CN113668018B - Electrolytic copper impurity online detection method - Google Patents
Electrolytic copper impurity online detection method Download PDFInfo
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- CN113668018B CN113668018B CN202110854298.2A CN202110854298A CN113668018B CN 113668018 B CN113668018 B CN 113668018B CN 202110854298 A CN202110854298 A CN 202110854298A CN 113668018 B CN113668018 B CN 113668018B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000012535 impurity Substances 0.000 title claims abstract description 67
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 57
- 239000010949 copper Substances 0.000 title claims abstract description 57
- 238000001514 detection method Methods 0.000 title claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 171
- 238000000034 method Methods 0.000 claims abstract description 53
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 13
- 238000005070 sampling Methods 0.000 claims description 14
- 238000012423 maintenance Methods 0.000 claims description 9
- 238000011156 evaluation Methods 0.000 claims description 6
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 239000012488 sample solution Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
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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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- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses an electrolytic copper impurity online detection method. The method aims to solve the problem that the prior art cannot detect the content of impurity elements in electrolyte at different positions; the invention comprises the following steps: s1: collecting electrolytes at different positions in an electrolytic cell at an initial frequency; s2: respectively detecting the content of elements in the electrolyte through a detection device, and comparing and judging the content with a preset electrolyte element content table; replacing electrolyte or continuing the copper electrolysis process according to the judgment result; s3: calling historical data, predicting the change of impurity elements in the electrolyte, adjusting the electrolyte acquisition frequency of different positions, and returning to the step S1 to sample the electrolyte by using the adjusted acquisition frequency; s4: and after the electrolytic copper process is finished, adding the data into a historical database. The electrolytes in different positions are sampled by adopting different acquisition frequencies, so that the content of impurity elements in the electrolytes in different positions can be detected on line, and the detection result is more accurate and reliable.
Description
Technical Field
The invention relates to the field of electrolytic copper, in particular to an electrolytic copper impurity online detection method.
Background
The efficiency of copper electrolysis is affected by the precipitation of impurity elements during the copper electrolysis, wherein the potential of some impurity elements is close to that of copper, but the impurity elements are more electronegative than the copper, such as arsenic, antimony and bismuth. Although the potentials of these three elements are relatively close to those of copper, the low content thereof generally makes it difficult to precipitate at the cathode during normal electrolysis. When the anode is dissolved, these elements become ions which enter the solution, mostly hydrolyze into solid oxides, and a part accumulates in the electrolyte. The harm degree of the three impurities to the electrolytic copper is far greater than that of other impurities, particularly antimony, and when the Sb content in the electrolyte exceeds 0.6g/L and reaches more than 0.8gL, floating anode mud is easily formed and attached to the upper part of the cathode, so that long particles are formed on the upper part of the cathode.
For example, a method for measuring the concentration of Fe2+ in an electrolyte disclosed in chinese patent document, which is referred to as CN111272684A, comprises the steps of: preparing a detection object solution; preparing a plurality of electrolytes containing Fe2 +; mixing the plurality of electrolytes with the detection object solution respectively to obtain a plurality of sample solutions; detecting the plurality of sample solutions by adopting an ultraviolet-visible spectrophotometry method to obtain the absorbance of the detection object in the plurality of sample solutions, and calculating to obtain a standard curve equation of the concentration of Fe2+ in the electrolyte and the absorbance of the detection object in the sample solutions; mixing the electrolyte to be detected with the solution of the detection object to obtain a solution to be detected, detecting the solution to be detected by adopting an ultraviolet-visible spectrophotometry method to obtain the absorbance of the detection object in the solution to be detected, and calculating through a standard curve equation to obtain the concentration of Fe2+ in the electrolyte to be detected.
The impurity element content at different positions in the electrolyte is different, the impurity element content at different positions cannot be detected by the scheme, and the result is inaccurate.
Disclosure of Invention
The invention mainly solves the problem that the prior art can not detect the content of impurity elements in electrolyte at different positions; the method for detecting the impurities in the electrolytic copper on line is provided, the electrolytes in different positions are collected to detect the content of the impurity elements, the collection frequency is adjusted according to historical data, and the accuracy and the efficiency of detection results are improved.
The technical problem of the invention is mainly solved by the following technical scheme:
an electrolytic copper impurity online detection method comprises the following steps:
s1: collecting electrolytes at different positions in an electrolytic cell at an initial frequency, and respectively sending the collected electrolytes to a detection device outside the electrolytic cell;
s2: respectively detecting the content of elements in the electrolyte through a detection device, and comparing and judging the content with a preset electrolyte element content table; executing maintenance action or continuing the copper electrolysis process according to the judgment result;
s3: taking the replacement of the once electrolyte as a period, calling historical data of each period, predicting the change of impurity elements in the electrolyte by combining the service time of the current electrolyte, respectively adjusting the electrolyte acquisition frequencies of different positions, and returning to the step S1 to sample the electrolyte by using the adjusted acquisition frequencies;
s4: and taking out the cathode copper after the electrolytic copper process is finished, analyzing the quality of the cathode copper, and adding a cathode copper quality result and an element content result of the electrolyte in the electrolytic copper process into a historical database.
The electrolyte at different positions is sampled by adopting different acquisition frequencies, the content of impurity elements in the electrolyte at different positions can be detected on line, whether the content of the impurity elements can influence the copper electrolysis process or not is judged by looking up the table at the acquired positions, whether the electrolyte is replaced or not is decided according to the judgment result, and the detection result is more accurate and reliable.
Preferably, the electrolyte at different positions in the electrolytic cell at least comprises electrolyte at two sides of each cathode plate and electrolyte at one side of the anode facing the cathode plate; each position includes at least three collection points in the depth direction, a bottom portion, a middle portion, and an upper portion. The impurity elements are simultaneously collected at different depths of the same position, and the content distribution of the impurity elements in the depth direction can be obtained.
Preferably, the element content of the electrolyte is detected by ICP-MS, the electrolytes at different positions respectively correspond to an electrolyte element content table, and the electrolyte element content table comprises element types and an element content allowable range; classifying the impurity elements according to the potentials of the impurity elements, wherein the impurity elements comprise first-class elements, second-class elements, third-class elements and fourth-class elements; the element of one type is more electronegative than copper; the second element is an element with a positive potential compared with copper; the three elements are elements with the potential close to that of copper but with electronegativity higher than that of copper; the four elements are other impurities. The method classifies the influence of impurity elements on the electrolytic copper process, and improves the service efficiency of the electrolyte because the standards for replacing the electrolyte are different after the content of different impurity elements exceeds the limit.
Preferably, when the detected element content of the electrolyte is within the corresponding element content allowable range, the copper electrolysis process is continuously executed;
when the element content of one of the three elements is detected to be out of the corresponding element content allowable range, alarming is carried out, and the electrolyte is replaced or the process is adjusted;
when the element content of three or more elements of one type or four types is detected to be out of the corresponding element content allowable range, alarming is carried out, and the electrolyte is replaced or the process is adjusted;
when detecting that the element content of one type of element or four types of elements exceeds the corresponding element content allowable range by 3 percent or more, alarming, replacing the electrolyte or adjusting the process;
and when the element content of the second-class elements is detected to be out of the corresponding element content allowable range, alarming, replacing the electrolyte or adjusting the process.
The standards for replacing the electrolyte after the content of different impurity elements exceeds the limit are different, so that the service efficiency of the electrolyte is improved.
Preferably, the step S3 includes the following steps:
s31: taking one maintenance action as one period in the historical database, and storing the content of each element at different positions in the electrolyte at different moments in each period;
s32: reading the current service time of the electrolyte, calling the electrolyte element content data of the same time period in each period in a historical database, and matching the closest period according to the comparison of the electrolyte element content of different positions;
s33: respectively adjusting the electrolyte acquisition frequencies at different positions according to the element content change at the next moment in the nearest period;
s34: returning to step S1, the electrolyte at different positions is collected at the adjusted electrolyte collection frequency.
The electrolyte collection frequency is adjusted according to the estimation of the element content of different positions, the collection and detection efficiency is improved, the invalid collection is reduced, and the energy cost is saved.
Preferably, the element contents of different positions are respectively taken and respectively differed from the element contents of the electrolyte in the same time period in each period to obtain a content difference value delta H;
taking the weighted sum of the content difference of each element as a difference value P;
P＝A*(ΔH a1 +…+ΔH am )+…+B*(ΔH b1 +…+ΔH bm )+…+C*(ΔH c1 +…+ΔH cm )+…+D*(ΔH d1 +…+ΔH dm )
wherein A is the coefficient of the content difference of the first-class elements;
b is the coefficient of the content difference of the two types of elements;
c is the coefficient of the content difference of the three elements;
d is the coefficient of the content difference of the four elements;
ΔH am is the difference value of the mth class element;
ΔH bm is the m second type element difference;
ΔH cm is the m three-type element difference value;
ΔH dm is the difference value of the mth four-type element;
the difference value P of the electrolyte close to the cathode plate side n Difference value P from electrolyte near anode side p Weighting to obtain an evaluation value K;
K＝E*(P n1 +…+P nn )+F*(P p1 +…+P pn )
wherein E is the difference value P of the electrolyte close to the cathode plate side n The weighting coefficient of (2);
f is the difference P of the electrolyte near the anode side p The weighting coefficient of (2);
P nn the difference value P of the electrolyte close to the cathode plate side of the nth collection point n ；
P pn The difference value P of the electrolyte close to the anode side of the nth collection point n ；
The cycle corresponding to the minimum evaluation value K is taken as the closest cycle.
The change of the element content is estimated by determining the nearest period through historical data.
Preferably, a maximum value f of the acquisition frequency is set max And minimum value f of acquisition frequency min ；
Dividing the acquisition frequency into X levels, and calculating an acquisition frequency interval delta f;
setting the standard content
Respectively adjusting the electrolyte acquisition frequencies at different positions according to the element content change at the next moment in the nearest period;
wherein f is i Electrolyte collection frequency of the ith sampling point;
ρ i，t+1 the total content of impurity elements of the electrolyte at the next moment in the closest period is the ith sampling point;
ρ i，t the total content of impurity elements in the electrolyte at the current moment of the ith sampling point.
And modifying the sampling frequency according to the estimation of the element content of different positions, and improving the sampling efficiency.
The invention has the beneficial effects that:
1. the electrolytes in different positions are sampled by adopting different acquisition frequencies, so that the content of impurity elements in the electrolytes in different positions can be detected on line, and the detection result is more accurate and reliable.
2. Whether the content of the impurity element can influence the copper electrolysis process is judged by looking up the table according to the collected position, whether the electrolyte is replaced is decided according to the judgment result, and the reliability of the detection result and the use efficiency of the electrolyte are improved.
3. The method is characterized in that the method is classified according to the influence of impurity elements on the electrolytic copper process, and the standards for replacing the electrolyte are different after the content of different impurity elements exceeds the limit, so that the service efficiency of the electrolyte is improved.
4. The electrolyte collection frequency is adjusted according to the estimation of the element content of different positions, the collection and detection efficiency is improved, the invalid collection is reduced, and the energy cost is saved.
Drawings
FIG. 1 is a flow chart of the electrolytic copper impurity online detection method of the present invention.
Detailed Description
The technical scheme of the invention is further specifically described by the following embodiments and the accompanying drawings.
Example (b):
the method for detecting impurities in electrolytic copper on line in the embodiment, as shown in fig. 1, includes the following steps:
s1: collecting electrolytes at different positions in the electrolytic cell at an initial frequency, and respectively sending the collected electrolytes to a detection device outside the electrolytic cell.
In this example, the electrolyte was tested for elemental content by ICP-MS.
The electrolyte in different positions in the electrolytic bath at least comprises the electrolyte at two sides of each cathode plate and the electrolyte at one side of the anode facing the cathode plate.
Each position includes at least three collection points in the depth direction, a bottom portion, a middle portion, and an upper portion. The elemental content values for a location were averaged over the elemental content detected at the bottom, middle and upper three collection points of the location.
The impurity elements are simultaneously collected at different depths of the same position, and the content distribution of the impurity elements in the depth direction can be obtained. And calculating standard deviation, comparing with a standard threshold value to judge whether the contents of the elements at different depths are uniform, if so, calculating the contents of all the elements at the position, and if not, giving an alarm to inform a worker.
S2: respectively detecting the content of elements in the electrolyte through a detection device, and comparing and judging the content with a preset electrolyte element content table; and executing maintenance action or continuing the copper electrolysis process according to the judgment result.
The maintenance action includes replacing the electrolyte or adjusting the process. The electrolytic plant mainly controls the quality of cathode copper, and the adjustment process comprises changing the process according to harmful components in the electrolyte to ensure the quality of the cathode copper. The feedback reminds the upstream station of the impurity removal problem.
The electrolytes at different positions correspond to the electrolyte element content tables, which in this embodiment include the cathode-side electrolyte element content table and the anode-side electrolyte element content table. The electrolyte element content table comprises element types and element content allowable ranges.
The impurity elements are classified according to their potentials, and include first-class elements, second-class elements, third-class elements, and fourth-class elements.
One type of element is an element that is more electronegative than copper; such as iron, tin, lead, cobalt, nickel.
During anode dissolution, the impurity elements enter the electrolyte as divalent ions, lead and tin generate insoluble oxides and are transferred into anode mud, and the rest is accumulated in the electrolyte.
The second element is an element with a positive potential compared with copper; such as silver, gold, platinum group elements.
Since the electrode potential of these elements is more positive than that of copper, almost all of them enter into the sludge during the electrolysis, and only a trace amount of electrolytic copper exists.
The three elements are elements with the potential close to that of copper but with electronegativity higher than that of copper; such as arsenic, antimony, bismuth.
Although the potentials of these three elements are relatively close to those of copper, the low content thereof generally makes it difficult to precipitate at the cathode during normal electrolysis.
When the anode is dissolved, these elements become ions which enter the solution, mostly hydrolyze into solid oxides, and a part accumulates in the electrolyte. The harm degree of the three impurities to the electrolytic copper is far larger than that of other impurities, particularly antimony, and when the Sb content in the electrolyte exceeds more than 0.6g/LO.8gL, floating anode mud is easily formed and attached to the upper part of the cathode, so that long particles are formed on the upper part of the cathode.
Generally, the three impurity contents in the electrolyte are specified as follows: as is less than 3.5gL, Sb is less than 0.6gL, and Bi is less than 0.5 g/L.
The four elements are other impurities; such as oxygen, sulfur, selenium, silicon, etc.
And when the detected element content of the electrolyte is within the corresponding element content allowable range, continuously executing the electrolytic copper process.
And when the element content of one of the three elements is detected to be out of the corresponding element content allowable range, alarming, replacing the electrolyte or adjusting the process. The third element has a greater influence on electrolytic copper.
And when the element content of three or more elements of one type or four types is detected to be out of the corresponding element content allowable range, alarming, replacing the electrolyte or adjusting the process.
And when detecting that the element content of one type of element or four types of elements exceeds the corresponding element content allowable range by 3 percent or more, alarming, replacing the electrolyte or adjusting the process.
And when the element content of the second-class elements is detected to be out of the corresponding element content allowable range, alarming, replacing the electrolyte or adjusting the process.
The method is characterized in that the method is classified according to the influence of impurity elements on the electrolytic copper process, and the standards for replacing the electrolyte are different after the content of different impurity elements exceeds the limit, so that the service efficiency of the electrolyte is improved.
The logic of whether or not to replace the electrolyte is determined based on the element content on the cathode plate side.
When the element content on the cathode plate side is within the allowable range of the element content but the element content on the anode side is outside the allowable range of the corresponding element content, the acquisition frequency on the cathode plate side is increased to the maximum value f of the acquisition frequency max (ii) a Sampling the anode side after the interval of the rated time T, and if the element content of the anode side is still outside the corresponding element content allowable range, keeping the maximum acquisition frequency of the cathode until the electrolyte is judged to need to be replaced; otherwise, the acquisition frequency on the cathode plate side is recovered.
S3: and taking the execution of one maintenance action as one period, calling historical data of each period, predicting the change of impurity elements in the electrolyte by combining the current service time of the electrolyte, respectively adjusting the electrolyte acquisition frequencies at different positions, and returning to the step S1 to sample the electrolyte by using the adjusted acquisition frequencies.
S31: and the historical database stores the content of each element at different positions in the electrolyte at different moments in each period by taking one maintenance action as one period.
S32: and reading the current service time of the electrolyte, calling the electrolyte element content data of the same time period in each period in the historical database, and matching the closest period according to the comparison of the electrolyte element contents of different positions.
And respectively taking the element contents of different positions, and respectively making a difference with the element contents of the electrolyte in the same time period of each period to obtain a content difference value delta H.
Taking the weighted sum of the content differences of the elements as a difference value P:
P＝A*(ΔH a1 +…+ΔH am )+…+B*(ΔH b1 +…+ΔH bm )+…+C*(ΔH c1 +…+ΔH cm )+…+D*(ΔH d1 +…+ΔH dm )
wherein A is the coefficient of the content difference of the first-class elements;
b is the coefficient of the content difference of the two types of elements;
c is the coefficient of the content difference of the three elements;
d is the coefficient of the content difference of the four elements;
ΔH am is the difference value of the mth class element;
ΔH bm is the m second type element difference;
ΔH cm is the m three-type element difference value;
ΔH dm is the mth difference of the four types of elements.
In the present embodiment, the number m of the four elements may take different values.
The difference value P of the electrolyte close to the cathode plate side n Difference value P from electrolyte near anode side p Weighting to obtain an evaluation value K:
K＝E*(P n1 +…+P nn )+F*(P p1 +…+P pn )
wherein E is the difference value P of the electrolyte close to the cathode plate side n The weighting coefficient of (2);
f is the difference P of the electrolyte near the anode side n Is weightedCounting;
the weighting coefficients E and F are obtained from a limited number of experiments.
P nn The difference value P of the electrolyte close to the cathode plate side of the nth collection point n ；
P pn The difference value P of the electrolyte close to the anode side of the nth collection point n 。
In the present embodiment, the number n of sampling points on the cathode-side and anode-side may take different values.
The cycle corresponding to the minimum evaluation value K is taken as the closest cycle.
S33: and respectively adjusting the electrolyte acquisition frequencies at different positions according to the element content change at the next moment in the nearest period.
Setting the maximum value f of the acquisition frequency max And minimum value f of acquisition frequency min ；
Dividing the acquisition frequency into X levels, and calculating an acquisition frequency interval delta f;
setting the standard content
Respectively adjusting the electrolyte acquisition frequencies at different positions according to the element content change at the next moment in the nearest period;
s.t.f min ≤f≤f max
wherein f is i Electrolyte collection frequency of the ith sampling point;
ρ i，t+1 the total content of impurity elements of the electrolyte at the next moment in the closest period is the ith sampling point;
ρ i，t the total content of impurity elements of the electrolyte at the current moment of the ith sampling pointAmount of the compound (A).
The electrolyte collection frequency is adjusted according to the estimation of the element content of different positions, the collection and detection efficiency is improved, the invalid collection is reduced, and the energy cost is saved.
S34: returning to step S1, the electrolyte at different positions is collected at the adjusted electrolyte collection frequency.
S4: and taking out the cathode copper after the electrolytic copper process is finished, analyzing the quality of the cathode copper, and adding a cathode copper quality result and an element content result of the electrolyte in the electrolytic copper process into a historical database.
The scheme of this embodiment adopts different collection frequency to sample to the electrolyte of different positions, can the on-line measuring go out the content of impurity element in the electrolyte of different positions, and the testing result is more accurate reliable. Whether the content of the impurity element can influence the copper electrolysis process is judged by looking up the table according to the collected position, whether the electrolyte is replaced is decided according to the judgment result, and the reliability of the detection result and the use efficiency of the electrolyte are improved.
The method is characterized in that the method is classified according to the influence of impurity elements on the electrolytic copper process, and the standards for replacing the electrolyte are different after the content of different impurity elements exceeds the limit, so that the service efficiency of the electrolyte is improved. The electrolyte collection frequency is adjusted according to the estimation of the element content of different positions, the collection and detection efficiency is improved, the invalid collection is reduced, and the energy cost is saved.
It should be understood that the examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Claims (5)
1. An electrolytic copper impurity online detection method is characterized by comprising the following steps:
s1: collecting electrolytes at different positions in an electrolytic cell at an initial frequency, and respectively sending the collected electrolytes to a detection device outside the electrolytic cell;
s2: respectively detecting the content of elements in the electrolyte through a detection device, and comparing and judging the content with a preset electrolyte element content table; executing maintenance action or continuing the copper electrolysis process according to the judgment result;
s3: taking the execution of one maintenance action as one period, calling historical data of each period, predicting the change of impurity elements in the electrolyte by combining the service time of the current electrolyte, respectively adjusting the electrolyte acquisition frequencies at different positions, and returning to the step S1 to sample the electrolyte by using the adjusted acquisition frequencies;
the step S3 includes the following steps:
s31: taking one maintenance action as one period in the historical database, and storing the content of each element at different positions in the electrolyte at different moments in each period;
s32: reading the current service time of the electrolyte, calling the electrolyte element content data of the same time period in each period in a historical database, and matching the closest period according to the comparison of the electrolyte element content of different positions;
respectively taking the element contents of different positions, and respectively making difference with the element contents of the electrolyte in the same time period of each period to obtain a content difference value
；
Taking the weighted sum of the content difference of each element as a difference value P;
wherein A is the coefficient of the content difference of the first-class elements;
b is the coefficient of the content difference of the two types of elements;
c is the coefficient of the content difference of the three elements;
d is the coefficient of the content difference of the four elements;
difference value of electrolyte near to cathode plate side
Difference value with electrolyte near anode side
Weighting to obtain an evaluation value K;
wherein E is the difference value of the electrolyte close to the cathode plate side
The weighting coefficient of (2);
f is the difference value of the electrolyte close to the anode side
The weighting coefficient of (2);
Taking the period corresponding to the minimum evaluation value K as the nearest period;
s33: respectively adjusting the electrolyte acquisition frequencies at different positions according to the element content change at the next moment in the nearest period;
s34: returning to the step S1, collecting the electrolytes at different positions by the adjusted electrolyte collection frequency;
s4: and taking out the cathode copper after the electrolytic copper process is finished, analyzing the quality of the cathode copper, and adding a cathode copper quality result and an element content result of the electrolyte in the electrolytic copper process into a historical database.
2. The method for detecting impurities in electrolytic copper on line as claimed in claim 1, wherein the electrolyte at different positions in the electrolytic cell comprises at least electrolyte at two sides of each cathode plate and electrolyte at one side of the anode facing the cathode plate; each position includes at least three collection points in the depth direction, a bottom portion, a middle portion, and an upper portion.
3. The method for detecting impurities in electrolytic copper on line according to claim 1 or 2, wherein the electrolytic solution is detected for element content by ICP-MS, the electrolytic solutions at different positions respectively correspond to an electrolytic solution element content table, and the electrolytic solution element content table comprises element types and element content allowable ranges; classifying the impurity elements according to the potentials of the impurity elements, wherein the impurity elements comprise a first-class element, a second-class element, a third-class element and a fourth-class element; the element of one type is more electronegative than copper; the second element is an element with a positive potential compared with copper; the three elements are elements with the potential close to that of copper but with electronegativity higher than that of copper; the four elements are other impurities.
4. The method for detecting impurities in electrolytic copper on line according to claim 3, wherein when the detected element contents of the electrolyte are all within the corresponding allowable element content ranges, the electrolytic copper process is continuously executed;
when the element content of one of the three elements is detected to be out of the corresponding element content allowable range, alarming is carried out, and the electrolyte is replaced or the process is adjusted;
when the element content of three or more elements of one type or four types is detected to be out of the corresponding element content allowable range, alarming is carried out, and the electrolyte is replaced or the process is adjusted;
when detecting that the element content of one type of element or four types of elements exceeds the corresponding element content allowable range by 3 percent or more, alarming, replacing the electrolyte or adjusting the process;
and when the element content of the second-class elements is detected to be out of the corresponding element content allowable range, alarming, replacing the electrolyte or adjusting the process.
5. The method of claim 1, wherein the maximum value of the sampling frequency is set
And minimum value of acquisition frequency
；
Dividing the collection frequency into X levels, calculating the collection frequency interval
；
Setting the standard content
(ii) a Respectively adjusting the electrolyte acquisition frequencies at different positions according to the element content change at the next moment in the nearest period;
wherein,
electrolyte collection frequency of the ith sampling point;
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