CN115078488B - Quantitative analysis method of organic additive in copper electrorefining - Google Patents
Quantitative analysis method of organic additive in copper electrorefining Download PDFInfo
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- 239000006259 organic additive Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 30
- 239000010949 copper Substances 0.000 title claims abstract description 30
- 238000004445 quantitative analysis Methods 0.000 title claims abstract description 14
- 239000012086 standard solution Substances 0.000 claims abstract description 25
- 238000012360 testing method Methods 0.000 claims abstract description 25
- 238000012417 linear regression Methods 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 46
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 23
- 239000002639 bone cement Substances 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 9
- 238000002484 cyclic voltammetry Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 238000000970 chrono-amperometry Methods 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- 238000003795 desorption Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 239000012087 reference standard solution Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000004832 voltammetry Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000007670 refining Methods 0.000 abstract description 3
- 238000005259 measurement Methods 0.000 abstract description 2
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000723347 Cinnamomum Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000024121 nodulation Effects 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/49—Systems involving the determination of the current at a single specific value, or small range of values, of applied voltage for producing selective measurement of one or more particular ionic species
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a quantitative analysis method of organic additives in copper electrolytic refining, which comprises the steps of firstly preparing a series of standard solutions containing organic additives with different concentrations, then measuring by using a time counting current method, repeating the measurement for three times to obtain the absolute value of a corresponding current average value, drawing a corresponding standard curve by taking the concentration of the organic additives as an abscissa and the absolute value of the current as an ordinate, and obtaining a corresponding linear regression equation; then, measuring the absolute value of current of different electrolytes to be measured, and calculating the content of the organic additive in the electrolytes to be measured according to a corresponding linear regression equation; the method can eliminate the interference of hydrogen evolution reaction by using a time-based current method, has simple testing steps and short measuring time, can accurately detect the content of the organic additive in the electrolyte, and provides a convenient means for quantitative testing of the organic additive in copper electrorefining production.
Description
Technical Field
The invention relates to the technical field of copper electrorefining production, in particular to a quantitative analysis method of an organic additive in copper electrorefining.
Background
In the copper electrorefining production process, in order to ensure that the obtained cathode copper crystals are compact, flat and smooth, a certain amount of organic additives are required to be added into the electrolyte. At present, the common organic additives in the domestic copper electrorefining industry mainly comprise bone glue and thiourea.
Electrolytic refining of copper is essentially a process in which copper is leached at the anode and subsequently reduced at the cathode. Numerous studies have shown that different additives affect the quality of the final cathode copper by affecting the copper cathode reduction process. Bone glue is often used as an inhibitor, is helpful for inhibiting nodulation, can be hydrolyzed to generate bone glue ions with positive charges, and is adsorbed on the area with too high copper deposition speed on the surface of a cathode to prevent copper reduction deposition. The thiourea has a brightening effect generally, and researches show that the thiourea can form a cuprous complex with copper ions, so that the copper ions cannot be directly reduced on a cathode, but are firstly resolved from the complex and then can be reduced and separated out on the cathode, and the effect of preventing copper reduction and deposition is also achieved. In general, the addition of bone glue and thiourea can influence the reduction process of copper ions at the cathode, and has a critical effect on obtaining a cathode copper surface with compact, flat and smooth crystals.
However, due to the limitation of process conditions or production requirements, the addition amount of the organic additive needs to be adjusted at intervals, the content of the additive is kept in a proper range, and if the adjustment is not timely, the quality of the cathode copper can be rapidly deteriorated, and the production cost is increased. In addition, because the organic additive is unstable and easy to hydrolyze in the acid electrolyte, quantitative analysis cannot be carried out by a conventional chemical means, engineers usually carry out analysis and judgment on the amount of the additive according to experience, the method has serious hysteresis, the adding amount of the additive is difficult to adjust in time, and symptoms of insufficient additive and excessive additive in the initial stage of electrolysis are relatively close, so that the judgment is easy to be wrong. Therefore, it is important to develop a method for determining the concentration of organic additives that is rapid and efficient.
At present, quantitative analysis methods for organic additives at home and abroad have some research results. In patent US4834842 a method is disclosed which uses a movable metal wire as the cathode and anode, and the concentration of animal glue or synthetic glue can be determined by measuring the cathode overpotential by constant current method. In this method, copper deposition is carried out at a given current, and the concentration of animal glue or synthetic glue in the electrolyte is monitored by measuring the overpotential according to the correlation of the "glue concentration-cathodic overpotential". However, when copper deposition is carried out under a given current, the method can cause overpotential fluctuation due to the existence of hydrogen evolution reaction, and cause test errors. The patent CN112798674a uses cyclic voltammetry to deposit copper in the negative scanning process, then scans positively, integrates the area of oxidized peak generated by scanning, establishes the correspondence between the area of oxidized peak and the gelatin concentration, and monitors the gelatin concentration in the solution by measuring the area of oxidized peak. However, the method cannot directly read the data of the oxidation peak, the area of the oxidation peak needs to be integrated, the steps are complicated, the influence of manually setting a base line is large when the integrated area is obtained, and particularly, the area of the peak obtained when the base line is not usual has a large error. Therefore, it is very significant to design a method which is simple to operate and can rapidly and accurately quantitatively analyze organic additives in copper electrorefining.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a quantitative analysis method of an organic additive in copper electrolytic refining, which aims to solve the problem that the dosage of the additive in copper electrolytic production is difficult to control timely and accurately.
The technical scheme of the invention is as follows:
a quantitative analysis method of organic additives in copper electrorefining comprises the following steps:
s1, electrode pretreatment
The method comprises the steps of forming a three-electrode system by taking a rotary disc platinum electrode as a working electrode, a platinum sheet electrode as an auxiliary electrode and a saturated Ag/AgCl electrode as a reference electrode, placing the three electrodes in an electrolytic tank, and connecting an electrochemical workstation; adding sulfuric acid aqueous solution into an electrolytic tank, pretreating an electrode by adopting a cyclic voltammetry, recording an obtained voltammetry curve until the curve is basically coincident with a characteristic curve, finishing the pretreatment of the electrode at the moment, and washing the electrode with deionized water for later use;
The diameter of the rotating disc platinum electrode is 3mm, and the area of the platinum sheet electrode is 1cm multiplied by 1cm;
The concentration of the sulfuric acid aqueous solution is 0.5mol/L;
The parameters of the cyclic voltammetry are set as follows: the potential window is-0.17-1.4V, the scanning speed is 100mV/s, and the cycle number is 10;
The characteristic curve is shown in fig. 1, and the requirement that the volt-ampere curve and the characteristic curve are basically coincident is as follows: a pair of adsorption peaks and a pair of desorption peaks of hydrogen appear on the curve at the same time;
s2, drawing a standard curve
Preparing a standard solution V by taking deionized water as a solvent, adding an organic additive into the standard solution V, and changing the amount of the added organic additive to prepare standard solutions V1, V2, V3, V4 and V5 containing organic additives with different concentrations respectively, wherein the concentrations of the organic additives are respectively marked as C 1、C2、C3、C4、C5;
Adding a standard solution V1 into an electrolytic tank, inserting a working electrode subjected to pretreatment in the step S1, inserting an auxiliary electrode and a reference electrode in the step S1 to form a three-electrode system, connecting an electrochemical workstation, setting the rotating speed of a rotating disc electrode, setting experimental parameters of a timing current method for testing, keeping the temperature at 25 ℃ in the testing process, repeating the steps for three times, recording the current value at the end of each test, taking the absolute value of the current average value measured for three times, and recording as I 1;
Respectively replacing standard solutions V2, V3, V4 and V5, respectively measuring corresponding current absolute values according to the step of measuring I 1, and marking the absolute values as I 2、I3、I4、I5; taking the concentration (C n, n=1-5) of the organic additive as an abscissa, taking the corresponding absolute value (I n, n=1-5) of the current as an ordinate, and obtaining a standard curve through linear fitting;
the reference standard solution V comprises the following components: 187g/L of cupric sulfate pentahydrate and 170g/L of sulfuric acid;
the organic additive is bone glue or thiourea;
the concentration range of the organic additive is 4-12 ppm;
the rotating speed of the rotating disc electrode is 2000rpm;
The experimental parameters of the chronoamperometry are set as follows: the initial potential is open circuit potential, the low potential is-0.15 to-0.2V, the high potential is open circuit potential, the initial steps are negative, the number of steps is 1, and the pulse width is 30-60 s;
Particularly preferred:
When the organic additive is bone glue, the concentration C 1、C2、C3、C4、C5 of the organic additive in the standard solutions V1, V2, V3, V4 and V5 is 4ppm, 5ppm, 6ppm, 7ppm and 8ppm respectively, the rest components are the same as those in the standard solution V, the linear regression equation of the fitted standard curve is y= -0.0027x+0.0364, and the linear correlation coefficient R=0.9984;
When the organic additive is thiourea, the concentration C 1、C2、C3、C4、C5 of the organic additive in the standard solutions V1, V2, V3, V4 and V5 is 4ppm, 6ppm, 8ppm, 10ppm and 12ppm respectively, the rest components are the same as those in the standard solution V, the linear regression equation of the fitted standard curve is y= -0.001x+0.0324, and the linear correlation coefficient R= 0.9991;
s3, sample detection
And adding the electrolyte to be tested containing the organic additive into an electrolytic tank, testing according to the timing current method in S2, obtaining the absolute value I Measuring of a corresponding current average value, and calculating according to the standard curve in S2 to obtain the corresponding concentration C Measuring of the organic additive.
The invention has the beneficial effects that:
The interference of hydrogen evolution reaction in the cathode process in the aqueous solution system can be effectively eliminated by using a timing current method, and the concentration of the organic additive in the electrolyte can be accurately measured; the current value can be directly read from the test result, complex data processing is not needed, and the test steps are simple; the measurement time is short, the test steps do not exceed 60 seconds, and the content of the organic additive in the electrolyte can be accurately detected. The invention provides a convenient means for quantitative testing of the organic additive in the copper electrorefining production.
Drawings
Fig. 1 is a characteristic curve of electrode pretreatment.
Fig. 2 is a timing current curve of bone cement.
Fig. 3 is a standard curve of the absolute value of the current of bone glue versus its concentration.
FIG. 4 is a timing current curve for thiourea.
Fig. 5 is a standard curve of current absolute value of thiourea versus its concentration.
Detailed Description
The invention will be further illustrated by the following examples for a better understanding of the invention, but the scope of the invention is not limited thereto.
Example 1
(1) Electrode pretreatment
A rotary disc platinum electrode with the diameter of 3mm is used as a working electrode, a platinum sheet electrode with the area of 1cm multiplied by 1cm is used as an auxiliary electrode, a saturated Ag/AgCl electrode is used as a reference electrode to form a three-electrode system, and the three electrodes are placed in an electrolytic tank and connected with an electrochemical workstation. Adding 0.5mol/L sulfuric acid aqueous solution into an electrolytic tank, and preprocessing an electrode by adopting a cyclic voltammetry, wherein parameters are set as follows: the potential window is-0.17-1.4V, the scanning speed is 100mV/s, and the cycle number is 10. And simultaneously generating a pair of adsorption peaks and a pair of desorption peaks of hydrogen on the curve to be tested and the characteristic curve, and after pretreatment, flushing the working electrode with deionized water for later use.
(2) Drawing a standard curve
Preparing a reference standard solution V by taking deionized water as a solvent, wherein the specific composition is as follows: 187g/L of cupric sulfate pentahydrate and 170g/L of sulfuric acid. Adding organic additive bone glue into standard solution V, and respectively preparing standard solutions V1, V2, V3, V4 and V5 containing bone glue with different concentrations, wherein the concentrations of bone glue are respectively 4ppm, 5ppm, 6ppm, 7ppm and 8ppm, and are respectively marked as C 1、C2、C3、C4、C5.
Adding a standard solution V1 into an electrolytic tank, inserting a pretreated working electrode, inserting a 1cm multiplied by 1cm platinum sheet electrode as an auxiliary electrode, inserting a saturated Ag/AgCl electrode as a reference electrode to form a three-electrode system, connecting a Cinnamomum Chemicals CHI660C electrochemical workstation, setting the rotating disk electrode rotating speed to 2000rpm, setting a timing amperometric experimental parameter for testing, wherein the parameter is set as follows: the initial potential is open circuit potential, the low potential is-0.2V, the high potential is open circuit potential, the initial steps are negative, the number of steps is 1, and the pulse width is 60s. The temperature is kept at 25 ℃ in the testing process, the current value at the end of each test is recorded, the absolute value of the current average value measured for three times is taken, and the absolute value is recorded as I 1.
Respectively replacing standard solutions V2, V3, V4 and V5, respectively measuring corresponding current absolute values according to the step of measuring I 1, and marking the absolute values as I 2、I3、I4、I5; taking the concentration of bone glue (C n, n=1-5) as an abscissa, and the corresponding absolute value of current (I n, n=1-5) as an ordinate, and obtaining a standard curve through linear fitting; the linear regression equation for the fitted standard curve is y= -0.0027x+0.0364, the linear correlation coefficient r=0.9984.
(3) Sample detection
Two parts of standard solution V were taken, to which 5.5ppm and 7.5ppm bone cement were added, respectively, to prepare solutions to be tested, designated N1 and N2. The absolute values of the currents corresponding to N1 and N2 were measured according to the procedure of measuring I 1, and are denoted as I N1 and I N2. Calculating the bone cement concentration in the solution to be measured according to a linear regression equation y= -0.0027x+0.0364 of the standard curve, wherein the bone cement concentration C Measuring 1 obtained by testing in N1 is 5.58ppm, and the relative error is 1.4%; the concentration C Measuring 2 of the bone glue obtained by testing in N2 is 7.32ppm, and the relative error is 2.4%.
(2) Example 2
This example differs from example 1 in that the organic additive is thiourea, and the thiourea concentrations in the standard solutions V1, V2, V3, V4, V5 are 4ppm, 6ppm, 8ppm, 10ppm, 12ppm, respectively, and the thiourea concentrations in the solutions N1 and N2 to be measured in the sample test are 5ppm and 9ppm, respectively. The remaining steps were the same as in example 1. The linear regression equation of the fitted standard curve is y= -0.001x+0.0324, the linear correlation coefficient r= 0.9991. Calculating the concentration of thiourea in the solution to be detected according to a linear regression equation y= -0.001x+0.0324 of a standard curve, wherein the concentration C Measuring 1 of thiourea obtained by testing in N1 is 4.9ppm, and the relative error is 2.0%; the thiourea concentration C Measuring 2 tested in N2 was 8.73ppm with a relative error of 3.0%.
(3) Example 3
The present embodiment is different from embodiment 1 in that the chronoamperometric experimental parameters are set as follows: the initial potential is open circuit potential, the low potential is-0.15V, the high potential is open circuit potential, the initial steps are negative, the number of steps is 1, and the pulse width is 30s. The remaining steps were the same as in example 1. The linear regression equation of the fitted standard curve is y= -0.0026x+0.0286, and the linear correlation coefficient r=0.9993. Calculating the bone cement concentration in the solution to be measured according to a linear regression equation y= -0.0026x+0.0286 of the standard curve, wherein the bone cement concentration C Measuring 1 obtained by testing in N1 is 5.37ppm, and the relative error is 2.3%; the bone glue concentration C Measuring 2 measured in N2 was 7.41ppm with a relative error of 1.2%.
(4) Example 4
The difference between this example and example 1 is that the organic additive is thiourea, and the concentration of thiourea in the standard solutions V1, V2, V3, V4 and in the standard solutions is 4ppm, 6ppm, 8ppm and 10ppm respectively; the experimental parameters of the chronoamperometry are set as follows: the initial potential is open circuit potential, the low potential is-0.15V, the high potential is open circuit potential, the initial steps are negative, the number of steps is 1, and the pulse width is 30s; the thiourea concentrations in the solutions N1 and N2 to be tested in the sample test were 5ppm and 9ppm, respectively. The remaining steps were the same as in example 1. The linear regression equation of the fitted standard curve is y= -0.001x+0.0222, the linear correlation coefficient r=0.9990. Calculating the concentration of thiourea in the solution to be detected according to a linear regression equation y= -0.001x+0.0222 of the standard curve, wherein the concentration C Measuring 1 of thiourea obtained by testing in N1 is 5.04ppm, and the relative error is 0.8%; the thiourea concentration C Measuring 2 measured in N2 was 9.1pm with a relative error of 1.1%.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the invention, but any modifications, equivalent changes, modifications and the like made to the above embodiments according to the technical matters of the present invention should be included in the scope of the present invention.
Claims (8)
1. A quantitative analysis method of organic additives in copper electrorefining is characterized by comprising the following steps:
s1, electrode pretreatment
The method comprises the steps of forming a three-electrode system by taking a rotary disc platinum electrode as a working electrode, a platinum sheet electrode as an auxiliary electrode and a saturated Ag/AgCl electrode as a reference electrode, placing the three electrodes in an electrolytic tank, and connecting an electrochemical workstation; adding sulfuric acid aqueous solution into an electrolytic tank, pretreating an electrode by adopting a cyclic voltammetry, recording an obtained voltammetry curve until the curve is basically coincident with a characteristic curve, finishing the pretreatment of the electrode at the moment, and washing the electrode with deionized water for later use;
s2, drawing a standard curve
Preparing a standard solution V by taking deionized water as a solvent, adding an organic additive into the standard solution V, and changing the amount of the added organic additive to prepare standard solutions V1, V2, V3, V4 and V5 containing organic additives with different concentrations respectively, wherein the concentrations of the organic additives are respectively marked as C 1、C2、C3、C4、C5;
Adding a standard solution V1 into an electrolytic tank, inserting a working electrode subjected to pretreatment in the step S1, inserting an auxiliary electrode and a reference electrode in the step S1 to form a three-electrode system, connecting an electrochemical workstation, setting the rotating speed of a rotating disc electrode, setting experimental parameters of a timing current method for testing, keeping the temperature at 25 ℃ in the testing process, repeating the steps for three times, recording the current value at the end of each test, taking the absolute value of the current average value measured for three times, and recording as I 1;
Respectively replacing standard solutions V2, V3, V4 and V5, respectively measuring corresponding current absolute values according to the step of measuring I 1, and marking the absolute values as I 2、I3、I4、I5; taking the concentration of the organic additive as an abscissa and the corresponding absolute value of current as an ordinate, and obtaining a standard curve through linear fitting;
the organic additive is bone glue or thiourea;
the reference standard solution V comprises the following components: 187g/L of cupric sulfate pentahydrate and 170g/L of sulfuric acid;
The experimental parameters of the chronoamperometry are set as follows: the initial potential is open circuit potential, the low potential is-0.15 to-0.2V, the high potential is open circuit potential, the initial steps are negative, the number of steps is 1, and the pulse width is 30-60 s;
s3, sample detection
And adding the electrolyte to be tested containing the organic additive into an electrolytic tank, testing according to the timing current method in S2, obtaining the absolute value I Measuring of a corresponding current average value, and calculating according to the standard curve in S2 to obtain the corresponding concentration C Measuring of the organic additive.
2. The method for quantitative analysis of organic additives in copper electrorefining according to claim 1, wherein the diameter of the rotating disk platinum electrode in S1 is 3mm, and the area of the platinum sheet electrode is 1cm. Times.1 cm.
3. The method for quantitatively analyzing an organic additive in copper electrorefining according to claim 1, wherein the concentration of the aqueous sulfuric acid solution in S1 is 0.5mol/L.
4. The method for quantitative analysis of organic additives in copper electrorefining according to claim 1, wherein the cyclic voltammetry parameters in S1 are set as follows: the potential window is-0.17-1.4V, the scanning speed is 100mV/s, and the cycle number is 10.
5. The method for quantitative analysis of organic additives in copper electrorefining according to claim 1, wherein the requirement that the voltammetric curve and the characteristic curve in S1 substantially coincide is: a pair of adsorption peaks and a pair of desorption peaks for hydrogen appear simultaneously on the curve.
6. The method for quantitatively analyzing an organic additive in copper electrorefining according to claim 1, wherein the organic additive in S2 is bone glue or thiourea, and the concentration of the organic additive is in the range of 4 to 12ppm.
7. The method for quantitative analysis of organic additives in copper electrorefining according to claim 1, wherein the rotating disk electrode in S2 has a rotation speed of 2000rpm.
8. The method for quantitative analysis of organic additives in copper electrorefining according to claim 1, wherein when the organic additive in S2 is bone glue, the concentration C 1、C2、C3、C4、C5 of the organic additive in the standard solutions V1, V2, V3, V4, V5 is 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, respectively, and the linear regression equation of the fitted standard curve is y= -0.0027x+0.0364, and the linear correlation coefficient r=0.9984;
When the organic additive is thiourea, the concentration C 1、C2、C3、C4、C5 of the organic additive in the standard solutions V1, V2, V3, V4 and V5 is 4ppm, 6ppm, 8ppm, 10ppm and 12ppm respectively, and the linear regression equation of the fitted standard curve is y= -0.001x+0.0324, and the linear correlation coefficient R= 0.9991.
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