CN115078488A - Quantitative analysis method for organic additive in copper electrolytic refining - Google Patents
Quantitative analysis method for organic additive in copper electrolytic refining Download PDFInfo
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- 239000006259 organic additive Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 32
- 239000010949 copper Substances 0.000 title claims abstract description 32
- 238000007670 refining Methods 0.000 title claims abstract description 15
- 238000004445 quantitative analysis Methods 0.000 title claims abstract description 14
- 238000012360 testing method Methods 0.000 claims abstract description 24
- 239000012086 standard solution Substances 0.000 claims abstract description 22
- 238000012417 linear regression Methods 0.000 claims abstract description 17
- 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 9
- 238000000970 chrono-amperometry Methods 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 238000005259 measurement Methods 0.000 claims abstract description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 44
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- 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
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 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
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 239000012087 reference standard solution Substances 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
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 3
- 238000003795 desorption Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 238000004832 voltammetry Methods 0.000 claims description 2
- 238000001075 voltammogram Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000012113 quantitative test Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 108010010803 Gelatin Proteins 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
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003112 inhibitor Substances 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
- 230000024121 nodulation Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
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- 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
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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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 chronoamperometry, repeating the measurement for three times to obtain absolute values of corresponding current average values, drawing corresponding standard curves by taking the concentration of the organic additives as horizontal coordinates and the absolute values of the current as vertical coordinates to obtain corresponding linear regression equations; then measuring the absolute value of the current of different electrolytes to be detected, and calculating the content of the organic additive in the electrolytes to be detected according to a corresponding linear regression equation; the method uses a timing current method, can eliminate the interference of hydrogen evolution reaction, has simple test steps and short measurement time, can accurately detect the content of the organic additive in the electrolyte, and provides a convenient means for quantitative test of the organic additive in copper electrolytic refining production.
Description
Technical Field
The invention relates to the technical field of copper electrolytic refining production, in particular to a quantitative analysis method of an organic additive in copper electrolytic refining.
Background
In the copper electrolytic refining production process, in order to ensure that the obtained cathode copper is compact, flat and smooth in crystallization, a certain amount of organic additives are required to be added into the electrolyte. At present, the organic additives commonly used in the domestic copper electrolytic refining industry mainly comprise bone glue and thiourea.
The electrolytic refining of copper is essentially a process in which copper is dissolved out at the anode and subsequently reduced at the cathode. Numerous studies have shown that different additives affect the quality of the finally obtained cathode copper by affecting the copper cathode reduction process. The bone glue is often used as an inhibitor, which is helpful for inhibiting nodulation, and the bone glue can be hydrolyzed to generate bone glue ions with positive charges, which are adsorbed on the area with the too high copper deposition speed on the surface of the cathode to prevent the reduction and deposition of copper. The thiourea generally has a brightening effect, 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 resolved from the complex firstly and then can be reduced and separated on the cathode, and the effect of inhibiting copper reduction and deposition is also achieved. In general, the addition of bone glue and thiourea can affect the reduction process of copper ions in the cathode and has a crucial effect on obtaining a cathode copper surface with compact, smooth and even crystals.
However, due to the limitation of process conditions or production requirements, the amount of the organic additive needs to be adjusted at variable times to keep the content of the additive within a proper range, and if the adjustment is not timely, the quality of the cathode copper may deteriorate rapidly, and the production cost may be increased. In addition, because the organic additive is unstable and easy to hydrolyze in the acidic electrolyte, quantitative analysis cannot be performed by conventional chemical means, and engineers generally analyze and judge the amount of the additive according to experience. Therefore, it is important to develop a method for quickly and efficiently determining the concentration of organic additives.
At present, quantitative analysis methods for organic additives at home and abroad have some research results. A method is disclosed in US4834842, which enables the determination of the concentration of animal or synthetic glues by measuring the cathode overpotential by a galvanostatic method using a movable metal wire as cathode and anode. In this method, the deposition of copper is carried out at a given current, and the concentration of the glue or synthetic glue in the electrolyte is monitored by measuring the overpotential, according to the correlation "glue concentration-cathode overpotential". However, when copper deposition is carried out under a given current, overpotential fluctuation is caused due to the existence of hydrogen evolution reaction, and test errors are caused. Patent CN112798674A utilizes cyclic voltammetry to perform copper deposition in the negative scanning process, then perform positive scanning, and integrate the oxidation peak area generated by scanning, establish the correspondence between the oxidation peak area and gelatin concentration, and monitor the gelatin concentration in the solution by measuring the oxidation peak area. However, this method cannot directly read the data of the oxidation peak, and needs to integrate the oxidation peak area, which is cumbersome, and when calculating the integrated area, it is greatly affected by artificially setting the baseline, and especially when the baseline is uneven, the peak area obtained has a large error. Therefore, it is very meaningful to design a method which is simple to operate and can rapidly and accurately quantitatively analyze the organic additive in the 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 for organic additives in copper electrolytic refining comprises the following steps:
s1 pretreatment of electrode
A rotating disc platinum electrode is used as a working electrode, a platinum sheet electrode 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 a sulfuric acid aqueous solution into an electrolytic cell, pretreating an electrode by adopting a cyclic voltammetry method, recording an obtained voltammetry curve until the curve is basically overlapped with a characteristic curve, finishing electrode pretreatment, and washing the electrode by using deionized water for later use;
the diameter of the rotary disk platinum electrode is 3mm, and the area of the platinum sheet electrode is 1cm multiplied by 1 cm;
the concentration of the sulfuric acid aqueous solution is 0.5 mol/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 time is 10 circles;
the characteristic curve is shown in fig. 1, and the requirement that the voltammogram and the characteristic curve are basically coincident is as follows: a pair of hydrogen adsorption peaks and a pair of hydrogen desorption peaks simultaneously appear on the curve;
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, changing the amount of the added organic additive, and respectively preparing standard solutions V1, V2, V3, V4 and V5 containing organic additives with different concentrations, wherein the concentrations of the organic additives are respectively marked as C 1 、C 2 、C 3 、C 4 、C 5 ；
The standard solution V1 was added to the electrolytic cell, inserted into the working electrode pretreated in S1, and inserted into the auxiliary electrode and reference electrode in S1Forming a three-electrode system, connecting an electrochemical workstation, setting the rotating speed of a rotating disc electrode, setting experimental parameters of a chronoamperometry method for testing, keeping the temperature at 25 ℃ in the testing process, repeating for three times, recording the current value at the end of each test, and taking the absolute value of the average value of the current measured for three times as I 1 ；
The standard solutions V2, V3, V4 and V5 were replaced respectively according to measurement I 1 Respectively measuring corresponding current absolute values, which are marked as I 2 、I 3 、I 4 、I 5 (ii) a In the concentration of organic additives (C) n N is 1 to 5, and the corresponding absolute value of current (I) is taken as the abscissa n N is 1-5) as a vertical coordinate, and obtaining a standard curve through linear fitting;
the composition of the reference standard solution V is as follows: 187g/L copper sulfate pentahydrate and 170g/L 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 2000 rpm;
the experimental parameters of the chronoamperometry are set as follows: the initial potential is an open-circuit potential, the low potential is-0.15 to-0.2V, the high potential is an open-circuit potential, the initial step is negative, the number of steps is 1, and the pulse width is 30 to 60 s;
particularly preferred is:
when the organic additive is bone glue, the concentration C of the organic additive in the standard solutions V1, V2, V3, V4 and V5 is 1 、C 2 、C 3 、C 4 、C 5 4ppm, 5ppm, 6ppm, 7ppm and 8ppm respectively, the components of the rest components are the same as those in the reference standard solution V, the linear regression equation of the fitted standard curve is that y is-0.0027 x +0.0364, and the linear correlation coefficient R is 0.9984;
when the organic additive is thiourea, the concentration C of the organic additive in the standard solutions V1, V2, V3, V4 and V5 1 、C 2 、C 3 、C 4 、C 5 4ppm, 6ppm, 8ppm, 10ppm and 12ppm, respectively, and the remaining components are the same as those in the reference standard solution V, and are fitted to the standardThe linear regression equation of the curve is that y is-0.001 x +0.0324, and the linear correlation coefficient R is 0.9991;
s3, detecting the sample
Adding electrolyte to be tested containing organic additive into electrolytic cell, testing according to the chronoamperometry method in S2 to obtain absolute value I of corresponding current average value Measuring And calculating according to a standard curve in S2 to obtain the corresponding organic additive concentration C Measuring 。
The invention has the beneficial effects that:
by utilizing a timing current method, the interference of hydrogen evolution reaction in the cathode process in an aqueous solution system can be effectively eliminated, and the concentration of an organic additive in the electrolyte can be accurately measured; the current value can be directly read from the test result without complex data processing, and the test step is simple; the measuring time is short, the measuring step is not more than 60 seconds, and the content of the organic additive in the electrolyte can be accurately detected. The invention provides a convenient means for quantitative test of the organic additive in copper electrolytic refining production.
Drawings
FIG. 1 is a characteristic curve of electrode pretreatment.
Fig. 2 is a plot of chronoamperometry 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 plot of the chronoamperometry of thiourea.
FIG. 5 is a standard curve of the absolute value of the current of thiourea versus its concentration.
Detailed Description
In order that the invention may be better understood, the invention will now be further described by way of specific examples, without limiting the scope of the invention thereto.
Example 1
(1) Electrode pretreatment
A rotating 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 cell, and pretreating an electrode by adopting a cyclic voltammetry method, wherein the parameters are as follows: the potential window is-0.17-1.4V, the scanning speed is 100mV/s, and the cycle time is 10 circles. And (4) simultaneously generating a pair of hydrogen adsorption peaks and a pair of hydrogen desorption peaks on the curve to be tested and the characteristic curve, finishing the pretreatment, and washing the working electrode with deionized water for later use.
(2) Drawing a standard curve
A standard solution V is prepared by taking deionized water as a solvent, and comprises the following specific components: 187g/L of blue vitriol and 170g/L of sulfuric acid. Adding organic additive bone glue into standard solution V, and preparing standard solutions V1, V2, V3, V4 and V5 respectively 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 、C 2 、C 3 、C 4 、C 5 。
Adding a standard solution V1 into an electrolytic cell, inserting a working electrode after pretreatment, inserting a platinum sheet electrode of 1cm multiplied by 1cm as an auxiliary electrode, inserting a saturated Ag/AgCl electrode as a reference electrode to form a three-electrode system, connecting a Chenghua CHI660C electrochemical workstation, setting the rotating speed of a rotating disc electrode to 2000rpm, setting experimental parameters of a timing current method for testing, and setting the parameters as: the initial potential is an open-circuit potential, the low potential is-0.2V, the high potential is an open-circuit potential, the initial step is negative, the number of steps is 1, and the pulse width is 60 s. Keeping the temperature at 25 ℃ in the test process, repeating for three times, recording the current value at the end of each test, taking the absolute value of the average value of the three measured currents, and recording as I 1 。
The standard solutions V2, V3, V4 and V5 were replaced respectively according to measurement I 1 Respectively measuring corresponding current absolute values, which are marked as I 2 、I 3 、I 4 、I 5 (ii) a In terms of bone glue concentration (C) n N is 1 to 5, and the corresponding absolute value of current (I) is taken as the abscissa n N is 1-5) as a vertical coordinate, and obtaining a standard curve through linear fitting; the linear regression equation for the fitted standard curve is-0.0027 x +0.0364 with a linear correlation coefficient R of 0.9984.
(3) Sample detection
Taking two partsThe standard solution V was added with 5.5ppm and 7.5ppm of bone glue, respectively, to prepare test solutions, which were designated as N1 and N2. According to measurement I 1 Measuring the absolute values of the currents corresponding to N1 and N2, and recording the absolute values as I N1 And I N2 . Calculating the concentration of the bone glue in the solution to be tested according to a linear regression equation y of the standard curve, wherein the linear regression equation y is-0.0027 x +0.0364, and the concentration C of the bone glue obtained by testing in N1 Side 1 5.58ppm, relative error 1.4%; bone glue concentration C obtained from the test in N2 Side 2 It was 7.32ppm with a relative error of 2.4%.
(2) Example 2
The difference between the example and the example 1 is that the organic additive is thiourea, the concentrations of thiourea in the standard solutions V1, V2, V3, V4 and V5 are respectively 4ppm, 6ppm, 8ppm, 10ppm and 12ppm, and the concentrations of thiourea in the solutions to be tested N1 and N2 in the sample detection are respectively 5ppm and 9 ppm. The remaining steps were the same as in example 1. The linear regression equation for the fitted standard curve is-0.001 x +0.0324 and the linear correlation coefficient R is 0.9991. Calculating the concentration of thiourea in the solution to be tested according to a linear regression equation y of the standard curve, wherein the linear regression equation y is-0.001 x +0.0324, and testing the concentration C of the thiourea obtained in N1 Side 1 4.9ppm, relative error 2.0%; thiourea concentration C obtained by testing in N2 Side 2 It was 8.73ppm with a relative error of 3.0%.
(3) Example 3
The difference between the present embodiment and embodiment 1 is that the chronoamperometry 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 step is negative, the number of steps is 1, and the pulse width is 30 s. The remaining steps were the same as in example 1. The linear regression equation of the fitted standard curve is-0.0026 x +0.0286, and the linear correlation coefficient R is 0.9993. Calculating the bone glue concentration in the solution to be tested according to the linear regression equation y of the standard curve of-0.0026 x +0.0286, and testing the obtained bone glue concentration C in N1 Side 1 5.37ppm, relative error 2.3%; bone glue concentration C obtained from the test in N2 Side 2 It was 7.41ppm with a relative error of 1.2%.
(4) Example 4
This example differs from example 1 in that the organic additive was thiourea and the standard solutionThe concentrations of V1, V2, V3 and V4 and thiourea in the mixture are respectively 4ppm, 6ppm, 8ppm and 10 ppm; 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 step is negative, the number of steps is 1, and the pulse width is 30 s; the concentration of thiourea in the solutions to be detected N1 and N2 in the sample detection is 5ppm and 9ppm respectively. The remaining steps were the same as in example 1. The linear regression equation for the fitted standard curve is-0.001 x +0.0222 and the linear correlation coefficient R is 0.9990. Calculating the concentration of thiourea in the solution to be tested according to a linear regression equation y of the standard curve, wherein the linear regression equation y is-0.001 x +0.0222, and testing the concentration of the thiourea in N1 to obtain the concentration C Side 1 5.04ppm with relative error of 0.8%; thiourea concentration C obtained by testing in N2 Side 2 9.1pm with a relative error of 1.1%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any modifications, equivalent variations, modifications, etc. made to the above embodiments according to the technical spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. A quantitative analysis method for organic additives in copper electrolytic refining is characterized by comprising the following steps:
s1 pretreatment of electrode
A rotating disc platinum electrode is used as a working electrode, a platinum sheet electrode 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 a sulfuric acid aqueous solution into an electrolytic cell, pretreating an electrode by adopting a cyclic voltammetry method, recording an obtained voltammetry curve until the curve is basically overlapped with a characteristic curve, finishing electrode pretreatment, and washing the electrode by using 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, changing the amount of the added organic additive, and respectively preparing standard solutions V1, V2, V3, V4 and V5 containing organic additives with different concentrations, wherein the concentrations of the organic additives are respectively marked as C 1 、C 2 、C 3 、C 4 、C 5 ；
Adding a standard solution V1 into an electrolytic cell, inserting the working electrode pretreated in S1, forming a three-electrode system by an auxiliary electrode and a reference electrode inserted in S1, connecting an electrochemical workstation, setting the rotating speed of a rotating disk electrode, setting experimental parameters of a timing current method for testing, keeping the temperature at 25 ℃ in the testing process, repeating the testing process three times, recording the current value at the end of each test, taking the absolute value of the average value of the current measured three times, and marking the absolute value as I 1 ；
The standard solutions V2, V3, V4 and V5 were replaced respectively according to measurement I 1 Respectively measuring corresponding current absolute values, which are marked as I 2 、I 3 、I 4 、I 5 (ii) a Taking the concentration of the organic additive as an abscissa and the corresponding absolute value of the current as an ordinate, and obtaining a standard curve through linear fitting;
s3, detecting the sample
Adding electrolyte to be tested containing organic additive into electrolytic cell, testing according to the chronoamperometry method in S2 to obtain absolute value I of corresponding current average value Measuring And calculating according to a standard curve in S2 to obtain the corresponding organic additive concentration C Measuring 。
2. The method of 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 x 1 cm.
3. The method for quantitative analysis of organic additives in copper electrorefining according to claim 1, wherein the concentration of the sulfuric acid aqueous solution in S1 is 0.5 mol/L.
4. A method for quantitative analysis of organic additives in copper electrorefining as claimed in claim 1, wherein the parameters of cyclic voltammetry in S1 are set as: the potential window is-0.17-1.4V, the scanning speed is 100mV/s, and the cycle times are 10 circles.
5. The method for quantitatively analyzing an organic additive in electrolytic refining of copper according to claim 1, wherein the requirement that the voltammogram curve substantially coincides with the characteristic curve in S1 is: a pair of hydrogen adsorption peaks and a pair of hydrogen desorption peaks simultaneously appear on the curve.
6. The method for quantitatively analyzing an organic additive in copper electrorefining as set forth in claim 1, wherein the composition of said reference standard solution V in S2 is: 187g/L of blue vitriol and 170g/L of sulfuric acid.
7. The method for quantitatively analyzing an organic additive in copper electrorefining as claimed in 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 12 ppm.
8. The method for quantitative analysis of organic additives in copper electrorefining according to claim 1, wherein the rotation speed of the rotating disk electrode in S2 is 2000 rpm.
9. The method for quantitative analysis of organic additives in copper electrorefining according to claim 1, wherein said chronoamperometric experimental parameters in S2 are set as: 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 step is negative, the number of steps is 1, and the pulse width is 30 to 60 s.
10. The method for quantitatively analyzing an organic additive in electrolytic refining of copper according to claim 1, wherein when the organic additive in S2 is bone glue, the concentration C of the organic additive in the standard solutions V1, V2, V3, V4 and V5 is C 1 、C 2 、C 3 、C 4 、C 5 4ppm, 5ppm, 6ppm, 7ppm and 8ppm respectively, the linear regression equation of the fitted standard curve is that y is-0.0027 x +0.0364, and the linear correlation coefficient R is 0.9984;
when the organic additive is thiourea, the standard solutions V1, V2, V3,Concentration C of organic additives in V4, V5 1 、C 2 、C 3 、C 4 、C 5 4ppm, 6ppm, 8ppm, 10ppm, 12ppm respectively, the linear regression equation of the fitted standard curve is-0.001 x +0.0324, and the linear correlation coefficient R is 0.9991.
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