CN109507181A - A kind of rapid quantitative detection zinc abstraction solution trace cobalt ferronickel ion concentration method - Google Patents
A kind of rapid quantitative detection zinc abstraction solution trace cobalt ferronickel ion concentration method Download PDFInfo
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Abstract
The invention discloses a kind of rapid quantitative detection zinc abstraction solution trace cobalt ferronickel ion concentration methods, and the present invention is by adjusting pH of buffer, color developing agent dosage, screening agent dosage, the temperature of detection architecture, the conditions such as chromogenic reaction time obtain experimental system and optimize serial scheme；Then design ion is linear, the experiment of stability, the additive property of mixed solution；Finally development properties of the research cobalt ferronickel ion under the test system, and pass through linearly dependent coefficient, stability relative error, additive property relative error, to assess test system effect of optimization.By the assessment of effect of optimization, optimal detection system is obtained；And the trace cobalt during zinc abstraction solution on-line checking, nickel, the spectrum Accurate Determining of iron ion are realized based on the optimal detection system.
Description
Technical field
The present invention relates to analysis and testing technology fields, more particularly, to a kind of rapid quantitative detection zinc abstraction solution trace
Measure cobalt ferronickel ion concentration method.
Background technique
Currently, zinc hydrometallurgy purification difficult point is purification process bad environments, the impurity gold such as critical process index cobalt ferronickel
Belong to ion concentration and be difficult to on-line checking, if purification rear impurity tenor is excessively high, to Zinc electrolysis technical-economic index and electric zinc
Quality has a significant impact.Therefore, how under existing resources supplIes, by innovating zinc abstraction detection means, rapidly and accurately
Obtain zinc abstraction purified solution in the more metal ions of trace concentration information, for subsequent real-time monitoring zinc powder additive amount provide according to
According to, for realize energy-saving and emission-reduction, efficiently produce zinc, have great importance.
According to on-line checking to detecting instrument simplicity, the requirement of rapidity and low cost, in recent years, UV, visible light are divided
Photometry becomes the detection method of emerging foreign metal.Spectrophotometry depends on langbobier law, more for low concentration
The continuous spectrum of component solution, any one wavelength points on wave band theoretically all meet linear and additivity.However, practical
Many solution are due to physics (suspension, the scattering processes such as emulsion, the environment such as temperature influence) or chemical (substrate solution in situation
Concentration is higher, the decomposition of complex compound) etc. factors interference, cause testing result unstable, to the substantial deviation of langbobier law；
In addition, in existing spectrographic determination zinc abstraction purified solution when cobalt ferronickel concentration mensuration, it is easily right since zinc ion content is excessively high
Trace metal ion causes masking action, so that the sensitivity of metal ion to be measured is low, signal is difficult to detect；Currently, actually answering
It is limited with spectrophotometry ionic species, and it is only limitted to single ion detection, it is difficult for the mixed solution of various metals ion
It is measured while different metal ions concentration under same detection architecture with realizing, high concentration is more same than the spectrum of lower more metal ions
When detection method operating condition application, at home and abroad still belong to advanced subject.
Therefore, for zinc abstraction solution, research is highly selective, highly sensitive, and the test system of high stability simultaneously uses section
Test system optimization means, developing a kind of rapid quantitative detection zinc abstraction solution trace cobalt ferronickel ion concentration method is mesh
It is preceding there is an urgent need for spectral detection key technology, have great theoretical and practical significance.
Summary of the invention
For the more metal ion spectral detection signal substantial deviation langbobier laws of zinc metallurgy solution, metal ion letter to be measured
It is number faint, it is difficult to while the problem of detection, the present invention provides a kind of methods of rapid quantitative detection cobalt ferronickel ion concentration.
A kind of rapid quantitative detection zinc abstraction solution trace cobalt ferronickel ion concentration method of the present invention, comprising:
S1: using the concentration of trace cobalt ferronickel ion in zinc abstraction solution as test object, with ultraviolet-visible spectrophotometry
The pH of liquid, the dosage of color developing agent, the dosage of screening agent are detected by adjusting to detect liquid as optimization object as detection means
And the temperature of detection architecture, chromogenic reaction time, it obtains experimental system and tentatively optimizes serial scheme；Based on preliminary optimization series
Scheme, selection so that zinc abstraction solution spectrum absorption curve available band range is wide, reagent blank absorbance less than 5, trace from
Suitable scheme of the sub- absorption peak absorbance greater than 0.2 is further tested；
S2: high Zinc standard solution, cobalt standard solution, nickel standard solution, iron standard solution are prepared respectively；
According to zinc ion in practical zinc abstraction solution and trace cobalt ferronickel ion concentration fluctuation range, respectively for cobalt, nickel,
Iron ion configuration only has the serial solution of a metal ion species in addition to zinc ion；In the serial solution, the concentration of zinc ion is
The concentration of zinc ion in practical zinc abstraction solution；Cobalt, nickel, iron ion concentration be practical zinc abstraction solution in correspond to the dense of ion
Degree；Using the serial solution as object, cobalt, nickel, each single ion Linear Experiment of iron are designed；
According to zinc ion in practical zinc abstraction solution and trace cobalt ferronickel ion concentration fluctuation range, prepare serial cobalt, nickel,
The mixed solution of four kinds of iron, zinc ions designs the stability experiment of Ar ion mixing solution；In the mixed solution, cobalt, nickel, iron,
The concentration range of four kinds of ions of zinc is that the concentration range of ion is corresponded in practical zinc abstraction solution；
According to zinc ion in practical zinc abstraction solution and trace cobalt ferronickel ion concentration fluctuation range, configuring metal ion is
The serial solution A of cobalt, zinc；Configuration metal ion is the serial solution B of nickel, zinc；Configuration metal ion is the serial solution of iron, zinc
In C, the serial solution A in cobalt, the concentration range of zinc ion and practical zinc abstraction solution cobalt, zinc ion concentration range one
It causes；In the serial solution B in nickel, the concentration range of zinc ion and practical zinc abstraction solution nickel, zinc ion concentration range one
It causes；In the serial solution C in iron, the concentration range of zinc ion and practical zinc abstraction solution iron, zinc ion concentration range one
It causes；A kind of solution arbitrarily chosen to every kind of ion from above-mentioned A, B, C serial solution, and with identical zinc in three kinds of solution,
Cobalt, nickel, iron concentration configure the mixed solution of zinc ferro-cobalt nickel ion, are one group of solution；It repeats to prepare according to the method described above more
Group solution；Design the additive property experiment of Ar ion mixing solution；
Serial solution, mixed solution tentatively optimize serial scheme according to gained experimental system in S1 in the S2, adjust
It detects the pH of liquid, the dosage of color developing agent, the dosage of screening agent and controls the temperature of detection architecture in the detection process and develop the color anti-
Between seasonable.
The detection method is ultraviolet-visible spectrophotometry, obtains the spectral absorption curve of all experimental solutions.
S3: the spectral absorption curve according to obtained in S2 calculates linearly dependent coefficient, stability relative error, additive property
Relative error, to assess test system effect of optimization；If the system monometallic ion linearly dependent coefficient is 0.95 or more, simultaneously
Mixed solution stability relative error is less than 5%, and additive property relative error is less than 5%；Think that scheme meets optimization in S1
Effect；If being unsatisfactory for any one in above-mentioned condition, testing scheme in S1 is reselected, S2 is repeated, is tested in S3 step
Design is verified again；If above-mentioned condition is not satisfied in all testing schemes in S1, expand pH of buffer, color developing agent is used
Amount, screening agent dosage, the temperature of detection architecture, the range of chromogenic reaction time (at least one parameter in 5 parameters) repeat
S2, S3 step carry out experiment test；
For all experimental programs for meeting above-mentioned condition, selects monometallic ion linearly dependent coefficient close to 1, mix
Stability of solution relative error is minimum, the preferred plan after the optimization of the smallest scheme of additive property relative error, as test system.
Preferably, the S1 includes:
S11 obtains solution in the spectral absorption curve of 500-800nm by ultraviolet-visible spectrophotometry；
The solution includes zinc abstraction solution to be measured and detection liquid；In the solution, zinc ion concentration 130-170g/L；
S12, adjusting pH of buffer are a~b；Adjust color developing agent dosage c~d；Adjust screening agent dosage e~f；Adjust detection
G~h DEG C of the temperature of system；Chromogenic reaction time i~j is adjusted, experimental system is obtained and tentatively optimizes serial scheme；Wherein, described
Adjusting pH of buffer is 3.0~6.5；Adjust 0.25~2.5ml of color developing agent dosage；Adjust 2.50~2.85ml of screening agent dosage；
Adjust 45~90 DEG C of temperature of detection architecture；Adjust chromogenic reaction time 2min~4min；
S13 optimizes serial scheme based on preliminary, selects so that zinc abstraction solution spectrum absorption curve available band range
Width, reagent blank absorbance less than 5, further tested by suitable scheme of the components absorption peak absorbance greater than 0.2；Its
In, pH of buffer is preferably 5.5, and color developing agent dosage is preferably 2.5ml, and screening agent dosage is preferably 2.7ml, the temperature of detection architecture
Preferably 60 DEG C of degree, the chromogenic reaction time is preferably 4min, as this testing scheme；Wherein, the available band range is
Refer to, when wavelength points spacing 1nm, the variable quantity of the absorbance of previous point and the latter point is no more than 0.3 wavelength segment limit；
The reagent blank absorbance refers to, buffer, color developing agent is added, and screening agent carries out the zinc abstraction solution reference after chromogenic reaction
The maximum absorbance of the absorbance curve of aqueous solution；The components absorption peak refers to the absorption peak of cobalt ferronickel ion.
Preferably, the S2 includes:
S21 prepares high Zinc standard solution, cobalt standard solution, nickel standard solution, iron standard solution respectively；
The concentration of high Zinc standard solution is 180g/L, and cobalt standard solution, nickel standard solution, iron concentration of standard solution are
50mg/L, agents useful for same are that analysis is pure.
S22, during more metal ions measure simultaneously, the modeling analysis of each heavy metal ion to be measured is all based on lambert
Beer 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
Good, the stable relative error of the linearity is small in concentration range, and when additive property is good, the spectral signal of acquisition could be used for high-precision point
Analysis.
Tentatively optimize serial scheme based on above-mentioned test system, design ion to be measured it is linear, it is stability, mixed solution plus
The detection limit of test system and the accuracy of assessment test system are determined with property experiment, study cobalt ferronickel ion in the test body
Development properties under system.
According to zinc ion in practical zinc abstraction solution and trace cobalt ferronickel ion concentration fluctuation range, respectively for cobalt, nickel,
Iron ion configuration only has the serial solution of a metal ion species in addition to zinc ion；In the serial solution, the concentration of zinc ion is
The concentration of zinc ion in practical zinc abstraction solution；Cobalt, nickel, iron ion concentration be practical zinc abstraction solution in correspond to the dense of ion
Degree；Using the serial solution as object, cobalt, nickel, each single ion Linear Experiment of iron are designed；When in solution containing only zinc, cobalt metal from
The period of the day from 11 p.m. to 1 a.m, the Concentration Testing range of the cobalt ions are as follows: 0.120-0.720mg/L；When in solution containing only zinc, nickel metal ion,
The Concentration Testing range of the nickel ion are as follows: 0.236-1.416mg/L；When in solution containing only zinc, iron metal ion, the iron
The Concentration Testing range of ion are as follows: 0.224-1.344mg/L；By ultraviolet-visible spectrophotometry, obtains above-mentioned solution and exist
The spectral absorption curve of 500-800nm.
Prepare the mixed solution of three kinds of ions, in cobalt ferronickel Ar ion mixing solution, the concentration of cobalt ions is q, nickel ion
Concentration is r, and the concentration of iron ion is s；Wherein, the concentration of cobalt ions is 0.240mg/L, the concentration of nickel ion are as follows:
0.236mg/L, the concentration of iron ion are as follows: 0.224mg/L；By ultraviolet-visible spectrophotometry, obtains Ar ion mixing solution and exist
The spectral absorption curve of 500-800nm, and Ar ion mixing solution is spaced in 2 hours rescan within 3 minutes it is primary, obtain from
Sub- mixed solution whole spectral absorption curve figure designs the stability experiment of Ar ion mixing solution.
According to zinc ion in practical zinc abstraction solution and trace cobalt ferronickel ion concentration fluctuation range, configuring metal ion is
The serial solution A of cobalt, zinc；Configuration metal ion is the serial solution B of nickel, zinc；Configuration metal ion is the serial solution of iron, zinc
The concentration of cobalt ions is t in C, the serial solution A, and the concentration of nickel ion is u in the serial solution B；The serial solution C
The concentration of middle iron ion is v；Configuration metal ion is the mixed solution of zinc, cobalt, iron, nickel；Cobalt ions in the mixed solution
Concentration is t, the concentration of nickel ion is u, the concentration of iron ion is v；Wherein, concentration of cobalt ions 0.240mg/L, nickel ion it is dense
Degree are as follows: 0.236mg/L, the concentration of iron ion are as follows: 0.224mg/L.By ultraviolet-visible spectrophotometry, obtains above-mentioned solution and exist
The spectral absorption curve of 500-800nm, the additive property experiment of design Ar ion mixing solution.
In above-mentioned solution, the concentration of zinc ion is the concentration of zinc ion in practical zinc abstraction solution.
Preferably, the S3 includes:
S31, three indexs of definition assessment spectrum test system optimization result；Three indexs are respectively as follows: monometallic
The linearly dependent coefficient r of the solion curve of spectrum, mixed solution curve of spectrum stability relative error Δ αstability, mixing
Solution spectrum curve additive property relative error Δ βadditivity；
S32 calculates linearly dependent coefficient, stability relative error, additive property relative error, assessment test system optimization effect
Fruit；
Linearly dependent coefficient r is the common counter for measuring linearly related degree between research variable.Match by above-mentioned laboratory
The solution and test system of system tentatively optimize serial scheme, carry out linear fit to the absorbance at Ions Absorption Wave crest and wave trough,
Measure monometallic ionic cobalt, the linear concentration range of three kinds of nickel, iron ions.
The linearly dependent coefficient r of the monometallic solion curve of spectrum are as follows:
In formula, xjFor under a certain preliminary prioritization scheme of step S1, containing only M in zinc ion and a kind of solution of M metal ion
J-th of concentration value of ion, yjFor containing only zinc ion and a kind of corresponding j-th of the absorbance value of solution of M ion,For containing only
The concentration of M ion in zinc ion and a kind of solution of M ion,For containing only the flat of zinc ion and a kind of solution absorbance of M ion
Mean value, n are the number of M metal ion solution in Linear Experiment, and r is the linear of the M metal ion solution concentration and absorbance
Related coefficient；Linear correlation of the linearly dependent coefficient closer to 1, then under the prioritization scheme, between the concentration and absorbance of ion
Degree is higher, ion it is linear better；When formula (1) operation, the M is selected from one of iron, cobalt, nickel；When M variety exchanging
Afterwards, operation is carried out by formula (1) again；
Since solution many in actual conditions are due to physics (suspension, the scattering processes such as emulsion, the environment shadow such as temperature
Ring) or the factors interference such as chemical (substrate solution concentration is higher, the decomposition of complex compound), cause solution absorbance unstable, detects
As a result substantial deviation langbobier law.Therefore, prioritization scheme preliminary for experimental system, need to be by repeatedly weighing in a period of time
Repetition measurement amount zinc abstraction mixed solution absorbance, carrys out the stability of quantitative analysis solution.
Mixed solution curve of spectrum stability relative error Δ αstabilityAre as follows:
In formula, P is the absorbance that mixed solution measures, PtAfter a period of time t, extinction that mixed solution measures again
Degree, Δ αstabilityFor the relative error percentage of the maximum variable quantity of mixed solution absorbance, i.e. stability relative error；Institute
The range for stating time t is 0~240min；
Additive property is another big property of langbobier law.When the multicomponent in mixture is carried out while being measured,
Each interionic additive property is better, the better separation of spectroscopic data.According to three kinds of single ion solution absorbance theories count plus suction
The curve of spectrum and the comparison with practical mixed solution absorption spectrum curve are received, the theory for calculating mixed ion solutions adds with practical
With property error.
Mixed solution curve of spectrum additive property relative error Δ βadditivityAre as follows:
In formula, AiFor the absorbance value containing only M ion in zinc ion and a kind of solution of M metal ion, A is containing zinc ion
The absorbance measured with the mixed ion solutions of three kinds of M metal ions, m are the type of M metal ion in additive property experiment
Number, Δ βadditivityFor the relative error percentage of mixed solution absorbance and each single ion solution absorbance adduction, that is, sum it up
Property relative error.When formula (3) operation, the M is selected from one of iron, cobalt, nickel.
S33, if surveying system result monometallic ion linearly dependent coefficient 0.95 or more, mixed solution stability is opposite accidentally
For difference less than 5%, additive property relative error shows that the testing scheme is feasible, it is believed that scheme meets effect of optimization in S1 less than 5%；
If being unsatisfactory for above-mentioned condition, testing scheme in S1 is reselected, repeats S2, experimental design is verified again in S3 step；
If above-mentioned condition is not satisfied in all testing schemes in S1, expand pH of buffer, color developing agent dosage, screening agent dosage, detection
The temperature of system, the range of chromogenic reaction time (at least one parameter in 5 parameters) repeat S2, and S3 step carries out experiment survey
Examination；
S34 selects monometallic ion linearly dependent coefficient close to 1 for all experimental programs for meeting above-mentioned condition,
Mixed solution stability relative error is minimum, best after the optimization of the smallest scheme of additive property relative error, as test system
Scheme.
Preferably, the volume of all test solution is 25mL.
Preferably, definition only includes cobalt, and nickel, the solution of Tie Zhongyi metal ion species is monometallic solion,
The monometallic solion and further include zinc ion, 5Br-PADAP color developing agent, EDTA screening agent, OP increase steady agent, acetic acid-vinegar
Sour sodium buffer.
Preferably, it defines while including cobalt, nickel, the solution of three metal ion species of iron is mixed ion solutions, institute
It states mixed ion solutions and further includes zinc ion, 5Br-PADAP color developing agent, EDTA screening agent, the steady agent of OP increasing, Acetic acid-sodium acetate
Buffer.
Preferably, color developing agent 5Br-PADAP, concentration 0.2wt%；Screening agent is EDTA, concentration 1mol/
L；Buffer is Acetic acid-sodium acetate buffer, and concentration 4.0mol/L, conjugate base acid molar ratio is 5.697.
Preferably, spectral absorption curve scanning range is 500-800nm, is divided into 1nm between spectral scan.
Beneficial effect
Present invention is generally directed to complicated component in zinc metallurgy feed liquid, high zinc background interference is seriously difficult to foreign metal ion
The problem of detection, innovatively proposes and the method that equivalent screening agent EDTA shelters high zinc background is added according to Zn content, and real
The spectral characteristic for the trace cobalt ferronickel ion probed under 5Br-PADAP color reagent of high sensitivity is tested, then to each reagent dosage, inspection
The temperature of survey system, pH, the factor designs unitary variant optimum experimental system such as chromogenic reaction time finally calculate single ion solution
The additive property of linearly dependent coefficient and mixed solution carrys out the feasibility and stability of evaluation system.
The present invention reappears the foreign metal ion spectrum signal of masking by chemical means, and the test system of design science is excellent
Change experiment, the interference bring unstability and langbobier law for farthest reducing matrix ions deviate, the present invention
Obtained test system has the high linearity, good more metal ion additive properties, stiff stability, pinpoint accuracy and precision
Degree.Suitable for trace cobalt ferronickel ion concentration in zinc metallurgy feed liquid while on-line checking and high accuracy analysis.
Detailed description of the invention
Fig. 1 is rapid quantitative detection zinc abstraction solution trace cobalt ferronickel ion concentration method provided in an embodiment of the present invention
Flow diagram.
Fig. 2 is color developing agent 5Br-PADAP (0.2wt%) different amounts provided in an embodiment of the present invention to zinc abstraction solution light
Compose the influence of absorption curve.
Fig. 3 is EDTA provided in an embodiment of the present invention (1mol/L) different amounts to zinc abstraction solution spectrum absorption curve
It influences.
Fig. 4 is the temperature of different detection architectures provided in an embodiment of the present invention to the extinction in zinc abstraction solution to measured ion
The influence of degree.
Fig. 5 is three kinds of ion spectras absorptions of zinc abstraction solution cobalt ferronickel after test system provided in an embodiment of the present invention optimization
The linearity pattern of curve.
Fig. 6 is three kinds of ion spectras absorptions of zinc abstraction solution cobalt ferronickel after test system provided in an embodiment of the present invention optimization
The stability test figure of curve.
Fig. 7 is three kinds of ion spectras absorptions of zinc abstraction solution cobalt ferronickel after test system provided in an embodiment of the present invention optimization
The additive property test chart of curve.
Specific embodiment
Below in conjunction with embodiment, the present invention is described further.
Particular technique or condition person are not specified in the embodiment of the present invention, according to the literature in the art described technology or
Condition, or carried out according to product description.Agents useful for same or instrument end indicate production firm person, and being can be by regular channel
Commercially available available conventional products.
Agents useful for same of the embodiment of the present invention and specification:
The ethanol solution of color developing agent 5Br-PADAP: 0.2wt%；EDTA solution: 1mol/L；Acetic acid-sodium acetate buffer:
4.0mol/L, conjugate base acid molar ratio are 5.697；OP solution: 20wt%.
Instrument of the embodiment of the present invention and test condition:
Instrument: Beijing Puxi General Instrument Co., Ltd T9 dual-beam ultraviolet-uisible spectrophotometer, attached association are micro-
Machine；The spectral absorption curve scanning range for surveying cobalt ferronickel complex compound is 500-800nm, is divided into 1nm between spectral scan.
Fig. 1 is rapid quantitative detection zinc abstraction solution trace cobalt ferronickel ion concentration method provided in an embodiment of the present invention
Flow diagram, as shown in Figure 1, comprising: S1: using zinc abstraction solution as optimization object, by adjusting pH of buffer, color developing agent is used
Amount, screening agent dosage, the temperature of detection architecture, the conditions such as chromogenic reaction time obtain experimental system and optimize serial scheme；It is based on
N kind prioritization scheme, selection so that zinc abstraction solution spectrum absorption curve available band range is wide, reagent blank absorbance less than 5,
Suitable scheme of the components absorption peak absorbance greater than 0.2 is further tested；
S2: according to zinc ion in practical zinc abstraction solution and trace cobalt ferronickel ion concentration fluctuation range, high zinc, trace are prepared
Measure cobalt ferronickel standard solution；In a certain amount of zinc solution, a series of single ion solution of various concentrations is prepared to every kind of ion,
Design cobalt, nickel, each single ion Linear Experiment of iron；The mixed solution of three kinds of ions is prepared, the stability of Ar ion mixing solution is designed
Experiment；Respectively prepare the single ion solution of three kinds of ions, and mixed ion solutions identical with concentration in single ion solution, design from
The additive property of sub- mixed solution is tested；It obtains under the testing scheme, the spectral absorption curve of all experimental solutions；
S3: spectral absorption curve of the research cobalt ferronickel ion under the test system scheme calculates linearly dependent coefficient, surely
Qualitative relative error, additive property relative error, to assess test system effect of optimization；If the system monometallic ion is linearly related
Coefficient is 0.95 or more, and for mixed solution stability relative error less than 5%, additive property relative error shows the test less than 5%
Concept feasible, it is believed that scheme meets effect of optimization in S1；If being unsatisfactory for above-mentioned condition, testing scheme in S1 is reselected, weight
S2 is answered, experimental design is verified again in S3 step；If above-mentioned condition is not satisfied in all testing schemes in S1, expand slow
Fliud flushing pH, color developing agent dosage, screening agent dosage, the temperature of detection architecture, the range of the conditions such as chromogenic reaction time repeat S2,
S3 step carries out experiment test；For all experimental programs for meeting above-mentioned condition, monometallic ion linearly dependent coefficient is selected
Close to 1, mixed solution stability relative error is minimum, the optimization of the smallest scheme of additive property relative error, as test system
Preferred plan afterwards.
Based on the above embodiment, wherein the step S1 includes: S11, by ultraviolet-visible spectrophotometry, is obtained molten
Spectral absorption curve of the liquid in 500-800nm；
The solution includes zinc abstraction solution to be measured；Its zinc ion concentration is 130-170g/L；
S12, adjusting pH of buffer are a~b；Adjust color developing agent dosage c~d；Adjust screening agent dosage e~f；Adjust detection
G~h DEG C of the temperature of system；Chromogenic reaction time i~j is adjusted, experimental system is obtained and optimizes serial scheme；Wherein, the adjusting
PH of buffer is 3.0~6.5；Adjust 0.25~2.5ml of color developing agent dosage；Adjust 2.50~2.85ml of screening agent dosage；It adjusts
45~90 DEG C of the temperature of detection architecture；Adjust chromogenic reaction time 2min~4min；
S13 is based on N kind prioritization scheme, and selection is so that zinc abstraction solution spectrum absorption curve available band range is wide, reagent
Blank absorbency less than 5, further tested by suitable scheme of the components absorption peak absorbance greater than 0.2；Wherein, it buffers
Liquid pH is preferably 5.5, and color developing agent dosage is preferably 2.5ml, and screening agent dosage is preferably 2.7ml, and the temperature of detection architecture is preferred
It is 60 DEG C, the chromogenic reaction time is preferably 4min, as this testing scheme；Wherein, the available band range refers to, wavelength
When point spacing 1nm, the variable quantity of the absorbance of previous point and the latter point is no more than 0.3 wavelength period；The reagent is empty
White absorbance refers to, buffer, color developing agent is added, and screening agent carries out the suction of the zinc abstraction solution reference aqueous solution after chromogenic reaction
The maximum absorbance of luminosity curve；The components absorption peak refers to the absorption peak of cobalt ferronickel ion.
Based on the above embodiment, wherein the step S2 includes: S21, according to zinc ion and trace in practical zinc abstraction solution
Cobalt ferronickel ion concentration fluctuation range is measured, high zinc, trace cobalt ferronickel standard solution are prepared；The concentration of zinc ion standard solution is
180g/L, the concentration of standard solution of cobalt ferronickel ion are 50mg/L, and agents useful for same is that analysis is pure.
S22 prepares a series of single ion solution of various concentrations to every kind of ion in a certain amount of zinc solution, design
Cobalt, nickel, each single ion Linear Experiment of iron；The Concentration Testing range of cobalt ions are as follows: k~l, the Concentration Testing range of nickel ion are as follows: m
~n, the Concentration Testing range of iron ion are as follows: o~p；Wherein, the Concentration Testing range of the cobalt ions are as follows: 0.120-
0.720mg/L, the Concentration Testing range of nickel ion are as follows: 0.236-1.416mg/L, the Concentration Testing range of iron ion are as follows:
0.224-1.344mg/L。
The mixed solution of three kinds of ions is prepared, the stability experiment of Ar ion mixing solution is designed；Cobalt ferronickel Ar ion mixing is molten
In liquid, the concentration of cobalt ions is q, and the concentration of nickel ion is r, and the concentration of iron ion is s；Wherein, the concentration of cobalt ions is
0.240mg/L, the concentration of nickel ion are as follows: 0.236mg/L, the concentration of iron ion are as follows: 0.224mg/L.
The mixed solution of three kinds of ions is prepared, the stability experiment of Ar ion mixing solution is designed；Each three kinds of ions of preparation
Single ion solution, and mixed ion solutions identical with concentration in single ion solution, the additive property for designing Ar ion mixing solution are real
It tests；In cobalt ferronickel Ar ion mixing solution, the concentration of cobalt ions is t, and the concentration of nickel ion is u, and the concentration of iron ion is v；Wherein,
Concentration of cobalt ions is 0.240mg/L, the concentration of nickel ion are as follows: 0.236mg/L, the concentration of iron ion are as follows: 0.224mg/L.
S23 is obtained under the testing scheme, spectral absorption curve of all experimental solutions in 500-800nm.
Based on the above embodiment, wherein the step S3 includes: S31, definition assessment spectrum test system optimization result
Three indexs；Three indexs are respectively as follows: the linearly dependent coefficient r of the monometallic solion curve of spectrum, mixed solution light
Spectral curve stability relative error Δ αstability, mixed solution curve of spectrum additive property relative error Δ βadditivity；
S32 calculates linearly dependent coefficient, stability relative error, additive property relative error, assessment test system optimization effect
Fruit；
S33, if surveying the system result monometallic ion linearly dependent coefficient 0.95 or more, mixed solution stability is opposite
For error less than 5%, additive property relative error shows that the testing scheme is feasible less than 5%, it is believed that scheme meets optimization effect in S1
Fruit；If being unsatisfactory for above-mentioned condition, testing scheme in S1 is reselected, repeats S2, experimental design is tested again in S3 step
Card；If above-mentioned condition is not satisfied in all testing schemes in S1, expand pH of buffer, color developing agent dosage, screening agent dosage, inspection
The temperature of survey system, the range of the conditions such as chromogenic reaction time repeat S2, and S3 step carries out experiment test；
S34 selects monometallic ion linearly dependent coefficient close to 1 for all experimental programs for meeting above-mentioned condition,
Mixed solution stability relative error is minimum, best after the optimization of the smallest scheme of additive property relative error, as test system
Scheme.
In step S31, specifically, three index definitions are all based on langbobier law, that is, the absorption surveyed
Spectrum needs to meet stringent linear and additive property.The linearly dependent coefficient r of the monometallic solion curve of spectrum are as follows:
In formula, xjFor under a certain color developing agent dosage, j-th of concentration value of monometallic solion, yjIt is molten for monometallic ion
Corresponding j-th of the absorbance value of liquid,WithIt is respectively the average value of the concentration of monometallic solion and absorbance；It is linearly related
Coefficient is closer to 1, then under the color developing agent dosage, the linearly related degree between the concentration and absorbance of ion is higher, ion
It is linear better；
Mixed solution curve of spectrum stability relative error Δ αstabilityAre as follows:
In formula, PiFor the absorbance of i-th kind of monometallic ion, P is the absorbance that mixed solution measures, Δ αstabilityFor
After a period of time t, the relative error percentage of mixed solution absorbance and each single ion solution absorbance adduction；The time t
Range be 0~240min；
Mixed solution curve of spectrum additive property relative error Δ βadditivityAre as follows:
In formula, AiFor the absorbance of i-th kind of monometallic ion, A is the absorbance that mixed solution measures, Δ βadditivityIt is mixed
The relative error percentage of solution absorbance and each single ion solution absorbance adduction is closed,
Based on the above embodiment, wherein the volume of all test solution is 25mL.The monometallic solion is only
It comprising cobalt, nickel, the solution of Tie Zhongyi metal ion species, and further include zinc abstraction solution, 5Br-PADAP color developing agent, EDTA masking
Agent, OP increase steady agent, Acetic acid-sodium acetate buffer.The mixed ion solutions are while including cobalt, nickel, three metal ion species of iron
Solution, and further include zinc abstraction solution, 5Br-PADAP color developing agent, EDTA screening agent, OP increases steady agent, Acetic acid-sodium acetate buffering
Liquid.
Trace cobalt ferronickel ion in rapid quantitative detection zinc abstraction solution provided in an embodiment of the present invention illustrated below
Concentration method.Survey when being detected simultaneously with the cobalt ferronickel ion of the zinc solution of 130-170g/L in zinc abstraction solution, 0.1-1.4mg/L
For the optimization of examination system, by design unitary variant experiment, 0.2wt%5Br-PADAP color developing agent dosage, 1mol/ are adjusted
LEDTA screening agent dosage, the temperature of detection architecture, the conditions such as chromogenic reaction time optimize experimental system, obtain laboratory operation
Regulation.Concrete scheme is implemented as follows:
In the zinc abstraction solution of highly concentrated ratio, color developing agent dosage has strong influence to the absorbance of solution.Fig. 2 is this
Shadow of color developing agent 5Br-PADAP (0.2wt%) different amounts that inventive embodiments provide to zinc abstraction solution spectrum absorption curve
It rings.As shown in Fig. 2, color developing agent dosage changes from 0.25ml to 2.5ml, and when being spaced 0.25ml, zinc abstraction solution reference distilled water
The ultraviolet-visible absorption spectroscopy figure of solution.
Color developing agent dosage is bigger it can be seen from the zinc metallurgy solution spectrum absorption curve of Fig. 2 color developing agent dosage variation, test
Available band range is smaller, is reduced to 520nm-800nm.But color developing agent is extremely dilute by measured ion (10 with concentration very little-5) anti-
Should be incomplete, so color developing agent dosage is as big as possible.As a result, in order on the one hand guarantee that color developing agent enough can make to be shown by measured ion
Color, and absorbance is higher, on the other hand makes available band range big as far as possible, reduces the strong noise wave band of redundancy, selection
2.5ml0.2wt%Br-PADAP is optimum amount
EDTA (ethylenediamine tetra-acetic acid) is a kind of organic compound, is white powder under normal temperature and pressure.It is it is a kind of can be with
Zn2+The chelating agent that equal bivalent metal ions combine can be used for the masking interference of heavy-metal ion removal.It is molten in zinc metallurgy to study EDTA
Complexing mechanism in liquid is the committed step of this test system optimization to obtain EDTA optimum amount.Fig. 3 is this hair
Influence of EDTA (1mol/L) different amounts that bright embodiment provides to zinc abstraction solution spectrum absorption curve.As shown in figure 3,
EDTA dosage changes from 2.5ml to 2.85ml, when being spaced 0.5ml, the ultravioletvisible absorption light of zinc abstraction solution reference distilled water
Spectrogram.
It can be seen from the zinc metallurgy solution spectrum absorption curve of Fig. 3 EDTA dosage variation when EDTA dosage is 0ml, ginseng
Than the zinc metallurgy solution for water since zinc ion content is excessively high, color developing agent reacts completely with zinc ion, leads to spectral absorption curve
480-580nm absorbance is excessive, is more than instrument test range, forms strong noise wave band, and the characteristic peak of cobalt ferronickel ion to be measured
It between 520-800nm, therefore, does not add in the 5Br-PADAP test system of EDTA, zinc ion treats measured ion masking
Seriously, ion signal to be measured can not obtain.When EDTA dosage is 2.5ml, zinc metallurgy solution spectrum curve is inhaled in 500n-580nm
Luminosity is greater than 1, which is mainly the characteristic absorption band of zinc ion, is shown under the EDTA dosage, zinc is not completely by EDTA
Masking still remains a small amount of zinc ion and participates in chromogenic reaction, and the complex compound of zinc still remains absorption peak, treats measured ion generation and covers
It covers, disturbs ion signal to be measured and obtain.With the increase of EDTA dosage, it can be seen that EDTA (1mol/L) dosage is more than or equal to
When 2.65ml, completely, zinc ion absorption peak of the zinc metallurgy solution in 500n-580nm disappears for masking, eliminates zinc ion and comes to measuring band
Interference, therefore select the EDTA dosage to be 2.7ml or more in testing.It is considered that reducing the extension rate to tested element, choose
The optimum amount of EDAT is 2.7ml.
Heating water bath can be such that testing liquid is heated evenly, and keep chromogenic reaction temperature stable and be easy to control, reduce room temperature
Change bring evaluated error.Fig. 4 be different detection architectures provided in an embodiment of the present invention temperature in zinc abstraction solution to
The influence of the absorbance of measured ion.By taking cobalt ions as an example, as shown in figure 4, for temperature DEG C variation from 45 DEG C to 90 of detection architecture
When, the influence to cobalt ions absorbance to be measured in zinc abstraction solution.It can be seen that at the absorption peak 591nm of cobalt ions, cobalt from
The absorbance of son is in first increases and then decreases trend as the temperature rises, it follows that conclusion, the temperature of detection architecture is for zinc
The absorbance for smelting solution has an impact.In order to obtain the maximum absorbance to measured ion, and the peace in view of laboratory operation
Quan Xing, the temperature for choosing detection architecture is 60 DEG C.
It may finally show that each reagent dosage of test system and laboratory procedures are as follows:
Take 4ml buffer (4.0mol/L Acetic acid-sodium acetate pH value of solution=5.5, conjugate base acid molar ratio 5.697), 1.0ml
Zinc abstraction solution, a certain amount of microelement standard liquid (cobalt, nickel, iron (10-5Mol/L it)) in 25ml colorimetric cylinder, is mended by isometric
After sufficient suitable quantity of water, adds 4ml20wt%OP to increase steady agent solution, shake up.Continuously add 2.5ml 0.2wt%Br-PADAP developer solution
Liquid shakes up and heats 4.0min taking-up in 60 C water baths, and 1.0M EDTA 2.7ml is added, sufficiently shakes to EDTA and reacts
(i.e. reagent reference is close with pure color developing agent color) completely, is finally settled to 25ml, shakes up.Simultaneously to be free of metal ion to be measured
Reagent do reference.Prepare liquid and reference solution are respectively placed in two 5cm cuvettes, it is limited with the general analysis all purpose instrument in Beijing
Responsible company T9 dual-beam ultraviolet-uisible spectrophotometer, the sweep measuring within the scope of 530nm-800nm.
During more metal ions measure simultaneously, the modeling analysis of each heavy metal ion to be measured is all based on lambert Bill
Law, the absorption spectrum surveyed need to meet stringent linear and additive property.Only when each metal ion to be measured is in concentration to be measured
Good, the stable relative error of the linearity is small in range, and when additive property is good, the spectral signal of acquisition could be used for high-precision analysis.
Based on above-mentioned test system optimum results and laboratory procedures, design that ion to be measured is linear, stability, mixing
The additive property of solution tests to determine the detection limit of test system and the accuracy of assessment test system, and research cobalt ferronickel ion exists
Development properties under the test system.
Linearly dependent coefficient r is the common counter for measuring linearly related degree between research variable.Fig. 5 is that the present invention is implemented
The linearity pattern of zinc abstraction solution cobalt three kinds of ion spectra absorption curves of ferronickel after the test system optimization that example provides.Such as Fig. 5
It is shown, by above-mentioned laboratory procedures, monometallic ionic cobalt, three kinds of nickel, iron ions are measured under test system after optimization
Linear concentration range.If certain in zinc abstraction solution waits for that measured ion absorbance is A, the concentration of ion is C, to Ions Absorption wave crest
Absorbance at trough carries out linear fit.
Under color reagent of high sensitivity 5Br-PADAP system, the single ion line spectrum of Co (II), Ni (II), Fe (II)
Absorbance-concentration relationship of figure and Wave crest and wave trough is as shown in figure 5, from scheming (a) and (b): Co (II) exists under the experimental method
There are two absorption peaks in the range of 500nm-800nmd, and Wave crest and wave trough is respectively at 559nm, 569nm, 589nm.By detection data
It is found that the Co (II) of one pack system shows good linear in full spectral region, line is carried out to the absorbance at Wave crest and wave trough
Property fitting, the linearly dependent coefficient that can obtain the C of absorbance A and concentration is respectively r=0.9984,0.9984,0.9985.
From (c) and (d) of Fig. 5: there are two inhale in the range of 500nm-800nmd by Fe (II) under the experimental method
Peak is received, Wave crest and wave trough is respectively at 556nm, 637nm, 747nm.By detection data it is found that the Fe (II) of one pack system is in Quan Guangpu
It shows good linear in range, linear fit is carried out to the absorbance at Wave crest and wave trough, the C of absorbance A and concentration can be obtained
Linearly dependent coefficient be respectively r=0.9976,0.9959,0.9992.
From (e) and (f) of Fig. 5: there are two inhale in the range of 500nm-800nmd by Ni (II) under the experimental method
Peak is received, Wave crest and wave trough is respectively at 535nm, 537nm, 570nm.By detection data it is found that the Ni (II) of one pack system is in Quan Guangpu
It shows good linear in range, linear fit is carried out to the absorbance at Wave crest and wave trough, the C of absorbance A and concentration can be obtained
Linearly dependent coefficient be respectively r=0.9984,0.9875,0.9998.
Since solution many in actual conditions are due to physics (suspension, the scattering processes such as emulsion, the environment shadow such as temperature
Ring) or the factors interference such as chemical (substrate solution concentration is higher, the decomposition of complex compound), cause solution absorbance unstable, detects
As a result substantial deviation langbobier law.
Fig. 6 is three kinds of ion spectras absorptions of zinc abstraction solution cobalt ferronickel after test system provided in an embodiment of the present invention optimization
The stability test figure of curve.Specifically, Fig. 6 (a) is 0.240mg/L Co (II), 0.236mg/L Ni (II), 0.112mg/L
The mixed solution of Fe (II) is spaced the spectral absorption curve figure of 3 minutes run-downs in 2 hours.Fig. 6 (b) is mixed solution 2
The variation tendency of the hour interior absorbance at 561nm, by Fig. 6 (b) it can be seen that the suction of mixed solution maximum absorption peak point
Luminosity general trend is first to rise to decline afterwards, this extent of reaction and ion different under the same time with three kinds of ions in solution are anti-
Stability after answering completely is related.Generally speaking, the total absorbance variation of mixed solution is 0.936-0.932=in 2 hours
0.004, mixed solution curve of spectrum stability relative error Δ αstability=0.43%.The variation of mixed solution absorbance with
The time variation it is smaller, be acceptable, the relative stability of this system is preferable.
Additive property is another big property of langbobier law.When the multicomponent in mixture is carried out while being measured,
Each interionic additive property is better, the better separation of spectroscopic data.Fig. 7 is zinc after test system provided in an embodiment of the present invention optimization
The additive property test chart of three kinds of ion spectra absorption curves of solution cobalt ferronickel is smelted, specifically, is 0.12mg/L Co (II),
0.224mg/L Ni (II), the zinc abstraction mixed solution of 0.236mg/L Fe (II).As shown in fig. 7, being inhaled according to three kinds of single ions
Luminosity theory counts the comparison of adduction and practical mixed solution absorption spectrum curve, calculate the theory of hybrid ionic with it is practical plus
With property error maximum in highest point 574nm, mixed solution curve of spectrum additive property relative error is Δ βadditivity=2.31%,
Show under the action of EDTA screening agent, the system have preferable additive property, suitable for zinc metallurgy feed liquid a variety of trace metals from
Son is carried out while being measured.
Present invention is generally directed to complicated component in zinc metallurgy feed liquid, high zinc background interference is seriously difficult to foreign metal ion
The problem of detection, innovatively proposes and the method that equivalent screening agent EDTA shelters high zinc background is added according to Zn content, and real
The spectral characteristic for the trace cobalt ferronickel ion probed under 5Br-PADAP color reagent of high sensitivity is tested, then to each reagent dosage, inspection
The temperature of survey system, pH, the factor designs unitary variant optimum experimental system such as chromogenic reaction time finally calculate single ion solution
The additive property of linearly dependent coefficient and mixed solution carrys out the feasibility and stability of evaluation system.
The test system that the present invention obtains have the high linearity, good more metal ion additive properties, stiff stability,
Pinpoint accuracy and precision.Suitable for trace cobalt ferronickel ion concentration in zinc metallurgy feed liquid, on-line checking and high-precision are divided simultaneously
Analysis.
Finally, it is emphasized that being not intended to limit guarantor of the invention the above is only preferred embodiment of the invention
Protect range.All other embodiments obtained according to the technique and scheme of the present invention by those skilled in the art, it is made any
Modification, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of rapid quantitative detection zinc abstraction solution trace cobalt ferronickel ion concentration method, it is characterised in that: including walking as follows
It is rapid:
S1: using the concentration of trace cobalt ferronickel ion in zinc abstraction solution as test object, using ultraviolet-visible spectrophotometry as
Detection means, to detect liquid as optimization object, by adjust the detection pH of liquid, the dosage of color developing agent, the dosage of screening agent and
The temperature of detection architecture, chromogenic reaction time obtain experimental system and tentatively optimize serial scheme；Based on preliminary optimization Serial Prescription
Case selects so that zinc abstraction solution spectrum absorption curve available band range is wide, and reagent blank absorbance is less than 5, components
Suitable scheme of the absorption peak absorbance greater than 0.2 is further tested；
S2: high Zinc standard solution, cobalt standard solution, nickel standard solution, iron standard solution are prepared respectively；
According to zinc ion in practical zinc abstraction solution and trace cobalt ferronickel ion concentration fluctuation range, respectively for cobalt, nickel, iron from
Son configuration only has the serial solution of a metal ion species in addition to zinc ion；In the serial solution, the concentration of zinc ion is practical
The concentration of zinc ion in zinc abstraction solution；Cobalt, nickel, iron ion concentration be that the concentration of ion is corresponded in practical zinc abstraction solution；
Using the serial solution as object, cobalt, nickel, each single ion Linear Experiment of iron are designed；
According to zinc ion in practical zinc abstraction solution and trace cobalt ferronickel ion concentration fluctuation range, prepare serial cobalt, nickel, iron,
The mixed solution of four kinds of ions of zinc designs the stability experiment of Ar ion mixing solution；In the mixed solution, cobalt, nickel, iron, zinc
The concentration range of four kinds of ions is that the concentration range of ion is corresponded in practical zinc abstraction solution；
According to zinc ion in practical zinc abstraction solution and trace cobalt ferronickel ion concentration fluctuation range, configuration metal ion be cobalt,
The serial solution A of zinc；Configuration metal ion is the serial solution B of nickel, zinc；Configuration metal ion is the serial solution C of iron, zinc,
Cobalt, the concentration range of zinc ion are consistent with cobalt, the concentration range of zinc ion in practical zinc abstraction solution in the serial solution A；
Nickel, the concentration range of zinc ion are consistent with nickel, the concentration range of zinc ion in practical zinc abstraction solution in the serial solution B；
Iron, the concentration range of zinc ion are consistent with iron, the concentration range of zinc ion in practical zinc abstraction solution in the serial solution C；
A kind of solution arbitrarily chosen to every kind of ion from above-mentioned A, B, C serial solution, and with identical zinc in three kinds of solution,
Cobalt, nickel, iron concentration configure the mixed solution of zinc ferro-cobalt nickel ion, are one group of solution；It repeats to prepare according to the method described above more
Group solution；Design the additive property experiment of Ar ion mixing solution；
Serial solution, mixed solution tentatively optimize serial scheme according to gained experimental system in S1 in the S2, adjust detection
The pH of liquid, the dosage of color developing agent, the dosage of screening agent and in the detection process control detection architecture temperature and chromogenic reaction when
Between.
The detection method is ultraviolet-visible spectrophotometry, obtains the spectral absorption curve of all experimental solutions.
S3: the spectral absorption curve according to obtained in S2, calculating linearly dependent coefficient, stability relative error, additive property are opposite
Error, to assess test system effect of optimization；If the system monometallic ion linearly dependent coefficient mixes simultaneously 0.95 or more
Stability of solution relative error is less than 5%, and additive property relative error is less than 5%；Think that scheme meets effect of optimization in S1；
If being unsatisfactory for any one in above-mentioned condition, testing scheme in S1 being reselected, repeating S2, experimental design is again in S3 step
It is secondary to be verified；If above-mentioned condition is not satisfied in all testing schemes in S1, expand pH of buffer, color developing agent dosage, masking
Agent dosage, the temperature of detection architecture, the range of chromogenic reaction time (at least one parameter in 5 parameters) repeat S2, S3 step
Carry out experiment test；
For all experimental programs for meeting above-mentioned condition, select monometallic ion linearly dependent coefficient close to 1, mixed solution
Stability relative error is minimum, the preferred plan after the optimization of the smallest scheme of additive property relative error, as test system.
2. the method according to claim 1, wherein the S1 includes:
S11 obtains solution in the spectral absorption curve of 500-800nm by ultraviolet-visible spectrophotometry；
The solution includes zinc abstraction solution to be measured and detection liquid；In the solution, zinc ion concentration 130-170g/L；
S12, adjusting pH of buffer are a~b；Adjust color developing agent dosage c~d；Adjust screening agent dosage e~f；Adjust detection architecture
G~h DEG C of temperature；Chromogenic reaction time i~j is adjusted, experimental system is obtained and tentatively optimizes serial scheme；Wherein, the adjusting
PH of buffer is 3.0~6.5；Adjust 0.25~2.5ml of color developing agent dosage；Adjust 2.50~2.85ml of screening agent dosage；It adjusts
45~90 DEG C of the temperature of detection architecture；Adjust chromogenic reaction time 2min~4min；
S13 optimizes serial scheme based on preliminary, and selection is so that zinc abstraction solution spectrum absorption curve available band range is wide, examination
Agent blank absorbency less than 5, further tested by suitable scheme of the components absorption peak absorbance greater than 0.2；Wherein, delay
Fliud flushing pH is preferably 5.5, and color developing agent dosage is preferably 2.5ml, and screening agent dosage is preferably 2.7ml, and the temperature of detection architecture is excellent
60 DEG C are selected as, the chromogenic reaction time is preferably 4min, as this testing scheme；Wherein, the available band range refers to, wave
When long point spacing 1nm, the variable quantity of the absorbance of previous point and the latter point is no more than 0.3 wavelength segment limit；It is described
Reagent blank absorbance refers to, is added buffer, color developing agent, and it is water-soluble that screening agent carries out the zinc abstraction solution reference after chromogenic reaction
The maximum absorbance of the absorbance curve of liquid；The components absorption peak refers to the absorption peak of cobalt ferronickel ion.
3. the method according to claim 1, wherein the S2 includes:
S21 prepares high Zinc standard solution, cobalt standard solution, nickel standard solution, iron standard solution respectively；
The concentration of high Zinc standard solution is 180g/L, and cobalt standard solution, nickel standard solution, iron concentration of standard solution are 50mg/L,
Agents useful for same is that analysis is pure.
S22, according to zinc ion in practical zinc abstraction solution and trace cobalt ferronickel ion concentration fluctuation range, respectively for cobalt, nickel,
Iron ion configuration only has the serial solution of a metal ion species in addition to zinc ion；In the serial solution, the concentration of zinc ion is
The concentration of zinc ion in practical zinc abstraction solution；Cobalt, nickel, iron ion concentration be practical zinc abstraction solution in correspond to the dense of ion
Degree；Using the serial solution as object, cobalt, nickel, each single ion Linear Experiment of iron are designed；When in solution containing only zinc, cobalt metal from
The period of the day from 11 p.m. to 1 a.m, the Concentration Testing range of the cobalt ions are as follows: 0.120-0.720mg/L；When in solution containing only zinc, nickel metal ion,
The Concentration Testing range of the nickel ion are as follows: 0.236-1.416mg/L；When in solution containing only zinc, iron metal ion, the iron
The Concentration Testing range of ion are as follows: 0.224-1.344mg/L；
The mixed solution of three kinds of ions is prepared, the stability experiment of Ar ion mixing solution is designed；In cobalt ferronickel Ar ion mixing solution,
The concentration of cobalt ions is q, and the concentration of nickel ion is r, and the concentration of iron ion is s；
Design the additive property experiment of Ar ion mixing solution；It is dense according to zinc ion in practical zinc abstraction solution and trace cobalt ferronickel ion
Fluctuation range is spent, configuration metal ion is the serial solution A of cobalt, zinc；Configuration metal ion is the serial solution B of nickel, zinc；Configuration
Metal ion is that the concentration of cobalt ions in the serial solution C, the serial solution A of iron, zinc is t, in the serial solution B nickel from
The concentration of son is u；The concentration of iron ion is v in the serial solution C；Configuration metal ion is that zinc, cobalt, iron, the mixing of nickel are molten
Liquid；The concentration of cobalt ions is t in the mixed solution, the concentration of nickel ion is u, the concentration of iron ion is v；
In above-mentioned solution, the concentration of zinc ion is the concentration of zinc ion in practical zinc abstraction solution.
S23 is obtained under testing scheme, spectral absorption curve of all experimental solutions in 500-800nm.
4. the method according to claim 1, wherein the S3 includes:
S31, three indexs of definition assessment spectrum test system optimization result；Three indexs are respectively as follows: monometallic ion
The linearly dependent coefficient r of solution spectrum curve, mixed solution curve of spectrum stability relative error Δ αstability, mixed solution
Curve of spectrum additive property relative error Δ βadditivity；
S32, calculates linearly dependent coefficient, stability relative error, and additive property relative error assesses test system effect of optimization；
S33, if surveying system result monometallic ion linearly dependent coefficient 0.95 or more, mixed solution stability relative error is small
In 5%, additive property relative error shows that the testing scheme is feasible, it is believed that scheme meets effect of optimization in S1 less than 5%；If no
Meet above-mentioned condition, then reselect testing scheme in S1, repeat S2, experimental design is verified again in S3 step；If S1
In all testing schemes above-mentioned condition is not satisfied, then expand pH of buffer, color developing agent dosage, screening agent dosage, detection architecture
Temperature, the range of at least one parameter in 5 parameters of chromogenic reaction time repeats S2, and S3 step carries out experiment test；
S34 selects monometallic ion linearly dependent coefficient close to 1, mixes for all experimental programs for meeting above-mentioned condition
Stability of solution relative error is minimum, the preferred plan after the optimization of the smallest scheme of additive property relative error, as test system.
5. method according to any one of claims 1 to 4, it is characterised in that:
Definition only includes cobalt, and nickel, the solution of Tie Zhongyi metal ion species is monometallic solion, the monometallic solion
It and further include zinc ion, color developing agent, screening agent, buffer；
Definition includes cobalt simultaneously, nickel, and the solution of three metal ion species of iron is mixed ion solutions, the mixed ion solutions and and also
Including zinc ion, color developing agent, screening agent, buffer.
6. the method according to claim 1, wherein the linearly dependent coefficient of the monometallic solion curve of spectrum
R is formula (1):
In formula, xjFor under a certain preliminary prioritization scheme of step S1, containing only M ion in zinc ion and a kind of solution of M metal ion
J-th of concentration value, yjFor containing only zinc ion and a kind of corresponding j-th of the absorbance value of solution of M ion,For containing only zinc ion
With the concentration of M ion in a kind of solution of M ion,For containing only zinc ion and a kind of average value of the solution absorbance of M ion,
N is the number of M metal ion solution in Linear Experiment, and r is the linear correlation of the M metal ion solution concentration and absorbance
Coefficient；Linearly related degree of the linearly dependent coefficient closer to 1, then under the prioritization scheme, between the concentration and absorbance of ion
It is higher, ion it is linear better；When formula (1) operation, the M is selected from one of iron, cobalt, nickel；After M variety exchanging,
Again operation is carried out by formula (1)；
Mixed solution curve of spectrum stability relative error Δ αstabilityFor formula (2):
In formula, P is the absorbance that mixed solution measures, PtAfter a period of time t, the absorbance that mixed solution measures again, Δ
αstabilityFor the relative error percentage of the maximum variable quantity of mixed solution absorbance, i.e. stability relative error；The time
The range of t is 0~240min；
Mixed solution curve of spectrum additive property relative error Δ βadditivityFor formula (3):
In formula, AiFor the absorbance value containing only M ion in zinc ion and a kind of solution of M metal ion, A is containing zinc ion and three
The absorbance that the mixed ion solutions of kind M metal ion measure；M is the type number of M metal ion in additive property experiment；Δ
βadditivityFor the relative error percentage of mixed solution absorbance and each single ion solution absorbance adduction, i.e. additive property is opposite
Error；When formula (3) operation, mixed ion solutions kind contains iron, cobalt, at least two metal ions in nickel.
7. described in any item methods according to claim 1~6, it is characterised in that: the volume of all test solution is 25mL.
8. described in any item methods according to claim 1~6, it is characterised in that: color developing agent 5Br-PADAP, concentration are
0.2wt%；Screening agent is EDTA, concentration 1mol/L；Buffer is Acetic acid-sodium acetate buffer, and concentration 4.0mol/L is total
Yoke alkali acid molar ratio is 5.697.
9. described in any item methods according to claim 1~6, it is characterised in that: the spectral absorption curve scanning range is
500-800nm is divided into 1nm between spectral scan.
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| US20220250979A1 (en) * | 2019-05-17 | 2022-08-11 | Imertech Sas | Method of increasing the stability of a slag |
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