detection method flow diagrams in a kind of solution of the present invention；
Fig. 2 is absorbance curve of 40 groups of metal mixed solution in different wave length；
Fig. 3 is zinc, copper, cobalt, the mixed spectra curve of nickel；
Fig. 4 is the curve of spectrum that zinc ion is eliminated by Ratio- derivative method；
Fig. 5 is that the range of wavelengths of Kalman filtering selects；
Fig. 6 is that Kalman filtering detects copper, cobalt, three metal ion species of nickel simultaneously；
Fig. 7 is the predicted value of zinc and the calibration curve of actual value.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical solution in the embodiment of the present invention is explicitly described, it is clear that described embodiment is the present invention
A part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.Below in conjunction with
The present invention is described further for embodiment.
Referring to Fig. 1, more concentration of metal ions detection methods in a kind of solution disclosed by the embodiments of the present invention, including walk as follows
It is rapid:
S1: according to the absorbance and concentration relationship of more metal mixed solution, every kind of ion is calculated by linear regression method
Integral absorptivity.It implements process such as D1-D2:
D1: acquisition and solution same ion ingredient to be measured, the absorption spectrum of the several groups solution of different ions concentration；Its
In, (number is organized using the absorption spectrum for preparing the metal mixed solution of multiple groups various concentration with design method and measure every group of solution
The present invention to it without specifically limiting, but the requirement of integral absorptivity can be calculated by least meeting).
D2: every kind of ion each wavelength in original wavelength section is calculated using linear regression method according to langbobier law
Corresponding integral absorptivity.Original wavelength section indicates the range of wavelengths of research, for example all band.Wherein, due to metal ion
Absorbance and the relationship of concentration meet langbobier law, in wavelength XiUnder, meet following relationship:
In formula,It indicates in wavelength points λiLocate the absorbance of solution,Indicate that n class ion is in wavelength points in solution
λiThe integral absorptivity at place, C1...CnRespectively indicate the concentration of one group of solution n class ion, AdIndicate low-frequency noise, λ indicates wave
It is long.Assume there is M, N, W in the present embodiment, tetra- metal ion species above-mentioned formula (1) of P then indicates are as follows:
Wherein,Indicate M, N, W, tetra- metal ion species of P are in wavelength points λiThe absorbance at place
Coefficient, CM,CN,CW, CPIndicate the concentration of four metal ion species.
Since the absorbance of mixed solution contains ambient noise, the precision and accuracy of ion detection are seriously affected, is used
The method of derivation eliminates error.Carrying out derivation to formula (1) can obtain:
Since ambient noise is smaller with frequency variation, it can be eliminated, be obtained in wavelength points λ by derivationiLocate the suction of solution
Concentration, the relationship of integral absorptivity of luminosity and ion each in solution are as follows:
Wherein, since integral absorptivity of the same ion under the same wavelength points is unrelated with ion concentration, base
Equation group can be constructed according to the multiple groups solution of different ions concentration in formula (4), can be calculated using linear regression method
The corresponding integral absorptivity of each wavelength in the original wavelength section of every kind of ion.
S2: the absorption spectrum of solution to be measured is obtained, and isolated to be measured using Ratio- derivative method progress overlap peak
The Ratio- derivative information of solution absorbance, wherein eliminate the metal for a kind of standard solution of ion as divisor factor
The influence of the other ions of ion pair.Standard solution is only comprising a kind of ion.
Assuming that selecting the standard solution of ion M as divisor factor (concentration CM0), then formula (4) can change are as follows:
Wherein, due to absorptivity of the same ion under Same Wavelength under different ions concentration be also it is identical, because
ThisFor constant K, therefore, formula (5) be can simplify are as follows:
To formula (6), further derivation obtains the Ratio- derivative of absorbance:
From formula (7) it is found that the Ratio- derivative of solution absorbance is only related with remaining n-1 ion concentration,
Interference of the ion M as divisor factor to other ions is eliminated, the separation of overlap peak is realized.For example, tetra- kinds of M, N, W, P
In metal ion, for the Ratio- derivative of solution absorbance only with N, tri- kinds of ion concentrations of W, P are related.This method of the present invention is normal
For wet zinc smelter industrial wastewater, the concentration of main component zinc and trace metal ion ratio is up to 10 in solution3, deposit in mixture
In serious overlapping and interference, therefore then select zinc ion as the ion of divisor factor, can eliminate zinc ion to trace from
The influence of son.
After the present invention gets the absorption spectrum of solution to be measured, multiple derivation is carried out according to the process in formula (7) and is obtained
The Ratio- derivative information of solution absorbance to be measured.
S3: by correlation coefficient threshold method, the with higher sensitivity range of wavelengths building target wavelength of more metal ions is selected
Section.Its process is as follows:
B1: the coefficient R of each wavelength points is calculated using correlation coefficient threshold method；Wherein, using with solution phase to be measured
Same ion component, the absorption spectrum of the several groups solution of different ions concentration calculate coefficient R (the solution group of each wavelength points
It counts and may be the same or different in step D1, the present invention is to this without specifically limiting).
In formula, RiIndicate wavelength points λ in original wavelength sectioniThe related coefficient at place, yiIndicate by it is identical as solution to be measured from
Subconstiuent, the several groups solution of different ions concentration is in wavelength points λiThe absorbance vector of the absorbance composition at place, for example chooses
The solution of 40 groups of various concentrations is calculated, ymIndicate absorbance vector yiMiddle absorbance mean value, siIndicate the extinction based on ion
Multiple groups solution described in coefficient linear fit is spent in wavelength points λiThe absorbance vector that the absorbance at place is constituted, wherein one group of solution
In wavelength points λiThe absorbance for locating linear fit is as follows:
In formula,Indicate one group of solution in wavelength points λiLocate the absorbance of linear fit,It indicates in solution
N class ion is in wavelength points λiThe integral absorptivity at place, C1,C2...CnRespectively indicate the concentration of n class ion in one group of solution.
B2: the wavelength points building target wavelength section that coefficient R is greater than threshold value is extracted.Coefficient R value is bigger, indicates
The wavelength points are bigger to the contribution of Kalman filter model, on the contrary then poorer.The wavelength points of selection of embodiment of the present invention R > 0.95
Construct target wavelength section, wherein each wavelength points for meeting the requirement are added in target wavelength section, target wavelength section
It is to be made of the wavelength points for meeting the requirement.
It should be noted that the embodiment of the present invention is successively executed according to the step of above-mentioned S1-S3, in other feasible realities
It applies in example, above-mentioned steps S2 actually can be before or after step S1 and S3, and the present invention is to this without specifically limiting.
S4: residual ion in solution to be measured is calculated using kalman filter spectrophotometry in target wavelength section
Concentration, then the densimeter based on residual ion calculate the ion concentration of the ion M as divisor factor.
It interferes with each other and influences each other for components, when causing the additive properties of hybrid ionic and single ion bad,
The algorithm for proposing Kalman's iterative filtering, eliminates interionic influence.Kalman filter spectrophotometry include system mode and
Two models are measured, are expressed as follows:
X(λk)=X (λk-1)+W(λk) (10)
Z(λk)=HT(λk)·X(λk-1)+V(λk) (11)
In the detection of uv-vis spectra multicomponent, λk、λk-1It respectively indicates in target wavelength section k-th, kth -1
The corresponding wavelength of wavelength points.W(λk) indicate system noise, X (λk-1) indicate concentration vector, its expression residual ion in the present invention
Concentration vector, be made of the concentration of residual ion, Z (λk) it is wavelength points λkThe Ratio- derivative of corresponding solution absorbance,
Such asHT(λk) it is residual ion in wavelength points λkIntegral absorptivity derivative ratio matrix H (λk)
Transposed matrix, integral absorptivity derivative ratio matrix H (λk) it is by residual ion in wavelength points λkIntegral absorptivity ratio lead
What number was constituted, i-th of ion is in wavelength points λ in residual ionkIntegral absorptivity derivative ratio indicate are as follows: It is i-th of ion in residual ion in wavelength points λkIntegral absorptivity.V(λk) indicate measurement
Noise.
For above-mentioned two model, the present invention is calculated in target wavelength section using kalman filter spectrophotometry
The process of the concentration of residual ion is as follows in solution to be measured:
A1: initialization concentration vector X (λk), initialization concentration vector estimated valueValue is zero；In addition, also just
Beginningization error covariance matrix P (λk), measurement noise V (λk), value is zero.
A2: the ratio light of concentration vector sum concentration vector estimated value, solution absorbance to be measured based on previous wavelength points
Compose derivative, ion integral absorptivity calculate in target wavelength section current wavelength point concentration vector estimated value；
In formula,Indicate wavelength points λ in target wavelength sectionk, previous wavelength points λk-1It is corresponding dense
Spend vector estimated value, X (λk-1) indicate previous wavelength points λ in target wavelength sectionk-1Corresponding concentration vector, K (λk) indicate
Kalman gain.Wherein, kalman gain K (λk) it is expressed as follows:
K(λk)=P (λk-1)H(λk)[HT(λk)P(λk-1)H(λk)+R(λk)]-1 (13)
Wherein, P (λk-1) indicate error covariance matrix, R (λk) indicate that apparatus measures noise, m indicate the number of iterations, meter
It calculates and more new formula is as follows:
P(λk)=[I-K (λk)HT(λk)]P(λk-1)[I-K(λk)HT(λk)]T+K(λk)R(λk)KT(λk) (15)
Wherein, the V (λ in formula (14)k-1) it is to be obtained according to formula (11), X (λ in formula (11)k-1) value be
Estimated value in iterative process
A3: the error of previous wavelength points and the concentration vector estimated value of current wavelength point in target wavelength section is calculated
Error mean in d (k) exports the corresponding concentration vector of current wavelength point and estimates if error mean is less than default error threshold
Evaluation obtains the concentration of residual ion described in solution to be measured.
Wherein, presetting error threshold value is 10-4If being less than default error threshold 10-4, then iteration ends, output are current
The corresponding concentration vector estimated value of wavelength points obtains the concentration of residual ion.
It obtains except the concentration as the ion of divisor factor after all ion concentrations, the absorbance of solution is only at this time
It is related with the ion M as divisor factor, then the concentration correction curve of ion M will can be constructed according to formula 1 or formula 4,
The concentration for calculating ion M realizes the Concentration Testing of all ions of solution to be measured, does not need to separate ion.
Four kinds of zinc, copper, cobalt, nickel ions are mainly contained in zinc hydrometallurgy industrial wastewater.By choosing test ion
The experimental data when absorbance of type and contrived experiment scheme, acquisition zinc and components changes with concentration, is based on overlapping spectra
Peak separation and more metal ions are detected as target simultaneously, realize towards in zinc hydrometallurgy industrial wastewater more metal ions it is same
When detect.The present invention is specifically described as example, and concrete scheme is implemented as follows:
1. contrived experiment simultaneously obtains data
The characteristics of according to testing requirements and zinc hydrometallurgy industrial wastewater, select EDTA (0.5mol/L) as screening agent；For
Dramatically increase components Zn2+, Cu2+, Co2+, Ni2+Absorbance, select to Zn2+, Cu2+, Co2+, Ni2+The nitrous all to develop the color
Base R salt (0.4%) is used as color developing agent；An important factor for due to pH value and influencing components absorbance, select acetic acid-
Sodium acetate adjusts pH value as buffer.The detectable concentration range of zinc is 10-70mg/L, and the detection of Cu, Co, Ni components are dense
Degree range is 0.2-1.4mg/L, prepares 40 groups of calibration set mixed solutions and 10 groups of verifying collection solution using uniform design.
The following are embodiment test conditions:
Instrument: the general analysis T9 ultraviolet-uisible spectrophotometer in Beijing
Test scope: all band, 350nm~800nm
Will contain various ratios zinc, copper, cobalt, nickel mixed standard solution, 0.5mol/L EDTA solution (1-10ml),
7.5ml buffer solution and 5.00ml colour reagent be placed in 25ml calibration flask in, with deionized water complete constant volume (final pH=
5.5) it, shakes up and stands 5min, measured on T9 ultraviolet specrophotometer.According to formula (1), absorbance curve is established.
Measurement result is as shown in Figure 2 (abscissa indicates that wave-length coverage/nm, ordinate indicate absorbance/Abs).According to not
The absorbance of the lower 40 groups of mixed solutions of co-wavelength and the corresponding relationship of concentration, establish zinc, copper, cobalt, nickel by linear regression method
Absorptivity matrix.
2. eliminating influence of the zinc to components using Derivative ratiospectrum
Measure 7.5ml buffer (acetic acid-sodium acetate), addition concentration is 20mg/L Zn, 0.3mg/L Cu, 0.5mg/L
0.5mol/L EDTA solution 6ml is added in the mixed solution of Co and 0.4mg/L Ni, and 0.4% R salt (5ml) is in the test tube of 25ml
In, it is settled to 25ml with distilled water, 5min is stood, is measured on T9 ultraviolet specrophotometer.
Measurement result is as shown in Figure 3 (abscissa indicates that wave-length coverage/nm, ordinate indicate absorbance/Abs).In waste water
Zinc concentration is significantly larger than the concentration of components, especially the spectral peak of the zinc peak shape of having sheltered nickel completely, and therefore, it is difficult to examine simultaneously
Survey four kinds of ions.
In order to eliminate influence of the zinc to components, we have proposed a kind of overlap peak separation sides of Ratio- derivative
Method, by formula (4)-(6) it is found that the Ratio- derivative of mixed solution absorbance and copper, cobalt, nickel ion concentration is related, complete
At interference of the metallic zinc to other ions is eliminated, the separation of overlap peak is realized.To make the copper of detection, cobalt, nickel can not
It is sheltered by zinc ion, improves the sensitivity of copper cobalt nickel components.Measurement result as shown in figure 4, using 20mg/L zinc standard
Solution can completely eliminate the influence of zinc ion as divisor.
3. selecting the with higher sensitivity range of wavelengths of more metal ions by correlation coefficient threshold method
Fig. 5 is that the range of wavelengths of Kalman filtering selects.The bigger expression wavelength points of the coefficient R value of more metal ions
It is bigger to the contribution of Kalman filter model, it should to select the biggish wavelength of R value as filtering section as far as possible.According to experimental calculation
As a result, in 430-540nm wave-length coverages, R > 0.95 shows at these wavelength, between the absorbance and concentration of hybrid ionic
Linear relationship is preferable.Meanwhile in order to save operation time, meet the real-time of detection, comprehensively consider, select 450-500nm this
Filtering section of the Duan Bochang as Kalman's spectrophotometry.
4. detecting copper, cobalt, nickel ion concentration simultaneously using kalman filter spectrophotometry
It prepares one group and contains 0.6mg/L Ni, the mixed solution of 0.8mg/L Co and 0.9mg/L Cu.True value is horizontal
Line indicates, estimates Cu by Kalman filtering, the iterative process of Co, Ni concentration are as shown in Figure 6.As can be seen that with filter point
Increase, filter value (i.e. estimated concentration) tends towards stability.Since 16 filters, filter value changes very greatly, but
In 17-31 filter region, filter value is stable and can terminate filtering.The final estimated concentration of Cu, Co, Ni are distinguished
It is 0.5929,0.8013 and 0.9278, very close true value.In general, 20-40 can be passed through if correctly selecting filtering area
A filter obtains satisfied result.
5. establish the calibration curve of zinc, zinc is realized, copper, cobalt, nickel detects simultaneously.
40 groups of zinc are configured using uniform design, copper, cobalt, nickel mixed solution is as calibration set, 10 groups of mixed solution conducts
Verifying collection, the detectable concentration range of zinc are 10-70mg/L, Cu, Co, and the detectable concentration range of Ni components is 0.2-1.4mg/
L will contain the zinc of various ratios, copper, cobalt, nickel mixed standard solution, 0.5mol/L EDTA solution (1-10ml), 7.5ml buffering
Solution and 5.00ml colour reagent are placed in 25ml calibration flask, are completed constant volume (final pH=5.5) with deionized water, are shaken up quiet
5min is set, is measured on T9 ultraviolet specrophotometer.
When obtaining the concentration of Cu, Co and Ni in one group of mixed solution by Kalman filtering algorithm.According to Eq. (1),
The absorbance of this four component mixture depends entirely on the concentration of Zn, therefore, can construct the calibration curve of Zn.Fig. 7 is shown
The prediction concentrations value and actual concentrations value of Zn in mixture solution.As can be seen that predicted value is almost consistent with actual value.It is average
Relative deviation is within 5%, completely within the scope of desired value.
The metal mixed solution for containing Zn, Cu, Co and Ni of 10 groups of different proportions is prepared, it is proposed by the present invention for assessing
RSD-KF (ratio composes derivative and Kalman filtering) model.Table 1 shows the prediction result of Zn, Cu, Co and Ni.As shown in Table 1,
The zinc of RSD-KF method prediction, copper, cobalt, the predicted root mean square error of nickel is respectively 0.364,0.082,0.127,0.372, average
Relative deviation is respectively less than 5%.The result shows that the method for the present invention not only simple express delivery, is easy to on-line analysis, meets real-time detection and want
It asks, is suitable for detection while four constituents mixt of peak overlap, will be with a wide range of applications.
Table 1. detects the result of Zn, Cu, Co and Ni simultaneously
| Index | Zn | Cu | Co | Ni |
| Root-mean-square error | 0.364 | 0.082 | 0.127 | 0.372 |
| Mean relative deviation (%) | 3.342 | 3.146 | 2.751 | 3.764 |
It is emphasized that example of the present invention be it is illustrative, without being restrictive, thus the present invention it is unlimited
Example described in specific embodiment, other all obtained according to the technique and scheme of the present invention by those skilled in the art
Embodiment does not depart from present inventive concept and range, and whether modification or replacement, also belong to protection model of the invention
It encloses.
Claims (9)
1. more concentration of metal ions detection methods in a kind of solution, it is characterised in that: implementation procedure is as follows:
The corresponding integral absorptivity of every kind of ion each wavelength in original wavelength section is calculated in solution to be measured, and is constructed to be measured
The target wavelength section of solution；
Wherein, the target wavelength section is made of the wavelength points that coefficient R is greater than threshold value, and the coefficient R indicates wave
The ion characteristic information for including at long point, coefficient R is bigger, bigger to the contribution of Kalman filter model；
Obtain the Ratio- derivative information of solution absorbance to be measured；
Wherein, the absorption spectrum of solution to be measured is obtained, and using the standard solution of ion M a kind of as divisor factor to solution to be measured
Extinction spectrum carry out Ratio- derivative handle to obtain the Ratio- derivative information of absorbance, the absorbance ratio spectrum
Derivative is related to residual ion concentration, unrelated with ion M；
Then, the integral absorptivity of Ratio- derivative, ion based on solution absorbance to be measured and in target wavelength section
The concentration of residual ion in solution to be measured, then the densimeter based on residual ion are calculated using kalman filter spectrophotometry
Calculate the ion concentration of the ion M as divisor factor.
2. according to the method described in claim 1, it is characterized by: calculating residual ion using kalman filter spectrophotometry
The process of concentration is as follows:
A1: initialization concentration vector X (λk), initialization concentration vector estimated valueValue is zero, concentration vector X (λk)
Indicate the concentration of residual ion, λ indicates wavelength, λkIndicate the corresponding wavelength of k-th of wavelength points in target wavelength section；
A2: the Ratio Spectrum of concentration vector sum concentration vector estimated value, solution absorbance to be measured based on previous wavelength points is led
It counts, the concentration vector estimated value of the integral absorptivity of ion calculating current wavelength point in target wavelength section；
In formula,Indicate wavelength points λ in target wavelength sectionk, previous wavelength points λk-1Corresponding concentration arrow
Measure estimated value, X (λk-1) indicate previous wavelength points λ in target wavelength sectionk-1Corresponding concentration vector, K (λk) indicate karr
Graceful gain, Z (λk) indicate wavelength points λkThe Ratio- derivative of corresponding solution absorbance to be measured, the ratio of solution absorbance to be measured
Being worth Spectra Derivative indicates are as follows: It is solution to be measured in wavelength points λkThe absorbance at place, CM0For from
The concentration of the standard solution of sub- M,It is ion M in wavelength points λkIntegral absorptivity；HT(λk) it is residual ion in wavelength points
λkIntegral absorptivity derivative ratio matrix H (λk) transposed matrix, i-th of ion is in wavelength points λ in residual ionkExtinction
Degree coefficient ratio derivative table is shown as: It is i-th of ion in residual ion in wavelength points λkExtinction
Spend coefficient；
A3: it is equal to calculate the error of previous wavelength points and the concentration vector estimated value of current wavelength point in target wavelength section
Value exports the corresponding concentration vector estimated value of current wavelength point and obtains described in solution to be measured if being less than default error threshold
The concentration of residual ion.
3. according to the method described in claim 2, it is characterized by: any wavelength points λiLocate the ratio light of solution absorbance to be measured
It composes derivative and the relational expression of residual ion concentration is as follows:
In formula, C1,C2...Cn-1Indicate in solution to be measured remaining n-1 ion concentration except deionization M,Table
Show that remaining n-1 ion pair should be in wavelength points λ except deionization M in solution to be measurediThe integral absorptivity at place, n are solution to be measured
Intermediate ion species number.
4. according to the method described in claim 2, it is characterized by: the corresponding default mistake of the error mean of concentration vector estimated value
Poor threshold value is 10-4。
5. according to the method described in claim 1, it is characterized by: constructing the process in the target wavelength section of solution to be measured such as
Under:
B1: the coefficient R of each wavelength points is calculated using correlation coefficient threshold method；
In formula, RiIndicate wavelength points λ in original wavelength sectioniThe related coefficient at place, yiIndicate by with solution same ion to be measured at
Point, the several groups solution of different ions concentration is in wavelength points λiThe absorbance vector of the absorbance composition at place, ymIndicate absorbance arrow
Measure yiMiddle absorbance mean value, siIndicate several groups solution described in the integral absorptivity linear fit based on ion in wavelength points λiPlace
Absorbance constitute absorbance vector, wherein one group of solution is in wavelength points λiThe absorbance for locating linear fit is as follows:
In formula,Indicate one group of solution in wavelength points λiLocate the absorbance of linear fit,Indicate n class in solution
Ion is in wavelength points λiThe integral absorptivity at place, C1,C2...CnIndicate the concentration of n class ion in one group of solution, n is ion
Species number；
B2: the wavelength points building target wavelength section that coefficient R is greater than threshold value is extracted.
6. according to the method described in claim 5, it is characterized by: the corresponding threshold value of coefficient R is 0.95.
7. according to the method described in claim 1, it is characterized by: calculating in solution to be measured every kind of ion in original wavelength section
The process of the corresponding integral absorptivity of interior each wavelength is as follows:
D1: acquisition and solution same ion ingredient to be measured, the absorption spectrum of the several groups solution of different ions concentration；
Wherein, integral absorptivity of the same ion under the same wavelength points is unrelated with ion concentration；
D2: every kind of ion each wavelength in original wavelength section is calculated using linear regression method according to langbobier law and is corresponded to
Integral absorptivity；
Wherein, in wavelength points λiConcentration, the relationship of integral absorptivity for locating each ion in the absorbance and solution of solution are as follows:
In formula,It indicates in wavelength points λiLocate the absorbance of solution,Indicate that n class ion is in wavelength points in solution
λiThe integral absorptivity at place, C1,C2...CnIndicate the concentration of n class ion in one group of solution, λ indicates wavelength, and n is ionic species
Number.
8. according to the method described in claim 1, it is characterized by: the densimeter based on residual ion, which calculates, is used as divisor factor
Ion M ion concentration process it is as follows:
The absorbance of solution to be measured and the relational expression of ion concentration are obtained according to langbobier law:
In formula,It indicates in wavelength points λiLocate the absorbance of solution,Indicate the n-1 class in solution except deionization M
Ion is in wavelength points λiThe integral absorptivity at place, C1...Cn-1Respectively indicate the n-1 class ion in one group of solution except deionization M
Concentration, CMIndicate the concentration of ion M,Indicate ion M in wavelength points λiThe integral absorptivity at place, AdIndicate low-frequency noise；
Absorption spectrum based on solution to be measured obtains the absorbance of solution, and by the concentration of residual ion and corresponds to integral absorptivity
Substitute into the ion concentration that relational expression calculates ion M.
9. according to the method described in claim 1, it is characterized by: the effects of ion be zinc ion and trace metal from
Son, the ion as divisor factor are zinc ion.
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