CN113447556B - Method for analyzing quality of electrolyte in copper electrolytic refining - Google Patents
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 31
- 239000010949 copper Substances 0.000 title claims abstract description 31
- 238000007670 refining Methods 0.000 title claims abstract description 14
- 239000006259 organic additive Substances 0.000 claims abstract description 73
- 230000008859 change Effects 0.000 claims abstract description 33
- 239000012086 standard solution Substances 0.000 claims abstract description 21
- 238000012360 testing method Methods 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 14
- 238000004769 chrono-potentiometry Methods 0.000 claims abstract description 10
- 239000012087 reference standard solution Substances 0.000 claims abstract description 10
- 238000004458 analytical method Methods 0.000 claims abstract description 7
- 238000012417 linear regression Methods 0.000 claims abstract description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000002639 bone cement Substances 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 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 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000002484 cyclic voltammetry Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000000840 electrochemical analysis Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 4
- 239000012088 reference solution Substances 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims 4
- 230000001629 suppression Effects 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000012544 monitoring process Methods 0.000 abstract description 5
- 238000002848 electrochemical method Methods 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000024121 nodulation Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle 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
- G01N27/416—Systems
- G01N27/4163—Systems checking the operation of, or calibrating, the measuring apparatus
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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
- G01N27/38—Cleaning of electrodes
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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
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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Abstract
The invention provides an analysis method for the quality of electrolyte in copper electrolytic refining, which comprises the following steps: firstly, preparing standard solutions containing two organic additives with different concentration ratios, then monitoring the standard solutions by adopting a chronopotentiometry to obtain corresponding potential change rates, drawing a standard curve by taking the concentration ratio of the two organic additives as a horizontal coordinate and the potential change rate ratio of the measured potential change rate and a reference standard solution as a vertical coordinate, and further obtaining a corresponding linear regression equation; then measuring corresponding potential change rates of different electrolytes to be tested, and analyzing whether the ratio of various additives in the electrolytes to be tested is an optimal value or not through comparison of a standard curve, so as to analyze the quality of the electrolytes; the method uses an electrochemical method, has short test time, can accurately analyze the quality of the electrolyte in the presence of various organic additives, and provides a convenient means for monitoring the content of the organic additives in the copper electrolytic refining production.
Description
Technical Field
The invention relates to the technical field of copper electrolytic refining production, in particular to an analysis method for the quality of electrolyte in copper electrolytic refining.
Background
In the copper electrolytic refining production process, a certain amount of organic additive must be added into the electrolyte, and the addition of the organic additive can adjust the quality of the electrolyte and improve the physical properties of cathode copper. At present, the organic additives commonly used in the domestic copper electrolytic refining industry mainly comprise bone glue and thiourea.
The electrorefining of copper is essentially a process in which copper is dissolved at the anode and subsequently reduced at the cathode. Numerous studies have shown that the effect of different additives on the quality of copper electrolytes can be attributed to the effect of the additives on the reduction process of copper cathodes. The bone glue is usually used as an inhibitor, is beneficial to inhibiting nodulation, can be hydrolyzed to generate ions with positive charges, is adsorbed in an area with an excessively high copper deposition speed on the surface of a cathode, prevents copper ion discharge, and shows the capabilities of increasing cathode overpotential, reducing cathode reduction reaction current, increasing cathode potential change rate and the like. The thiourea generally has a bright effect, cuprous sulfide particles can be formed on cathode copper by the low-concentration thiourea to serve as growth sites of the copper, and therefore the effects of reducing cathode overpotential, increasing cathode reduction reaction current and reducing cathode potential change rate are achieved. In general, the addition of different additives affects the quality of the electrolyte, which can be reflected in the changes of reaction parameters such as cathode overpotential, cathode reduction reaction current and cathode potential change rate. Of particular note are: when a plurality of additives exist in the electrolyte, the influence of the additives on the quality of the electrolyte becomes very complicated due to the interaction between the components of the electrolyte and the additives, and the analysis on the quality of the electrolyte cannot be determined by simply superposing the influences of single additives.
In order to obtain cathode copper with good phase, proper organic additives need to be added, and the action effect of the organic additives can be visually judged by analyzing the quality of the electrolyte. On one hand, different organic additives have different influences on the quality of the electrolyte, and in an actual production process, multiple organic additives are often required to be mixed for use, so that the effect of the mixed multiple organic additives cannot be judged by simply overlapping the functions of the single-component organic additives. Therefore, the effect of the organic additive can be accurately judged by analyzing the quality of the electrolyte. On the other hand, due to the limitation of factors such as process conditions or production requirements, the content of the organic additive in the electrolyte is unstable, the adding amount of the organic additive needs to be adjusted irregularly, the content of the additive is kept within a proper range, and if the adjustment is not timely, the physical properties of the cathode copper may be rapidly deteriorated, and the production cost is increased. Therefore, the quality of the electrolyte in the copper electrolytic refining production can be analyzed, and the adding amount of the organic additive can be adjusted in time, so that the cathode copper with good quality phase can be obtained.
At present, the analysis methods for the quality of the electrolyte at home and abroad mainly comprise methods such as a direct observation method, a chromatographic analysis method, an electrochemical analysis method and the like, the direct observation method and the chromatographic analysis method have the defects of large hysteresis and inaccurate judgment result, and compared with the former two methods, the electrochemical analysis method has the advantages of timely and accurate detection and the like. Electrochemical analysis methods analyze the quality of an electrolyte by measuring the effect of organic additives on the copper anodic oxidation or cathodic reduction process, but most studies have focused on measuring only a single type of organic additive when measuring the effect of organic additives on the copper cathodic reduction reaction. Patent CN1059475C discloses a method for determining the optimum glue concentration by applying a constant current to a movable cathode, measuring the change in the overpotential of the cathode. Another method is mentioned in US4834842, which uses a movable metal wire as cathode and anode, and determines the concentration of animal or synthetic gums by measuring the cathode overpotential by galvanostatic method. Patent JP2002105683A uses a rotating disc electrode to determine the concentration of glue in the copper electrolyte by a galvanostatic method. The method only analyzes the concentration change of a single type of organic additive, and does not consider the influence of a plurality of types of organic additives on the quality of the electrolyte. Therefore, it is very meaningful to design a method capable of rapidly and accurately analyzing the quality of the electrolyte when a plurality of kinds of organic additives are contained in the actual copper electrorefining production process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an analysis method for the quality of electrolyte in copper electrolytic refining. When a plurality of organic additives exist in the electrolyte, the method can analyze the quality of the electrolyte more quickly and accurately.
Firstly, preparing standard solutions containing two organic additives with different concentration ratios, then monitoring the standard solutions by adopting a chronopotentiometry method to obtain corresponding potential change rates, drawing a standard curve by taking the concentration ratio of the two organic additives as a horizontal coordinate and the ratio of the measured potential change rate to the potential change rate of a reference standard solution as a vertical coordinate, and further obtaining a corresponding linear regression equation; and then measuring corresponding potential change rates of different electrolytes to be detected, and analyzing whether the ratio of various additives in the electrolytes to be detected is an optimal value or not through comparison of a standard curve, thereby analyzing the quality of the electrolytes.
The method uses an electrochemical method, has short test time, can accurately analyze the quality of the electrolyte in the presence of various organic additives, and provides a convenient means for monitoring the content of the organic additives in the copper electrolytic refining production.
The technical scheme of the invention is as follows:
a method for analyzing the quality of electrolyte in copper electrolytic refining comprises the following steps:
s1, electrode cleaning:
a micro-disk platinum electrode (with the radius of 250 mu m) is used as a working electrode, the platinum electrode is used as an auxiliary electrode, and a saturated Ag/AgCl electrode is used as a reference electrode to form a three-electrode system, the working electrode and the auxiliary electrode are placed in an electrolytic cell, the reference electrode is connected with the electrolytic cell through a salt bridge and is connected with an electrochemical workstation, a sulfuric acid aqueous solution is injected into the electrolytic cell, the working electrode is electrochemically cleaned by adopting a time potential method and a cyclic voltammetry method respectively, and then the working electrode is cleaned by deionized water for later use;
the concentration of the sulfuric acid aqueous solution is 0.5mol/L;
the parameters of the chronopotentiometry are set as follows: anode current 6X 10 -4 A, anode time is 10-100 s, and initial polarity is set as an anode;
the parameters of the cyclic voltammetry are set as follows: the potential window is-0.15 to 1.5V, the scanning speed is 50mV/s, and the cycle time is 10 circles;
s2, drawing a standard curve:
preparing a standard solution containing an organic additive a and an organic additive b by taking deionized water as a solvent, and recording the concentration of the organic additive a as C a The concentration of the organic additive b is denoted C b With C b /C a A standard solution of =1 as a reference standard solution a;
adding the standard reference solution A into an electrolytic cell, inserting the standard reference solution A into the working electrode and the auxiliary electrode which are washed in the step S1, communicating the reference electrode with the electrolytic cell through a salt bridge, connecting an electrochemical workstation, setting a timing potentiometric experiment parameter for testing, keeping the temperature at 60-65 ℃ (preferably 64 ℃) constant in the testing process, repeating the step three times, recording the potential change rate corresponding to each testing curve, taking the average value of the potential change rates measured in the three times, and recording the average value as K 0 ；
Changing the concentration ratio of the organic additive a and the organic additive b in the standard solution, respectively preparing standard solutions A1, A2, A3, A4, A5 and A6, and measuring K 0 Respectively measuring the corresponding potential change rate average value, and recording as K 1 、K 2 、K 3 、K 4 、K 5 、K 6 (ii) a By concentration of organic additives b and aDegree ratio (C) b /C a ) As the abscissa, the ratio (K) of the corresponding rate of change in potential to that of the reference standard solution A n /K 0 N = 1-6) as a vertical coordinate, and obtaining a standard curve through linear fitting;
the organic additive a is bone glue, and the organic additive b is thiourea; the organic additives a and b have no special meaning, and the marks of a and b are only used for distinguishing different organic additives, and other marks are the same;
concentration C of organic additive a in the standard solution a 0.5-1.5 mg/L, concentration C of organic additive b b 0.5-1.5 mg/L; preferably C in the reference standard solution a Is 1.0mg/L, C b 1.0mg/L;
the reference standard solution A comprises the following specific components: 187g/L copper sulfate pentahydrate, 170g/L sulfuric acid, 1.0mg/L bone glue and 1.0mg/L thiourea;
the parameters of the chronopotentiometry are set as follows: cathode current 6X 10 -5 A, cathode time is 100-300 s, and initial polarity is set as a cathode;
the potential change rate is the maximum value of the slope of the curve obtained by a chronopotentiometry;
specifically, the concentration ratio C of the organic additive b to the organic additive a in the standard solutions A1, A2, A3, A4, A5 and A6 is preferably selected b /C a Respectively 0.5, 0.75, 1.0, 1.33, 1.5 and 2.0, and the rest components are the same as those in the reference standard solution A; the linear regression equation of the constructed standard curve is y = -0.3286x +1.3123, the linear correlation coefficient R =0.9962, and the concentration C of thiourea is b 0.5-1.5 mg/L, bone glue concentration C a 0.5-1.0 mg/L, C b /C a When 0.5 to 2.0, C b /C a Ratio K to rate of change of potential n /K 0 A good linear relationship exists;
s3, sample detection:
adding electrolyte to be tested into the electrolytic cell, and testing according to the same electrochemical test method as S2 to obtain corresponding potential change rate K Measuring Analyzing the standard curve to be measured according to the standard curve obtained in S2The mass of the electrolyte;
the quality analysis method of the electrolyte to be detected comprises the following steps:
(1) Concentration ratio C of two organic additives in electrolyte to be measured b /C a It is known that: calculating K Side survey /K 0 Theoretical value K read from the standard curve Theory of things /K 0 By contrast, a relative error of less than 2.0% is required, then according to K Measuring /K 0 Determining the electrochemical quality of the solution to be tested; k is Measuring /K 0 >1, showing that the solution to be detected has an inhibitor effect, can effectively inhibit the formation of cathode copper nodules, and has excellent electrolyte quality; k Measuring /K 0 <1, the inhibition effect is weakened, and the quality of the electrolyte begins to deteriorate;
(2) Concentration ratio C of two organic additives in electrolyte to be measured b /C a Unknown: calculating K Measuring /K 0 Judging the concentration ratio of the two organic additives according to a standard curve; c b /C a >1, the concentration of the organic additive b is high, and the dosage of the additive b needs to be reduced; c b /C a <1, the organic additive a has large concentration, and the dosage of the additive a needs to be reduced.
The invention has the beneficial effects that:
through an electrochemical method, compared with a standard curve, the quality of the electrolyte in the presence of various organic additives can be accurately analyzed. The time consumption is short, the testing process only needs 300 seconds, and the proportion of the organic additive can be adjusted in time. Provides a convenient means for monitoring the content of the organic additive in the copper electrolytic refining production.
Drawings
Fig. 1 is a schematic diagram of calculating a potential change rate.
FIG. 2 is a chronopotentiometric plot of a standard solution containing two organic additives in different ratios.
FIG. 3 is a graph showing the ratio K of the rate of change in potential of the above-mentioned standard solution n /K 0 Concentration ratio to two organic additives C b /C a The standard curve of (2).
Detailed Description
For a better understanding of the present invention, the following examples are given to illustrate the present invention without limiting the scope of the present invention thereto.
Example 1
In this example, the electrolytic cell was a three-electrode glass electrolytic cell, the working electrode was a microdisk platinum electrode with a radius of 250 μm, the auxiliary electrode was a platinum electrode with an area of 1cm × 1cm, and the reference electrode was a saturated Ag/AgCl electrode.
The composition of the standard solution A is as follows: 187g/L of blue vitriol, 170g/L of sulfuric acid, 1.0mg/L of bone glue and 1.0mg/L of thiourea.
The electrolyte to be tested consists of: 187g/L of blue vitriol, 170g/L of sulfuric acid, 1.0mg/L of bone glue and 0.5mg/L of thiourea.
60mL of 0.5mol/L sulfuric acid is injected into the electrolytic cell, a chronopotentiometry is firstly used for carrying out electrochemical cleaning on a working electrode, and the parameters are as follows: anode current 6X 10 -4 And A, anode time 10s, and initial polarity is set as an anode. The working electrode was then further electrochemically cleaned using cyclic voltammetry with parameters set to: the potential window is-0.15V-1.5V, the scanning speed is 50mV/s, and the cycle times are 10 circles. And then the working electrode is washed clean by deionized water for standby.
Adding 60mL of standard reference solution A into an electrolytic cell, inserting a working electrode and an auxiliary electrode, communicating the reference electrode with the electrolytic cell through a salt bridge, connecting a Chenhua CHI660C electrochemical workstation, and setting experimental parameters of a chronopotentiometry for testing, wherein the parameters are as follows: cathode current 6X 10 -5 And A, cathode time 300s, and initial polarity is set as cathode. The test temperature is 64 ℃, the test is repeated for three times, the potential change rate corresponding to each test curve is recorded, the average value of the potential change rates measured for three times is taken and is marked as K 0 。
And (3) taking 60mL of electrolyte to be tested, and injecting the electrolyte into the electrolytic cell under the same test condition as the measurement standard solution A. Repeating the steps three times, recording the potential change rate corresponding to each test curve, and taking the average value of the potential change rates measured three times as K Measuring . To obtain K Measuring /K 0 =1.1605, test solution C b /C a =0.5, reading the corresponding theoretical value K according to the standard curve Theory of things /K 0 =1.1480, relative error 1.09%, K Measuring /K 0 ＝1.1605>1, the solution to be detected has a strong effect of inhibiting cathode copper nodulation, and the quality of the electrolyte is excellent.
Example 2
The difference between the present embodiment and embodiment 1 is that the electrolyte to be tested has the following composition: 187g/L of blue vitriol, 170g/L of sulfuric acid, 0.5mg/L of bone glue and 1.0mg/L of thiourea. The remaining test procedures were the same as in example 1. To obtain K Measuring /K 0 =0.6543, test solution C b /C a =2, reading the corresponding theoretical value K from the calibration curve Theory of things /K 0 =0.6551, relative error 0.13%, K Measuring /K 0 ＝0.6543<1, the inhibition ability of the solution to be tested is weakened, and the quality of the electrolyte may begin to deteriorate.
Example 3
The difference between the present embodiment and embodiment 1 is that the electrolyte to be tested has the following components: 187g/L of blue copperas, 170g/L of sulfuric acid, bone glue and thiourea are unknown in proportion. The remaining test procedures were the same as in example 1. To obtain K Measuring /K 0 =1.0393, and is known as y = -0.3286x +1.3123 according to the standard curve linear regression equation, C b /C a ＝0.83，K Side survey /K 0 ＝1.0393>1, the electrolyte to be detected has excellent quality, and the concentration ratio of the organic additive bone glue to the thiourea is 0.83.
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 (8)
1. A method for analyzing the quality of electrolyte in copper electrolytic refining is characterized by comprising the following steps:
s1, electrode cleaning:
the method comprises the following steps of (1) forming a three-electrode system by taking a micro-disk platinum electrode as a working electrode, a platinum electrode as an auxiliary electrode and a saturated Ag/AgCl electrode as a reference electrode, placing the working electrode and the auxiliary electrode in an electrolytic cell, connecting the reference electrode with the electrolytic cell through a salt bridge, connecting an electrochemical workstation, injecting a sulfuric acid aqueous solution into the electrolytic cell, respectively carrying out electrochemical cleaning on the working electrode by adopting a time potential method and a cyclic voltammetry method, and then washing the working electrode by using deionized water for later use;
s2, drawing a standard curve:
preparing a standard solution containing an organic additive a and an organic additive b by taking deionized water as a solvent, and marking the concentration of the organic additive a as C a The concentration of the organic additive b is denoted C b With C b /C a A standard solution of =1 as a reference standard solution a;
adding the standard reference solution A into an electrolytic cell, inserting the working electrode and the auxiliary electrode which are cleaned in the step S1, communicating the reference electrode with the electrolytic cell through a salt bridge, connecting an electrochemical workstation, setting experimental parameters of a timing potential method for testing, keeping the temperature at 60-65 ℃ in the testing process, repeating the testing process for three times, recording the potential change rate corresponding to each testing curve, taking the average value of the potential change rates measured for three times, and recording the average value as K 0 ；
Changing the concentration ratio of the organic additive a and the organic additive b in the standard solution, respectively preparing standard solutions A1, A2, A3, A4, A5 and A6, and measuring K 0 Respectively measuring the corresponding potential change rate average value, and recording as K 1 、K 2 、K 3 、K 4 、K 5 、K 6 (ii) a Taking the concentration ratio of the organic additive b to the organic additive a as an abscissa, taking the ratio of the corresponding potential change rate to the potential change rate of the reference standard solution A as an ordinate, and obtaining a standard curve through linear fitting;
the organic additive a is bone glue, and the organic additive b is thiourea;
s3, sample detection:
adding electrolyte to be tested into the electrolytic cell, and testing according to the same electrochemical test method as S2 to obtain corresponding potential change rate K Side survey Analyzing the quality of the electrolyte to be tested according to the standard curve obtained in the S2;
the quality analysis method of the electrolyte to be detected comprises the following steps:
(1) Concentration ratio C of two organic additives in electrolyte to be measured b /C a It is known that: calculating K Measuring /K 0 Theoretical value K read from the standard curve Theory of things /K 0 By contrast, a relative error of less than 2.0% is required, then according to K Side survey /K 0 Determining the electrochemical quality of the solution to be tested; k is Side survey /K 0 >1, the solution to be detected has an inhibitor effect, can effectively inhibit the formation of cathode copper nodules, and has excellent electrolyte quality; k is Side survey /K 0 <1, the suppression effect is weakened, and the quality of the electrolyte begins to deteriorate;
(2) Concentration ratio C of two organic additives in electrolyte to be measured b /C a Unknown: calculating K Side survey /K 0 Judging the concentration ratio of the two organic additives according to a standard curve; c b /C a >1, the concentration of the organic additive b is high, and the dosage of the additive b needs to be reduced; c b /C a <1, the organic additive a has high concentration, and the dosage of the additive a needs to be reduced.
2. The method of analyzing the quality of an electrolytic solution in copper electrorefining according to claim 1, wherein the concentration of said sulfuric acid aqueous solution in S1 is 0.5mol/L.
3. The method for analyzing the quality of an electrolytic solution in copper electrorefining as claimed in claim 1, wherein the parameters of said chronopotentiometry in S1 are set as: anode current 6X 10 -4 And A, setting the anode time to be 10-100 s and the initial polarity as the anode.
4. A method for analyzing the quality of an electrolyte in copper electrorefining as claimed in claim 1, wherein the parameters of the cyclic voltammetry in S1 are set as: the potential window is-0.15-1.5V, the scanning speed is 50mV/s, and the cycle time is 10 circles.
5. The method for analyzing electrolyte quality in copper electrorefining as claimed in claim 1, wherein the concentration C of the organic additive a in said standard solution in S2 a 0.5-1.5 mg/L, concentration C of organic additive b b Is 0.5-1.5 mg/L.
6. The method for analyzing the quality of an electrolytic solution in copper electrorefining according to claim 1, wherein the reference standard solution a in S2 has the following composition: 187g/L of blue vitriol, 170g/L of sulfuric acid, 1.0mg/L of bone glue and 1.0mg/L of thiourea.
7. The method for analyzing the quality of an electrolyte in copper electrorefining as claimed in claim 1, wherein the parameters of said chronopotentiometry in S2 are set as: cathode current 6X 10 -5 A, cathode time is 100-300 s, and initial polarity is set as a cathode; the potential change rate is the maximum value of the slope of the curve obtained by the chronopotentiometry.
8. The method for analyzing the quality of an electrolytic solution in copper electrorefining as claimed in claim 1, wherein the concentration ratio C of the organic additive b to the organic additive a in the standard solutions A1, A2, A3, A4, A5, A6 in S2 is set to b /C a 0.5, 0.75, 1.0, 1.33, 1.5, 2.0, respectively; concentration of Thiourea in Standard solution C b 0.5-1.5 mg/L, bone glue concentration C a 0.5-1.0 mg/L; the linear regression equation of the constructed standard curve is y = -0.3286x +1.3123, and the linear correlation coefficient R =0.9962.
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