CN108931487A - Masking test system optimization method towards zinc solution components Concentration Testing - Google Patents
Masking test system optimization method towards zinc solution components Concentration Testing Download PDFInfo
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Abstract
The invention discloses a kind of masking test system optimization method towards zinc solution components Concentration Testing, the single goal based on two constraint condition building masking optimal inspection systems.It is operated are as follows: first calculates theory EDTA dosage；Then range is selected according to theoretical EDTA dosage；Then EDTA dosage, color developing agent nitroso-R-salt dosage, influence of the pH value of measurement system to absorption spectrum quality are studied；The optimization constraint condition under two systems: the turnover critical point of EDTA dosage and R salt noiseless wave-length coverage is defined, and establishes fitting function；Then by the fitting function of foundation, it is integrated into the optimal inspection system model of single goal multivariable；It solves；Obtain Optimal Parameters, the test system that the present invention obtains has the wide linearity, low detection limit, selectivity good and highly sensitive, it does not need to carry out zinc electrolyte pre-separation, easily realizes automation, the dosage optimization suitable for high concentration than the screening agent of components Concentration Testing under background.
Description
Technical field
The present invention relates to test system optimisation technique fields, dense towards zinc solution components more particularly, to one kind
Spend the masking test system optimization method of detection.
Background technique
It in hydrometallurgical processes, leaches and contains various metals ion in feed liquid, excessive components not only influence electricity
Current efficiency in solution preocess, and influence deposition zinc surface topography and cathodic polarization, during electrodepositing zinc influence compared with
Big components mainly have copper iron-cobalt-nickel etc., need real-time detection components content thus, accomplish strictly to monitor to flow into be electrolysed
The content of these types of components in the zinc electrolyte of slot.
During more metal ions measure simultaneously, the modeling analysis of each heavy metal ion to be measured is all based on bright Bobi
That law, the absorption spectrum surveyed need to meet stringent linear and additive property.Only when each metal ion to be measured is to be measured dense
When the linearity is good, additive property is good, wavelength available information is more in degree range, the spectral signal of acquisition could be used for high-precision point
Analysis.However, the Zn in zinc electrolyte2+Content be up to 130~170g/L, the mass ratio of zinc and components can reach
107Times or more, thus in severe jamming zinc electrolyte components measurement.For this purpose, appropriate EDTA can be added to Gao Xinjin
The measurements of components is realized in row masking, and the dosage of color developing agent and buffer to the additive properties of more metal ions, absorb
The wavelength available range of curve has strong influence, therefore this patent proposes one kind and is different from generally with certain ion-sensitive
Degree is up to the method for the reagent dosage optimization of target, converts a single goal multivariable for masking test system optimization problem
The problem of Optimization Solution.
Summary of the invention
The non-linear strong, additive property of measured ion is waited for than trace in more metallic ion mixed liquors under background for high concentration
The detection problems such as difference, detection signal overlap, signal masking, the present invention provides one kind towards zinc solution components Concentration Testing
Masking test system optimization method.
Screening agent optimization method provided by the invention, Integral Thought are as follows: first: in high concentration than zinc abstraction leachate
In, first the Zn content accurate calibration in solution is come out, appropriate EDTA masking zinc is then added.In order to make the screening agent being added
EDTA is only preferentially complexed with zinc, without being complexed with other components, so being stablized using trace metal ion concentration and complexing
Constant quantitatively calculates each trace metal element and starts maximum acceptable concentration when being complexed with EDTA, determines as standard theoretical
EDTA additional amount；
Then, in the system, the additional amount and pH value of color developing agent nitroso-R-salt are also to influence each Metal Ions Absorption peak
Principal element.The present invention is provided with the optimization constraint condition under a kind of system: the turnover critical point of EDTA dosage and R salt are without making an uproar
Sound wave-length coverage, contrived experiment simultaneously obtain experimental data.
Then；The optimization of two constraint conditions of application definition, and binding isotherm calculated value, building single goal multivariable is surveyed
System method is tried, which is solved based on fmincon function, finally obtains the optimum amount of optimal inspection system
Value.
Masking test system optimization method of the present invention towards zinc solution components Concentration Testing, which is characterized in that packet
It includes:
S1: in high concentration than first calibrating the Zn content in solution to come in zinc abstraction leachate, EDTA masking is calculated
The theoretical amount of zinc；The theoretical amount of the EDTA masking zinc are as follows: the screening agent EDTA being added only preferentially is complexed with zinc, without
It is complexed with other components；
S2: design is using EDTA dosage, color developing agent nitroso-R-salt dosage, the pH value of measurement system as the experiment of variable；Measurement
Absorbance curve；Define the optimization constraint condition under experimental system are as follows: the turnover critical point of EDTA dosage and R salt noiseless wavelength model
Enclose NWR；
The EDTA dosage turnover critical point is defined as: with being gradually added into for EDTA, gradually increased in additional amount same
When, the absorbance curve of high zinc solution will appear variation；Determine that a certain wave band is observation object；When any in the observation object
One wave number, its absorbance is positive number when EDTA is added in i-th；Its absorbance is negative when EDTA is added in i+1 time；Then define
It is critical indicator that EDTA amount, which is added, in the amount of i addition EDTA to i+1 time；I.e. the optimal addn of EDTA is real just in this section
Existing dosage optimization；
The R salt noiseless wave-length coverage NWR is defined as: with the increase of color developing agent dosage, absorbance curve negative peak
Occurring can be increasingly severe；Color developing agent dosage is continuously increased, and the appearance of interference can be more and more mobile to red wave direction；According to can
R salt noiseless wave-length coverage is defined with the start-stop wavelength points of wave band；
NWR=| λ2-λ1| (3)
Wherein, λ1The starting point of absorption curve, λ can be used in the ultraviolet-visible absorption spectroscopy of 200-800nm for solution2For can
With the terminal of absorption curve；λ1For near shortwave direction, and in divided wave band, when spacing 1nm, previous point and the latter
The variable quantity of the absorbance of point is no more than 0.3 wavelength points；λ2For any point in 610-800nm；The λ2Greater than λ1；
S3: two constraint conditions of application definition, and binding isotherm calculated value construct the optimal inspection of single goal multivariable
System method solves the single-object problem based on fmincon function, finally obtains the optimum amount of optimal inspection system
Value；The single goal are as follows: so that AP value is equal to 0 or is substantially equal to 0；The expression of the AP are as follows:
Wherein A is the true absorbance of mixed solution, AiFor the absorbance of heavy metal ion to be measured in i-th；
The multivariable is successively are as follows: dosage, the color developing agent nitroso-R-salt dosage, the pH value of measurement system of EDTA.
Masking test system optimization method of the present invention towards zinc solution components Concentration Testing；In S1, in high concentration
Than first coming out the Zn content accurate calibration in solution in zinc abstraction leachate, appropriate EDTA masking zinc is then added.In order to make
The screening agent EDTA of addition is only preferentially complexed with zinc, without being complexed with other components, so dense using trace metal ion
Degree and complexing stability constant quantitatively calculate each trace metal element start with EDTA complexing when maximum acceptable concentration, as mark
Accurate theorem opinion EDTA additional amount.When more metal ions coexist, shadow of the reagent to metal ion absorbance in masking test system
Sound has differences, and causes the additive property effect in Ar ion mixing solution bad, to make ion additive property reach satisfactory effect
Fruit must first determine that the relative error between the true absorbance of Ar ion mixing solution and the true absorbance arithmetic adduction of single ion is minimum,
Ion reaches minimum with respect to additive property i.e. at wave crest, then using this minimum value as optimization aim, realizes masking test system
Optimization.
The additional amount of screening agent EDTA influences entire test system very big.Screening agent EDTA additional amount is excessive, will lead to
Components also will be masked, and the detection of components concentration cannot be achieved；Screening agent EDTA additional amount is very few, high zinc interference
It still has, components masking, overlapping are still serious.It, be first before taking zinc electrolyte to be measured to react with the detection architecture
Calculate the additional amount of EDTA, it is ensured that masking is not generated to components while sheltering a large amount of zinc, according to copper, iron, cobalt and nickel
Concentration and stability constant can calculate prevent each trace metal element start and EDTA be complexed when maximum acceptable concentration.
Since EDTA does not have selectivity to metal shadowing, the zinc that the EDTA being added need to be less than in zinc electrolyte contains
Amount, just can guarantee that high zinc is largely sheltered and do not shelter other components in this way.
According to metallurgy industry standard it is found that the concentration of iron, cobalt, nickel and copper ion in zinc electrolyte is approximately equal, and
Iron, cobalt, nickel and copper stability constant be respectively as follows: KFe=1016.46(relative atomic weight 55.85), KCo=1016.31(relative atomic weight
58.93), KNi=1018.62(relative atomic weight 58.69)；KCu=1018.80(relative atomic weight 63.55), KZn=1016.50It is (opposite
Atomic weight 65.39).Due to KCu=1018.80Maximum, then according to thermodynamical equilibrium principle, two metal ion species all start by EDTA
When complexing, there is following formula to set up:
CZnKZnY=CCuKCuY (1)
When the maximum possible concentration C of copperCuWhen determining, the Cmin C of remaining zinc after maskingZnCalculating formula are as follows:
CZn=CCuKCuY/KZnY (2)
It is electrolysed Cu in zinc solution2+Maximum concentration is CCuWhen, the remaining Zn after EDTA is sheltered2+As long as ion concentration
Greater than CZn, Cu2+Just do not sheltered by EDTA.As long as Cu2+It is not masked, other components Fe2+、Co2+、Ni2+It would not be covered
It covers.
Masking test system optimization method of the present invention towards zinc solution components Concentration Testing；In S1, EDTA is added
After system；When the content concn ratio of the content of EDTA in system and Zn ion is CEDTA:CZnWhen=1:1.1~1:1.25；I.e.
It is determined as the terminal of EDTA masking Zn；The end point values are as reference, in S2.Masking effect is best at this time.
Research also found that the additional amount of color developing agent R salt is also one of the important factor in order of masking test.Color developing agent R salt
Additional amount is very few, although zinc is largely sheltered, the zinc retained is still bigger than components concentration, remaining when R salt is very few
Zn2+It is complexed and develops the color with R salt, cause not extra R salt and components that colour developing is sufficiently complexed, make the Determination of trace gold of whole system
It is too small to belong to metal ion imbibition, test effect is not achieved；Color developing agent R salt additional amount is excessive, so that interference is increasingly to red wave direction
Mobile, available band becomes smaller.Also research discovery pH value has a great impact to the quality of wave spectrum simultaneously；So the present invention is towards zinc
The masking test system optimization method of solution components Concentration Testing；In S2, separately design with EDTA dosage, color developing agent nitrous
Base R salt dosage, the experiment that the pH value of measurement system is unitary variant；Measure absorbance curve.
R salt noiseless wave-length coverage as wide as possible in order to obtain；The present invention passes through analysis spectroscopic data intermediate ion extinction
The characteristics of spending defines two constraint conditions: EDTA dosage is transferred critical point and R salt noiseless wave-length coverage, building description EDTA and
The constraint that R salt dosage influences components absorbance.The turnover critical point of EDTA dosage and R salt noiseless wave-length coverage are fixed respectively
Justice are as follows:
EDTA dosage turnover critical point: with being gradually added into for EDTA, while additional amount gradually increases, high zinc solution
Absorbance curve will appear reversion, according to critical indicator, it is known that the optimal addn of EDTA realizes that dosage is excellent just in this section
Change.
R salt noiseless wave-length coverage NWR: with the increase of color developing agent dosage, the appearance of negative peak can be increasingly severe.Colour developing
Agent dosage is continuously increased, and the appearance of interference can be more and more mobile to red wave direction.According to the start-stop wavelength of smooth available band
It selects to define R salt noiseless wave-length coverage.
NWR=| λ2-λ1| (3)
λ in formula1It is the starting point of the smooth absorption spectra of noiseless, λ2It is the terminal of the smooth absorption spectra of noiseless.Difference between the two
Value means that more greatly wavelength available is more.
Masking test system optimization method of the present invention towards zinc solution components Concentration Testing；In S2, by ultraviolet
Visible spectrophotometry obtains system to be measured in all band absorbance of 200-800nm.
Masking test system optimization method of the present invention towards zinc solution components Concentration Testing；It include that lower part walks in S2
It is rapid:
S21 configures the sample solution containing only zinc ion；The concentration of the zinc ion is that zinc leaches in feed liquid in hydrometallurgy
The M of zinc concentration1Times；First according to the theoretical amount of the S1 EDTA masking zinc calculated；Select an amount ranges Y；Then with
Different dosage point values is selected to be tested in amount range Y；Measure all band absorbance；Using 291~312nm as observation object,
Observation any one wave number in the observation object；Its absorbance is positive number when whether there is the addition that EDTA is added in i-th；I-th+
Its absorbance is negative when 1 addition EDTA；If it is not, redefining the range of Y；It is tested again；If there is then
Defining i-th and the section of amount to the i+1 time addition EDTA amount of EDTA is added is E；I-th is defined simultaneously, and the amount of EDTA is added extremely
It is critical indicator that EDTA amount, which is added, in i+1 time；
S22 configures the sample solution containing only zinc ion；The concentration of the zinc ion is that zinc leaches in feed liquid in hydrometallurgy
The M of zinc concentration1Times；Under conditions of EDTA additional amount, pH value are definite value；Using color developing agent dosage as variable；Carry out second group
Experiment；Measure the absorbance of second group of experiment all samples；Work as λ1It is solution in the ultraviolet-visible absorption spectroscopy of 200-800nm
The starting point of absorption curve, λ can be used2For the terminal that absorption curve can be used；λ1For near shortwave direction, and in divided wave band,
When away from 1nm, the variable quantity of the absorbance of previous point and the latter point is no more than 0.3 wavelength points；λ2For in 610-800nm
Any point；The λ2Greater than λ1；Work as λ1When minimum；Then defining the color developing agent dosage point value is P；The then preferred model of color developing agent dosage
Enclose P ± P* (0.1~0.3)；Defining P ± P* (0.1~0.3) is B；
S23
PH is 3~6.5, color developing agent amount ranges are that B, EDTA amount are arbitrarily selected one group of ginseng in critical indicator range E
Number；Determine for parameter group Q；
Under the conditions of the setting of parameter group Q, using the type of metal ions M as variable；It is back with fixed Zn ion concentration
Scape detects absorbance of the single metal ion in test system；The metal ions M is selected from high concentration than zinc abstraction leachate
In metal ion in addition to Zn；Its concentration is equal to the permitted maximum concentration of industry and any one value below, is preferably
The M of the permitted maximum concentration of industry1Times；
Under the conditions of the setting of parameter group Q, absorbance of the detection high concentration than zinc abstraction leachate；
Dosage, color developing agent dosage, the pH value of EDTA continues to test in replacement parameter group Q；Obtain serial absorbance data；
According to the measured value of S23, ion is obtained with respect to the trend that additive property changes with EDTA, R salt and pH dosage；And respectively
Establish fitting function g (x1)、g(x2)、g(x3)；Wherein g (x1) indicate that each metal ion is in mixed solution under different EDTA dosages
Gaussian function fitting and function of the opposite additive property of 319nm about EDTA dosage at wave crest；g(x2) indicate different R salt dosages
Under each metal ion 319nm at mixed solution wave crest polynomial fit function of the opposite additive property about R salt dosage；g
(x3) indicate that the opposite additive property of each metal ion 319nm at mixed solution wave crest under different pH value is quasi- about the multinomial of pH
Close function.
In practical application, can taking human as select the preferred scope of pH for 3-6.5.
In practical application, M1Value interval be 0.001-0.2.
In the present invention, using fixed Zn ion concentration as background, suction of the single metal ion in test system is detected
Luminosity；It refers to: first configuring the Zn ionic liquid of fixed concentration；Then one of other metal ions to be measured are added,
Detect the absorbance of the metal ion species.(when practical operation, deducting the background of Zn)
Masking test system optimization method of the present invention towards zinc solution components Concentration Testing；S30: in preferred reagent
On the basis of, in order to improve EDTA test system to the masking effect of high zinc, need to advanced optimize the dosage of reagent；To height
The masking problem of components is defined under zinc, if A is the true absorbance of mixed solution, AiFor i-th kind of heavy metal to be measured from
The absorbance of son, Δ A are the relative error between the true absorbance of mixed solution and the true absorbance arithmetic adduction of single ion, and Δ A is got over
The small additive property for showing solion is better, and masking effect is better, and ion is with respect to additive property (additive at definition wave crest
Property, AP) be formula (4):
It is defined by formula (4), the target of reagent optimization should be such that AP value is equal to 0 or is substantially equal to 0；
S31: the difference of reagent dosage makes the additive property of four kinds of ions change, therefore converts one for this problem
Single-object problem, optimization aim such as (5):
minJ(xi)=minAP=min | Δ A | (5)
Wherein xi=[x1,x2,x3]T, respectively indicate EDTA, the dosage and pH value of R salt；
S32: according to the experiment of design, and being analyzed the statistical data of data, be fitted using corresponding function, fitting
Function is as follows:
minJ(xi)=AP=| Δ A |=f (x1,x2,x3) (6)
S33: problem above is described as single-object problem, and excellent constraint condition is x1, and x2, x3 constrain item in two above
Selected range in part analysis is asked using the fmincon function for solving minimum value in matlab R2013a Optimization Toolbox
Solution, optimization aim and constraint condition such as formula (7):
X in formula1,x2,x3EDTA, the dosage and pH value of nitroso-R-salt are respectively indicated, E is the value model of EDTA dosage
It encloses, B is the value range of color developing agent nitroso-R-salt dosage, and C is the value range of pH value；It is inhaled by the spectrum in analysis target
Variation between luminosity and reagent dosage obtains final screening agent dosage optimization system, and passes through the experimental verification screening agent
The feasibility of dosage optimization system.
Masking test system optimization method of the present invention towards zinc solution components Concentration Testing；All test solution
Volume is 25mL.
Masking test system optimization method of the present invention towards zinc solution components Concentration Testing；Color developing agent is nitroso
R salt.
Masking test system optimization method of the present invention towards zinc solution components Concentration Testing；Color developing agent is nitroso
The concentration of R salt is 0.4wt%
Masking test system optimization method of the present invention towards zinc solution components Concentration Testing；When measuring absorbance；
Within the scope of 200-800nm；At interval of the absorbance of 1nm measurement solution.
Principle and advantage
The present invention is based on the single goals of two constraint condition building masking optimal inspection systems, and high concentration is first compared zinc abstraction
Zinc concentration accurate calibration in leachate comes out, and is then quantitatively calculated respectively using trace metal ion concentration and complexing stability constant
Trace metal element starts maximum acceptable concentration when being complexed with EDTA, determines theory EDTA additional amount as standard, in order to
Realization advanced optimizes reagent dosage, defines the optimization constraint condition under two systems: EDTA dosage turnover critical point
With R salt noiseless wave-length coverage, contrived experiment simultaneously obtains experimental data.Two constraint conditions of application definition, and binding isotherm
Calculated value constructs the optimal inspection system method of single goal multivariable, solves the single object optimization based on fmincon function and ask
Topic, finally obtains the optimum amount value of optimal inspection system.By between the spectral absorbance and reagent dosage in analysis target
Variation, obtain final screening agent dosage optimization system, and pass through the feasible of the experimental verification screening agent dosage optimization system
Property.The test system that the present invention obtains has the wide linearity, low detection limit, selectivity good and highly sensitive, does not need to zinc electricity
It solves liquid and carries out pre-separation, automation is easily realized, suitable for high concentration than the screening agent of components Concentration Testing under background
Dosage optimization.Meanwhile the present invention also detects high concentration for Fast synchronization provide than metal ion each in zinc abstraction leachate must
Want condition.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is this hair
Bright some embodiments for those of ordinary skill in the art without creative efforts, can be with root
Other attached drawings are obtained according to these attached drawings.
Fig. 1 is a kind of masking test system optimization method embodiment towards zinc solution components Concentration Testing of the present invention
Flow diagram；
Fig. 2 is that EDTA provided in an embodiment of the present invention (0.5mol/L) different additional amounts influence song to high zinc solution absorbance
Line；
The absorption curve of zinc when Fig. 3 is color developing agent R salt (0.4%) dosage difference provided in an embodiment of the present invention；
The absorption curve of copper iron-cobalt-nickel when Fig. 4 is not optimised for system；
Fig. 5 is that EDTA provided in an embodiment of the present invention is sheltered under zinc optimization system, the absorption curve of copper iron-cobalt-nickel.
As can be seen from Figure 1 the process of optimization method designed by the present invention.
As can be seen from Figure 2 influence of the different additional amounts of EDTA (0.5mol/L) to high zinc solution absorbance.Wherein base
Line, which refers to, deducts 3ml buffer (Acetic acid-sodium acetate), 16g/L zinc (8.00ml standard zinc solution), 0.5mol/L EDTA solution
(1ml), the absorbance curve of 0.4% R salt (0.4ml).
As can be seen from Figure 3 R salt (0.4%) dosage not influence to high zinc solution absorbance simultaneously.Wherein baseline is
Refer to and deducts 3ml buffer (Acetic acid-sodium acetate), 16g/L zinc (8.00ml standard zinc solution), 0.5mol/L EDTA solution
(9ml), the absorbance curve of 0.4% R salt (0.2ml).As can be seen from Figure 4 mixed solution when system is not optimised plus
It is very poor with property.Wherein baseline refer to deduct 3ml buffer (Acetic acid-sodium acetate), 16g/L zinc (8.00ml standard zinc solution),
0.5mol/L EDTA solution (6ml), the absorbance curve of 0.4% R salt (0.4ml).
Figure 4, it is seen that when system is not optimised, the absorbing state of nickel cobalt copper and iron.
As can be seen from Figure 5 after system optimization, the arithmetic adduction of the absorbance curve of mixed solution and four kinds of ions
Curve essentially coincides at 300~370nm, 480~800nm, has preferable additive property.Wherein baseline refers to that deducting 3ml delays
Fliud flushing (Acetic acid-sodium acetate), 16g/L zinc (8.00ml standard zinc solution), 0.5mol/LEDTA solution (10ml), 0.4% R salt
The absorbance curve of (1.2ml).
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.
Referring to Fig. 1, the present embodiment discloses a kind of masking test system optimization towards zinc solution components Concentration Testing
Method, comprising:
S1: it in high concentration than first coming out the Zn content accurate calibration in solution in zinc abstraction leachate, is then added suitable
It measures EDTA and shelters zinc.In order to which the screening agent EDTA being added is complexed only preferentially with zinc, without being complexed with other components, so
It is quantitatively calculated when each trace metal element starts to be complexed with EDTA most using trace metal ion concentration and complexing stability constant
Big safe level determines theory EDTA additional amount as standard；
S2: in the system, the additional amount and pH value of color developing agent nitroso-R-salt are also to influence each Metal Ions Absorption peak
Principal element.The present invention is provided with the optimization constraint condition under a kind of system: the turnover critical point of EDTA dosage and R salt noiseless
Wave-length coverage, contrived experiment simultaneously obtain experimental data；
S3: two constraint conditions of application definition, and binding isotherm calculated value construct the optimal inspection of single goal multivariable
System method solves the single-object problem based on fmincon function, finally obtains the optimum amount of optimal inspection system
Value.
Wherein, high zinc solution can for containing zinc, copper, iron, cobalt, nickel mixed solution.By choosing test system pilot scale
The type and contrived experiment scheme of agent obtain experimental data when components absorbance changes with reagent dosage, based on experiment
The optimization aim of the constraint condition and building of data and definition, the solution for the single goal Multi-variables optimum design problem that application invention proposes
Method realizes the masking test system optimization method towards zinc solution components Concentration Testing.Concrete scheme is implemented as follows:
Contrived experiment simultaneously obtains data
The characteristics of according to testing requirements and zinc liquid to be measured, to inhibit matrix composition Zn2+Absorbance, select EDTA
(0.5mol/L) is used as screening agent；To dramatically increase components Cu2+, Fe2+, Co2+, Ni2+Absorbance, select to Cu2+, Fe2 +, Co2+, Ni2+The nitroso-R-salt (0.4%) all to develop the color is used as color developing agent；Due to pH value and influence components absorbance
Key factor, therefore Acetic acid-sodium acetate is selected to adjust pH value as buffer.In entire experiment, the volume of solution to be measured is
25ML；
The dosage and pH value of EDTA, R salt, the numerical value change range of three kinds of factors such as table 1:
1 reagent (x of tablei) amount ranges
The following are embodiment test conditions:
Instrument: the general general T9 ultraviolet-uisible spectrophotometer of analysis
Test scope: all band, 200nm~800nm
Sample 1.EDTA (0.5mol/L) difference additional amount influences high zinc solution absorbance
It is added in the case where measuring 3ml buffer (Acetic acid-sodium acetate), 16g/L zinc (8.00ml standard zinc solution)
0.5mol/L EDTA solution (1-10ml), the R salt of 0.4ml 0.4% are settled to 25ml with distilled water in the test tube of 25ml,
It shakes up and stands 5min, measured on T9 ultraviolet specrophotometer.
Measurement result is as shown in Figure 2 (abscissa indicates that wave-length coverage/nm, ordinate indicate absorbance/Abs).With compared with
High concentration EDTA's is gradually added into, and when additional amount is between 9-10ml, the absorbance curve of high zinc occurs at 291~312nm
Reversion, according to the turnover critical point constraint of EDTA dosage, it is known that the optimal addn of EDTA just in this section, obtains EDTA dosage
Value range.Described to be reversed in the section 291~312nm under any one wave number, when 9ml is added, corresponding absorbance is
Positive number；And when 10ml is added, under the wave number, the absorbance of system is negative value, and assert that reversion occurs in the section.
The trap variation of zinc when sample 2. color developing agent R salt (0.4%) dosage difference
It is added in the case where measuring 3ml buffer (Acetic acid-sodium acetate), 16g/L zinc (8.00ml standard zinc solution)
0.5mol/L EDTA solution 9ml, 0.4% R salt (0.2-1.8ml) are settled to 25ml with distilled water in the test tube of 25ml,
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).With aobvious
The appearance of the increase of toner dosage, negative peak can be increasingly severe.Color developing agent dosage is continuously increased, and the appearance of interference can increasingly
It is mobile to red wave direction, so that available band becomes smaller.It is constrained according to R salt noiseless wave-length coverage NWR, when R salt influence of noise wave
Additional amount of the long point range within 273nm is then optimum amount.By experimental data it can be seen that the best of 0.4% R salt is added
Amount ranges are between 0.6-1.5ml.
Sample 3. seeks the functional relation in masking system between optimization aim and reagent dosage
On the basis of sample 1 and sample 2, the work of sample 3 is carried out.Each reagent and chemical reaction by measured ion
Complicated mechanism needs to determine functional relation by big and amount experiment, using the method for control experiment, in a certain factor of discussion
Other factors remain unchanged when influence, and according to the aforementioned analysis discussion to absorbance, table 2 is the initial value that plurality of reagents is analyzed simultaneously
Setting:
2 reagent initial value design of table
Determination of the plurality of reagents analyst coverage and table 2 determined according to table 1 to reagent initial value, selects Zn2+Ion concentration
For 16g/L, Cu2+, Fe2+, Co2+, Ni2+Four kinds of ion concentrations are tested when being respectively 0.8mg/L, and available ion is opposite
The trend that additive property changes with EDTA, R salt and pH dosage.
The statistical property of these data is analyzed it is found that it meets Gaussian function, multinomial respectively, is based on least square method,
Available fitting result.
It is as follows with respect to function expression of the additive property for reagent dosage to be fitted obtained ion:
(1) under difference EDTA dosage the opposite additive property of each metal ion 319nm at mixed solution wave crest about EDTA
Gaussian function fitting result are as follows:
(2) under difference R salt dosage the opposite additive property of each metal ion 319nm at mixed solution wave crest about R salt
Fitting of a polynomial result are as follows:
AP=g (x2)=0.6619 × X2 4-3.094X2 3+5.101X2 2-3.472X2+0.8741 (9)
(3) under different pH value the opposite additive property of each metal ion 319nm at mixed solution wave crest about the multinomial of pH
Formula fitting result are as follows:
AP=g (x3)=- 0.09067x3 3+1.244x3 2-0.5655x3+8.564 (10)
It is analyzed by many experiments data it can be found that between three kinds of screening agent, R salt and buffer (pH) reagents and uncontested
Reaction, thus can by different reagents to ion at wave crest with respect to additive property influence be considered as it is independent, by the letter of single reagent
Number relational expression merges into the functional relation of multiple reagents, remains unchanged in the variable part of parametric function, constant part passes through
Experimental data, which is brought into, to be acquired, therefore by calculating, can be changed to formula (11):
AP=g1(x1)+g2(x2)+g3(x3) (11)
Problem above is described as single-object problem after the completion of parameter identification, excellent constraint condition is x1, x2, x3?
Selected range in the analysis of two above constraint condition utilizes solution minimum value in matlab R2013a Optimization Toolbox
Fmincon function is solved, and optimization aim and constraint condition such as formula (10), single object optimization result are listed in table 3:
3 single object optimization result of table
Table 3 respectively illustrates three kinds of reagents by the optimal solution after Optimization Solution and the opposite adduction of ion at wave crest
Minimum value, that is, Cu of property2+, Fe2+, Co2+, Ni2+Four kinds of ions are with the true absorbance of the mixed solution of the variation of reagent dosage and list
Relative error minimum value between the true absorbance of ion.
Opposite additive property and the turnover of EDTA dosage in analytic process above-mentioned from four kinds of ions at wave crest is critical
It selects and masking system is optimized in three aspects of R salt noiseless wave-length coverage, selected from final optimum results range
Masking measurement system basis of certain dosage as spectrum analysis under high zinc background, the concentration and dosage of reagent are listed in table 4:
Table 4 shelters system factor and dosage
Sample 4.EDTA is sheltered under zinc optimization system, the trap situation of copper iron-cobalt-nickel
Under the basis of sample 1, sample 2 and sample 3, using the reagent of table 4 to five component metals ion (Zn2+,Cu2+,
Fe2+, Co2+, Ni2+) mixed solution carries out colour developing masking reaction.Measure 3ml buffer (Acetic acid-sodium acetate), 16g/L zinc
0.5mol/L EDTA solution 10ml is added in the case where (8.00ml standard zinc solution), it is respectively 0.8mg/ that copper iron-cobalt-nickel, which is added,
L, 0.4% R salt 1.2ml are settled to 25ml in the test tube of 25ml, with distilled water, 5min are stood, in T9 uv-spectrophotometric
It is measured on meter.
Measurement result is as shown in Figure 5 (abscissa indicates that wave-length coverage/nm, ordinate indicate absorbance/Abs).By in figure
Curve can be seen that in the case where sheltering high zinc background, and components copper iron-cobalt-nickel all plays peak, and the extinction of mixed solution is write music
The arithmetic of line and four kinds of ions adduction curve essentially coincides at 300~370nm, 480~800nm, has preferable additive property,
Resolution ratio is improved, and the work measured simultaneously for four component components creates advantageous condition.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. the masking test system optimization method towards zinc solution components Concentration Testing characterized by comprising
S1: in high concentration than first calibrating the Zn content in solution to come in zinc abstraction leachate, EDTA masking zinc is calculated
Theoretical amount；The theoretical amount of EDTA masking zinc are as follows: the screening agent EDTA being added only preferentially is complexed with zinc, without with its
He is complexed components；
S2: design is using EDTA dosage, color developing agent nitroso-R-salt dosage, the pH value of measurement system as the experiment of variable；Measure extinction
It writes music line；Define the optimization constraint condition under experimental system are as follows: the turnover critical point of EDTA dosage and R salt noiseless wave-length coverage
NWR；
The EDTA dosage turnover critical point is defined as: high while additional amount gradually increases with being gradually added into for EDTA
The absorbance curve of zinc solution will appear variation；Determine that a certain wave band is observation object；When wave any one in the observation object
Number, its absorbance is positive number when EDTA is added in i-th；Its absorbance is negative when EDTA is added in i+1 time；Then define i-th
It is critical indicator that EDTA amount, which is added, in amount to the i+1 time that EDTA is added；I.e. the optimal addn of EDTA is realized and is used just in this section
Amount optimization；
The R salt noiseless wave-length coverage NWR is defined as: with the increase of color developing agent dosage, the appearance of absorbance curve negative peak
It can be increasingly severe；Color developing agent dosage is continuously increased, and the appearance of interference can be more and more mobile to red wave direction；According to wave can be used
The start-stop wavelength points of section define R salt noiseless wave-length coverage；
NWR=| λ2-λ1| (3)
Wherein, λ1The starting point of absorption curve, λ can be used in the ultraviolet-visible absorption spectroscopy of 200-800nm for solution2It is inhaled to be available
Receive the terminal of curve；λ1For near shortwave direction, and in divided wave band, when spacing 1nm, previous point and the latter point
The variable quantity of absorbance is no more than 0.3 wavelength points；λ2For any point in 610-800nm；The λ2Greater than λ1；
S3: two constraint conditions of application definition, and binding isotherm calculated value construct the optimal inspection system of single goal multivariable
Method solves the single-object problem based on fmincon function, finally obtains the optimum amount value of optimal inspection system；Institute
State single goal are as follows: so that AP value is equal to 0 or is substantially equal to 0；The expression of the AP are as follows:
Wherein A is the true absorbance of mixed solution, AiFor the absorbance of heavy metal ion to be measured in i-th；
The multivariable is successively are as follows: dosage, the color developing agent nitroso-R-salt dosage, the pH value of measurement system of EDTA.
2. the masking test system optimization method according to claim 1 towards zinc solution components Concentration Testing,
It is characterized in that: in S1, after EDTA addition system；When the content concn ratio of the content of EDTA in system and Zn ion is CEDTA:
CZnWhen=1:1.1~1:1.25；It is determined as the terminal of EDTA masking Zn；The end point values are as reference, in S2.
3. the masking test system optimization method according to claim 1 towards zinc solution components Concentration Testing,
It is characterized in that: in S2, separately designing using EDTA dosage, color developing agent nitroso-R-salt dosage, the pH value of measurement system as unitary variant
Experiment；Measure absorbance curve.
4. the masking test system optimization method according to claim 1 towards zinc solution components Concentration Testing,
It is characterized in that: in S2, by ultraviolet-visible spectrophotometry, obtaining system to be measured in all band absorbance of 200-800nm.
5. the masking test system optimization method according to claim 3 towards zinc solution components Concentration Testing,
It is characterized in that:
Include lower part step in S2:
S21 configures the sample solution containing only zinc ion；The concentration of the zinc ion is that zinc leaches zinc in feed liquid in hydrometallurgy
The M of concentration1Times；First according to the theoretical amount of the S1 EDTA masking zinc calculated；Select an amount ranges Y；Then in dosage model
It encloses and different dosage point values is selected to be tested in Y；Measure all band absorbance；Using 291~312nm as observation object, observation
Any one wave number in the observation object；Its absorbance is positive number when whether there is the addition that EDTA is added in i-th；I+1 time
Its absorbance is negative when EDTA is added；If it is not, redefining the range of Y；It is tested again；If there is then fixed
The section that EDTA amount is added in amount to the i+1 time that EDTA is added in adopted i-th is E；I-th is defined simultaneously, and the amount of EDTA is added to the
I+1 addition EDTA amount is critical indicator；
S22 configures the sample solution containing only zinc ion；The concentration of the zinc ion is that zinc leaches zinc in feed liquid in hydrometallurgy
The M of concentration1Times；Under conditions of EDTA additional amount, pH value are definite value；Using color developing agent dosage as variable；Carry out second group of experiment；
Measure the absorbance of second group of experiment all samples；Work as λ1It can be used in the ultraviolet-visible absorption spectroscopy of 200-800nm for solution
The starting point of absorption curve, λ2For the terminal that absorption curve can be used；λ1For near shortwave direction, and in divided wave band, spacing
When 1nm, the variable quantity of the absorbance of previous point and the latter point is no more than 0.3 wavelength points；λ2To appoint in 610-800nm
Meaning is a bit；The λ2Greater than λ1；Work as λ1When minimum；Then defining the color developing agent dosage point value is P；Then color developing agent dosage preferred scope P
± P* (0.1~0.3)；Defining P ± P* (0.1~0.3) is B；
S23
PH is 3-6.5, color developing agent amount ranges are that B, EDTA amount are arbitrarily selected one group of parameter in critical indicator range E；It is fixed
Justice is parameter group Q；
Under the conditions of the setting of parameter group Q, using the type of metal ions M as variable；Using fixed Zn ion concentration as background, inspection
Survey absorbance of the single metal ion in test system；The metal ions M is selected from high concentration than removing in zinc abstraction leachate
Metal ion outside Zn；Its concentration is equal to the M of the permitted maximum concentration of industry1Times；
Under the conditions of the setting of parameter group Q, absorbance of the detection high concentration than zinc abstraction leachate；
Dosage, color developing agent dosage, the pH value of EDTA continues to test in replacement parameter group Q；Obtain serial absorbance data；
According to the measured value of S23, ion is obtained with respect to the trend that additive property changes with EDTA, R salt and pH dosage；And it establishes respectively
Fitting function g (x1)、g(x2)、g(x3)；Wherein g (x1) indicate that each metal ion is in mixed solution wave crest under different EDTA dosages
Locate Gaussian function fitting and function of the opposite additive property of 319nm about EDTA dosage；g(x2) indicate each under different R salt dosages
Polynomial fit function of the opposite additive property of metal ion 319nm at mixed solution wave crest about R salt dosage；g(x3) table
Show fitting of a polynomial letter of the opposite additive property of each metal ion 319nm at mixed solution wave crest under different pH value about pH
Number.
6. the masking test system optimization method according to claim 1 towards zinc solution components Concentration Testing,
It is characterized in that:
S30: it on the basis of preferred reagent, in order to improve EDTA test system to the masking effect of high zinc, needs to reagent
Dosage advanced optimizes；The masking problem of components under high zinc is defined, if A is the true absorbance of mixed solution, Ai
For the absorbance of i-th kind of heavy metal ion to be measured, Δ A is that the true absorbance of mixed solution and the true absorbance arithmetic of single ion sum it up it
Between relative error, the smaller additive property for showing solion of Δ A is better, and masking effect is better, define wave crest at ion it is opposite
Additive property (additive property, AP) is formula (4):
It is defined by formula (4), the target of reagent optimization is so that AP value is equal to 0 or is substantially equal to 0；
S31: the difference of reagent dosage makes the additive property of four kinds of ions change, therefore converts a monocular for this problem
Optimization problem is marked, optimization aim such as (5):
minJ(xi)=minAP=min | Δ A | (5)
Wherein xi=[x1,x2,x3]T, respectively indicate EDTA, the dosage and pH value of R salt；
S32: according to the experiment of design, and the statistical data of data is analyzed, is fitted using corresponding function, fitting function
It is as follows:
minJ(xi)=AP=| Δ A |=f (x1,x2,x3) (6)
S33: problem above is described as single-object problem, and excellent constraint condition is x1, and x2, x3 are in two above constraint condition point
Selected range in analysis is solved using the fmincon function for solving minimum value in matlab R2013a Optimization Toolbox,
Optimization aim and constraint condition such as formula (7):
X in formula1,x2,x3EDTA, the dosage and pH value of nitroso-R-salt are respectively indicated, E is the value range of EDTA dosage, and B is
The value range of color developing agent nitroso-R-salt dosage, C are the value range of pH value；By analysis target in spectral absorbance with
Variation between reagent dosage obtains final screening agent dosage optimization system.
7. optimizing according to the masking test system as claimed in any one of claims 1 to 6 towards zinc solution components Concentration Testing
Method, it is characterised in that: the volume of all test solution is 25mL.
8. optimizing according to the masking test system as claimed in any one of claims 1 to 6 towards zinc solution components Concentration Testing
Method, it is characterised in that: color developing agent is nitroso-R-salt.
9. optimizing according to the masking test system as claimed in any one of claims 1 to 6 towards zinc solution components Concentration Testing
Method, it is characterised in that: color developing agent is that the concentration of nitroso-R-salt is 0.4wt%.
10. excellent according to the masking test system as claimed in any one of claims 1 to 6 towards zinc solution components Concentration Testing
Change method, it is characterised in that: when measurement absorbance；Within the scope of 200-800nm；At interval of the absorbance of 1nm measurement solution.
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