Method for compensating concentration of electrolyte in real time in copper-zinc electrodeposition process

Abstract

The invention relates to the technical field of electrolytic deposition, and discloses an electrolyte concentration real-time compensation method in a copper-zinc electrodeposition process. Comprising the following steps: synchronously acquiring copper ion concentration data, zinc ion concentration data, sulfate ion concentration data and chloride ion concentration data in an upper layer fixed sampling position set, a middle layer fixed sampling position set, a lower layer fixed sampling position set and an electrode adjacent region fixed sampling position set according to a fixed time sampling window; performing time continuity verification, space consistency verification and ratio change track consistency verification on the concentration data, establishing a reference interval, and generating a deviation level and state label set; and executing a segmented compensation path according to the state label set, and carrying out sequence adjustment on copper salt solution adding rate setting data, zinc salt solution adding rate setting data, water supplementing dilution amount setting data, circulating flow setting data and stirring rotation speed setting data. According to the invention, fast steady state recovery can be realized and the overcompensation risk can be reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrolytic deposition, in particular to a method for real-time compensation of electrolyte concentration in copper-zinc electrodeposition process. BACKGROUND

[0002] Copper-zinc electrodeposition is to make metal ions reduced and deposited on the cathode with constant or segmented current density. The concentration stability of copper ions, zinc ions, sulfate ions and chloride ions in the electrolyte directly affects the current efficiency, cathode grain morphology, impurity entrainment rate and unit energy consumption. In industrial field, off-line results of laboratory titration / spectroscopic test are often combined with shift adjustment, and on-line single-point or indirect quantity of ion selective electrode, photometric probe, cell voltage, conductivity and redox potential are used for process control. The addition of salt, water, circulation and stirring intensity are determined by experience threshold or historical model.

[0003] The key defects of the prior art mainly include: single-point or indirect quantity cannot identify the spatial non-uniformity of the tank in the same time window, cannot distinguish the concentration gradient and boundary layer effect of the upper layer, the middle layer, the lower layer and the electrode adjacent area, and local disturbance is easily regarded as overall deviation, which causes false compensation and oscillation; the fixed threshold and the historical model have poor adaptability to changes in incoming liquid composition, load and temperature, the threshold needs to be manually adjusted for a long time, and over-compensation or under-compensation may occur during working condition switching, resulting in decreased current efficiency, increased chemical consumption and energy consumption, and fluctuation of cathode quality.

[0004] Therefore, it is necessary to provide a method for real-time compensation of electrolyte concentration in copper-zinc electrodeposition process, so as to accurately identify the concentration deviation and implement stable and rapid compensation control in the running period, thereby inhibiting oscillation, shortening the adjustment time, and improving the current efficiency and product consistency. SUMMARY

[0005] In view of this, the present application provides a method for real-time compensation of electrolyte concentration in copper-zinc electrodeposition process to solve the above problems.

[0006] The method for real-time compensation of electrolyte concentration in copper-zinc electrodeposition process provided by the present application comprises:

[0007] The copper ion concentration data, the zinc ion concentration data, the sulfate ion concentration data and the chloride ion concentration data are collected at the fixed sampling position set of the upper layer, the fixed sampling position set of the middle layer, the fixed sampling position set of the lower layer and the fixed sampling position set of the electrode adjacent area at the same fixed time sampling window to form the concentration data arranged by position and time;

[0008] The concentration data is subjected to time continuity verification and spatial consistency verification based on the change relationship of the same fixed sampling position in adjacent fixed time sampling windows and the relative deviation between the same fixed sampling positions in the same fixed time sampling window, and the concentration data is subjected to ratio change trajectory consistency verification based on the ratio change relationship between metal ions and anions, to obtain verified concentration data;

[0009] A reference interval is established and the verified concentration data is compared with the reference interval to generate a deviation level and a state label set;

[0010] A segmented compensation path is performed according to the state label set, and sequence adjustment is performed on the copper salt solution addition rate setting data, the zinc salt solution addition rate setting data, the water dilution amount setting data, the circulation flow rate setting data and the stirring speed setting data until the copper ion concentration data and the zinc ion concentration data meet the reference interval and the sulfate ion concentration data and the chloride ion concentration data are in a stable interval.

[0011] Further, at least two fixed sampling positions are arranged in each of the upper fixed sampling position set, the middle fixed sampling position set, the lower fixed sampling position set and the electrode adjacent zone fixed sampling position set, and the copper ion concentration data, the zinc ion concentration data, the sulfate ion concentration data and the chloride ion concentration data are recorded synchronously in the same fixed time sampling window; when the concentration data of a single fixed sampling position is missing in a single fixed time sampling window, the average of the concentration data of the two adjacent fixed sampling positions in the same fixed time sampling window is backfilled once; when the concentration data of the same fixed sampling position is missing in two or more consecutive fixed time sampling windows, the fixed sampling position is excluded from the time continuity verification and the comparison, and only participates in the layerwise statistics of the spatial consistency verification.

[0012] Further, the time continuity verification is based on the change direction and change amplitude of the copper ion concentration data, the zinc ion concentration data, the sulfate ion concentration data and the chloride ion concentration data of the same fixed sampling position in three consecutive fixed time sampling windows, when the direction alternates and the change amplitude is lower than a preset micro-amplitude threshold, the linear extrapolation value of the previous fixed time sampling window and the next fixed time sampling window of the fixed sampling position is used to replace the concentration data of the middle fixed time sampling window; when the direction alternates for the second time and the change amplitude is lower than the preset micro-amplitude threshold, the subsequent concentration data of the fixed sampling position in the comparison is counted according to a preset weight reduction coefficient.

[0013] Further, the spatial consistency check takes the relative deviation between the fixed sampling positions of the same layer within the same fixed time sampling window as the basis, sorts the deviation of the fixed sampling positions of the same layer from the median value in the layer, and eliminates the single fixed sampling position with the largest deviation as the outlier fixed sampling position; when the relative deviation direction of the upper fixed sampling position set and the lower fixed sampling position set is opposite and the concentration difference between the electrode adjacent area fixed sampling position set and the main body area fixed sampling position set increases, the elimination of the outlier fixed sampling position is cancelled, and all fixed sampling positions in the fixed time sampling window are uniformly counted according to the preset weight reduction coefficient.

[0014] Further, the establishment of the reference interval includes initialization sampling window and sliding update: the initialization sampling window remains without compensation, and the upper and lower limits are determined as the initialization reference interval by the checked copper ion concentration data, the checked zinc ion concentration data, the checked sulfate ion concentration data and the checked chloride ion concentration data respectively; in the running process, the checked copper ion concentration data, the checked zinc ion concentration data, the checked sulfate ion concentration data and the checked chloride ion concentration data of the last several fixed time sampling windows are used to update the sliding reference interval, and the sliding reference interval is frozen in the main compensation execution section and the setting verification section of the segmented compensation path.

[0015] Further, the ratio change trajectory consistency check takes the ratio change trajectory between the copper ion concentration data and the zinc ion concentration data, and the ratio change trajectory of the copper ion concentration data and the zinc ion concentration data relative to the sum of the sulfate ion concentration data and the chloride ion concentration data as the basis, extracts the ratio reference interval in the initialization sampling window, updates the ratio reference interval in the running process, and freezes the ratio reference interval in the main compensation execution section and the setting verification section of the segmented compensation path; when any ratio change trajectory deviates from the ratio reference interval in two or more consecutive fixed time sampling windows and the sulfate ion concentration data or the chloride ion concentration data continuously increases in the same fixed time sampling window, it is recorded as direction away and the weight is increased in the deviation level determination.

[0016] Further, the state label set comprises a single ion deficiency state label, a double ion coupling deficiency state label, an impurity rising interference state label and a spatial distribution imbalance state label, wherein: the single ion deficiency state label corresponds to the verified copper ion concentration data or the verified zinc ion concentration data falling out of the corresponding reference interval in two or more consecutive fixed time sampling windows; the double ion coupling deficiency state label corresponds to the verified copper ion concentration data and the verified zinc ion concentration data falling out of the corresponding reference interval in the same fixed time sampling window; the impurity rising interference state label corresponds to the verified sulfate ion concentration data or the verified chloride ion concentration data rising in two or more consecutive fixed time sampling windows and causing the ratio change trajectory to fall out of the ratio reference interval; the spatial distribution imbalance state label corresponds to the spatial difference degree of multiple fixed sampling positions in the same fixed time sampling window expanding and the concentration difference between the electrode adjacent region fixed sampling position set and the main body region fixed sampling position set increasing; when the double ion coupling deficiency state label and the impurity rising interference state label are both true, the impurity rising interference state label corresponding path is preferentially executed.

[0017] Further, the segmented compensation path comprises a pilot small dose test segment, a main compensation execution segment and a setting verification segment: in the pilot small dose test segment, the copper salt solution addition rate setting data and the zinc salt solution addition rate setting data are adjusted in small amplitude in sequence, the last fixed time sampling window without compensation is taken as the baseline to calculate the recovery sensitivity and determine the main compensation execution order; in the main compensation execution segment, multi-segment addition is implemented according to the main compensation execution order, and at the end of each compensation segment, it is determined whether to maintain the compensation intensity or reduce the compensation intensity by a preset proportion according to the inter-segment retention condition; in the setting verification segment, when the verified copper ion concentration data and the verified zinc ion concentration data return to the reference interval, and the verified sulfate ion concentration data and the verified chloride ion concentration data no longer rise and the spatial difference degree no longer expands, the segmented compensation path is ended.

[0018] Further, the inter-segment retention condition consists of three indexes: recovery amplitude, stable time and spatial balance degree, when any two of them are improved at the same time, the current compensation intensity is retained, otherwise the compensation intensity is reduced by a preset proportion in the next compensation segment; wherein the recovery amplitude is the net increment of the verified copper ion concentration data and the verified zinc ion concentration data at the start and end time of the compensation segment, the stable time is the duration that the verified copper ion concentration data and the verified zinc ion concentration data remain in the reference interval after the end of the compensation segment, and the spatial balance degree is the degree of decline of the relative deviation between the fixed sampling positions in the same layer in the same fixed time sampling window.

[0019] Further, the priority resolution and collaborative adjustment of the segmented compensation path comprises: when there is an impurity rising interference state label, first adjusting the water dilution amount setting data and the circulating flow setting data, and then adjusting the copper salt solution addition rate setting data and the zinc salt solution addition rate setting data; when there is a space distribution imbalance state label and at the same time there is a single ion deficiency state label, first adjusting the stirring speed setting data and the circulating flow setting data, and then performing segmented compensation on the copper salt solution addition rate setting data or the zinc salt solution addition rate setting data corresponding to the direction of the metal ion.

[0020] Compared with the prior art, the beneficial effects of the present application are that:

[0021] By collecting concentration data at fixed time sampling windows in the upper layer fixed sampling position set, the middle layer fixed sampling position set, the lower layer fixed sampling position set, and the electrode adjacent zone fixed sampling position set, the differences between interlayers and boundary layers are directly presented; when there is an interlayer deviation, the priority adjustment of the stirring speed setting data and the circulating flow setting data is triggered by the space distribution imbalance state label, avoiding the error of adding salt based on local abnormalities as a whole deviation.

[0022] The time continuity verification is based on the change direction and change amplitude of the same fixed sampling position in adjacent fixed time sampling windows, eliminating the micro-fluctuation and burr with alternating direction; the spatial consistency verification eliminates outliers and preserves real structural deviation through intra-layer sorting; the ratio change trajectory consistency verification distinguishes apparent metal ion deficiency caused by impurity rising by taking the ratio change trajectory of metal ions and anions as a constraint, reducing false triggering and secondary fluctuations.

[0023] The initialization reference interval is obtained without compensation in the initialization sampling window, and the sliding reference interval is updated with the verified concentration data of the latest window; the reference interval is frozen in the main compensation execution section and the setting verification section, ensuring that the compensation target is stable and does not move with short-term fluctuations in data, thereby shortening the recovery time and reducing the risk of reverse tracking.

[0024] The state label set separates the single ion deficiency, double ion coupling deficiency, impurity rising interference, and space distribution imbalance: for single ion deficiency or double ion coupling deficiency, the copper salt solution addition rate setting data and the zinc salt solution addition rate setting data are adjusted first; for impurity rising interference, the water dilution amount setting data and the circulating flow setting data are adjusted first; for space distribution imbalance, the stirring speed setting data and the circulating flow setting data are adjusted first. In this way, "wrong channel" compensation is avoided, and drug consumption is reduced.

[0025] The back-up sensitivity of the copper salt solution addition rate setting data and the zinc salt solution addition rate setting data is determined by small-scale trial, the main compensation sequence is determined, and the initial intensity is limited; when the response is delayed or asymmetric, the more effective sequence is automatically selected, and the subsequent multi-stage addition is based on the verified sensitivity.

[0026] The main compensation execution section improves any two of the three indicators of back-up amplitude, stable time and spatial balance degree at the same time as the inter-section reservation condition; if it is not met, the intensity of the next section is adjusted down by a preset ratio or a more conservative path is switched to. This mechanism limits the divergence of intensity and reduces the cycle of "over-compensation - withdrawal - re-compensation".

[0027] When there is an impurity rising interference state tag, the water dilution amount setting data and the circulation flow rate setting data are processed first to reduce the ionic strength and improve mass transfer, and then the copper salt solution addition rate setting data and the zinc salt solution addition rate setting data are executed; when there is a spatial distribution imbalance state tag, the mixing and boundary layer are improved through the stirring speed setting data and the circulation flow rate setting data first, and then the salt is added. The sequence optimization reduces invalid addition and waste of electric energy.

[0028] Fixed time sampling window, fixed sampling position and explicit judgment-execution-verification rules form a standardized closed loop; when the sensor is missing or the data is abnormal, the backfilling and weight reduction mechanism is used to maintain operability; when cross-shift and cross-condition reuse, there is no need to re-explore, the tuning cost and human fluctuation are reduced, and the current efficiency and cathode plate consistency are improved. BRIEF DESCRIPTION OF DRAWINGS

[0029] By reading the detailed description of the preferred embodiments below, various other advantages and benefits will become apparent to those of ordinary skill in the art. The drawings are for the purpose of illustrating the preferred embodiments only and are not to be considered as limiting of the present application. Moreover, the same reference numerals are used throughout the various drawings to designate the same or similar parts. In the drawings:

[0030] Figure 1 A flowchart of a real-time electrolyte concentration compensation method in a copper-zinc electrodeposition process is provided for the embodiments of the present application. DETAILED DESCRIPTION

[0031] The exemplary embodiments of the present application will be described in detail with reference to the accompanying drawings. Although exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure can be implemented in various forms and should not be limited by the embodiments described herein. Rather, these embodiments are provided so that the present disclosure can be more thoroughly understood and the scope of the present disclosure can be accurately conveyed to those skilled in the art. It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict. The present application will be described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.

[0032] Referring to Figure 1 As shown in the drawings, the embodiment of the present application provides a method for real-time compensation of electrolyte concentration in copper-zinc electrodeposition process, comprising:

[0033] S1: Collecting copper ion concentration data, zinc ion concentration data, sulfate ion concentration data and chloride ion concentration data at fixed sampling position sets in upper, middle and lower layers and electrode adjacent area at the same fixed time sampling window to form concentration data arranged by position and time;

[0034] S2: Performing time continuity check and spatial consistency check on the concentration data based on the change relationship of the same fixed sampling position in adjacent fixed time sampling windows and the relative deviation between the same layer fixed sampling positions in the same fixed time sampling window, and performing ratio change trajectory consistency check on the concentration data based on the ratio change relationship between metal ions and anions to obtain the checked concentration data;

[0035] S3: Establishing a reference interval and comparing the checked concentration data with the reference interval to generate a deviation level and a state label set;

[0036] S4: Performing segmented compensation path according to the state label set, and sequentially adjusting copper salt solution addition rate setting data, zinc salt solution addition rate setting data, water dilution amount setting data, circulation flow rate setting data and stirring speed setting data until the copper ion concentration data and the zinc ion concentration data meet the reference interval and the sulfate ion concentration data and the chloride ion concentration data are in a stable interval.

[0037] It can be understood that step S1 is collected at the same time in the fixed sampling position sets in the upper, middle and lower layers and the electrode adjacent area, which eliminates the single point blind area, timely exposes the interlayer difference in the concentration data arranged by position and time, and reduces the misjudgment of the miscompensation starting point.

[0038] Step S2 performs time continuity check and spatial consistency check on the concentration data, and performs consistency check on the ratio change trajectory of metal ions and anions, outputs the checked concentration data, suppresses burrs, outliers and short-time pulsations, and reduces false triggering.

[0039] Step S2 performs ratio change trajectory consistency check, distinguishes the apparent low caused by the increase of sulfate ion concentration data or chloride ion concentration data, and avoids improper increase of copper salt solution addition rate setting data or zinc salt solution addition rate setting data.

[0040] Step S3 generates deviation level and state label set with reference interval, triggers condition standardization, reduces artificial subjectivity, and accelerates the decision link from finding deviation to execution.

[0041] Step S4 performs segmented compensation path according to the state label set, and sequentially adjusts the data of copper salt solution addition rate setting, zinc salt solution addition rate setting, water dilution amount setting, circulation flow rate setting, and stirring speed setting, verifies the intensity segment by segment, and reduces one-time excessive adjustment and reverse shock.

[0042] In some embodiments of the present application, at least two fixed sampling positions are arranged in the upper layer fixed sampling position set, the middle layer fixed sampling position set, the lower layer fixed sampling position set, and the electrode adjacent area fixed sampling position set, and the copper ion concentration data, the zinc ion concentration data, the sulfate ion concentration data, and the chloride ion concentration data are synchronously recorded in the same fixed time sampling window. When the concentration data of a single fixed sampling position is missing in a single fixed time sampling window, the average of the concentration data of the two adjacent fixed sampling positions in the same layer in the same fixed time sampling window is backfilled once. When the concentration data of the same fixed sampling position is missing in two or more consecutive fixed time sampling windows, the fixed sampling position is excluded from the time continuity verification and comparison, and only participates in the layer internal statistics of the space consistency verification.

[0043] Specifically, a tank coordinate system is established, taking the center of the tank bottom as the origin, the length direction as X, the width direction as Y, and the liquid level direction as Z. The effective liquid level height H, the tank length L, the tank width W, and the projection range of the electrode plate in the X-Y plane are measured. To prevent interference from wall surface and free liquid surface effects, the normal safety distance of all fixed sampling positions is not less than 0.05W (side wall) and 0.10H (free liquid surface / tank bottom).

[0044] The upper layer fixed sampling position set is set according to the strip interval of Z∈[0.80H, 0.90H], and at least two fixed sampling positions are arranged in the height strip. If only two fixed sampling positions are set, X≈0.25L and X≈0.75L are taken along the X direction, and Y≈0.5W is taken along the Y direction. If three or more are set, points are arranged at equal intervals along the X direction in the same height strip, and the X interval of adjacent fixed sampling positions is made to be ≥0.20L as much as possible. The Z coordinates of all upper layer fixed sampling positions are consistent or fall within the tolerance of ±0.02H.

[0045] The middle layer fixed sampling position set is set according to Z ∈ [0.45H, 0.55H], and the X and Y points of the fixed sampling position form a staggered relationship with the upper layer fixed sampling position set: when the upper layer fixed sampling position set is X ≈ 0.25L and X ≈ 0.75L, the middle layer fixed sampling position set takes X ≈ 0.50L and X ≈ 0.90L-0.50L mirror or equidistant staggered points, and Y remains Y ≈ 0.5W or is symmetrically arranged on the left and right as needed. The Z tolerance of the middle layer fixed sampling position set is also controlled within ±0.02H.

[0046] The lower layer fixed sampling position set is set according to Z ∈ [0.10H, 0.20H], and the points on the X and Y planes are aligned with the upper layer fixed sampling position set (preferably the same X and Y coordinates as the upper layer fixed sampling position set) to form a vertical corresponding column, facilitating cross-layer comparison for spatial consistency verification. The lower layer fixed sampling position set is kept away from the deposition and boundary layer with a safety distance of ≥0.10H from the slot bottom.

[0047] The electrode adjacent area fixed sampling position set is set at an electrode surface normal distance de, de takes a fixed value in the range of 10-30mm (select one value according to the configuration and safety requirements and keep consistent), at least two fixed sampling positions are arranged at a Z height close to the middle layer fixed sampling position set, preferably at the electrode inlet side and the electrode outlet side (upstream and downstream along the main circulation direction) respectively, the X coordinate takes the upstream edge and the downstream edge of the electrode projection inward by 0.05L, and the Y coordinate takes the electrode plate center line ±0.15W to avoid direct proximity to the edge. If the electrode is arranged in multiple columns, the above two point arrangement is repeated in the representative electrode column.

[0048] The upper layer fixed sampling position set, the middle layer fixed sampling position set and the lower layer fixed sampling position set are respectively sorted in ascending order according to the X coordinate, and the two adjacent fixed sampling positions of each fixed sampling position are the two closest fixed sampling positions in the same layer; when there are only two fixed sampling positions in the same layer, the adjacent fixed sampling positions are each other. The adjacent relationship of the electrode adjacent area fixed sampling position set is established separately, and the nearest two fixed sampling positions on the same side (inlet side or outlet side) and with the same de are preferentially selected; if not enough, cross over to make up but keep the Z height band consistent.

[0049] All Z coordinates are updated proportionally with H, keeping the percentage stratification of each height band relative to H unchanged; when the liquid level gauge calibration or working condition changes cause H to change more than ±0.05H, the target coordinates of the upper fixed sampling position set, the middle fixed sampling position set, the lower fixed sampling position set and the electrode adjacent area fixed sampling position set are automatically recalculated, and are aligned to the nearest accessible point according to the nearest available hole or sampling port, with a deviation of no more than the constraint of the height band and the side wall safety distance of each height band; if the deviation exceeds the constraint due to structural limitations, an alternative fixed sampling position is added to the layer and its number and adjacent relationship are updated in the system.

[0050] In the upper fixed sampling position set, the middle fixed sampling position set, the lower fixed sampling position set and the electrode adjacent area fixed sampling position set, a unique number, physical coordinates and main flow direction marker are first established for each fixed sampling position, and two adjacent fixed sampling positions are assigned to each fixed sampling position in each layer, preferably determined as the nearest two points in physical distance or along the main flow direction. The fixed time sampling window sets the start time, end time and step length, and sets the synchronization tolerance, so that the four fixed sampling position sets are synchronized in the same fixed time sampling window. In the data structure, a timestamp, layer identifier, fixed sampling position number, copper ion concentration data, zinc ion concentration data, sulfate ion concentration data, chloride ion concentration data and data status marker are set for each record, and a continuous missing count is maintained for each fixed sampling position and initialized to zero.

[0051] When a fixed time sampling window reaches the end time, the copper ion concentration data, zinc ion concentration data, sulfate ion concentration data and chloride ion concentration data are written into the record. If all four types of values are normal, the data status marker is set to "valid" and the continuous missing count of the fixed sampling position is cleared; if there is no reading, error code or out-of-range value, the data status marker is set to "missing" and the continuous missing count of the fixed sampling position is incremented by one.

[0052] When a single fixed sampling position is marked as "missing" in a single fixed time sampling window, the same layer backfilling is started once. The specific method is to call the adjacent relationship of the layer, read the copper ion concentration data, zinc ion concentration data, sulfate ion concentration data and chloride ion concentration data of the same fixed time sampling window from the two adjacent fixed sampling positions, and require that both adjacent fixed sampling positions are "valid". The average of the two points is calculated respectively and written back to the four ion fields of the missing fixed sampling position corresponding window, and the data state is marked as "backfilling once". In order to accurately judge the scene of "missing for two or more consecutive fixed time sampling windows", backfilling once does not change the continuous missing count of the fixed sampling position. If any one of the adjacent fixed sampling positions is "missing" or "backfilling once" in the same fixed time sampling window, backfilling once is not performed, and the "missing" is maintained and the continuous missing count is increased by one.

[0053] When the continuous missing count of a certain fixed sampling position reaches two or more, the fixed sampling position is marked as excluded in the current time continuity check, and the copper ion concentration data, zinc ion concentration data, sulfate ion concentration data and chloride ion concentration data of the fixed sampling position in any fixed time sampling window in the current collection period are no longer read into the time continuity check; At the same time, it is marked as excluded in the current comparison, and does not participate in the reference interval comparison and deviation level generation. In order to avoid misjudgment of hierarchical statistics, the fixed sampling position is also added to the layer internal statistics of the current spatial consistency check as a "placeholder with no value", that is, only used to judge whether the number of valid fixed sampling positions of the layer meets the minimum number threshold of spatial consistency check and whether the hierarchical weight is triggered, and does not provide copper ion concentration data, zinc ion concentration data, sulfate ion concentration data and chloride ion concentration data to the numerical calculation of the layer internal median value and the layer internal deviation degree.

[0054] The recovery rule is that once the fixed sampling position obtains "valid" readings of the four types of ions in any subsequent fixed time sampling window, the continuous missing count is cleared, and the exclusion mark in the current time continuity check and the current comparison is cancelled, so that it reenters the normal numerical calculation link of time continuity check, reference interval comparison and spatial consistency check.

[0055] In the boundary condition, if the number of valid fixed sampling positions of a layer in a fixed time sampling window is less than two, the layer does not calculate the intra-layer deviation and the intra-layer median value in the fixed time sampling window, and only participates in the level weight reduction of the spatial consistency check as a sign of insufficient number of valid layers; if a layer is configured with only two fixed sampling positions and one of the fixed sampling positions is "missing", since the mean value of the two adjacent fixed sampling positions cannot be obtained, the fixed sampling position is directly promoted according to the continuous missing counting rule, and may enter the rejection state until it is restored to "valid". In order to ensure traceability, each backfilling generates a complete audit log, recording the fixed sampling position number, the fixed time sampling window, the two adjacent fixed sampling position numbers participating in the backfilling, the two-point original value and the mean value of the four types of ions, and the data state change; the events of entering the rejection and recovery also record the time stamp and the reason.

[0056] Taking the set of three fixed sampling positions A, B and C as an example, in the fixed time sampling window t1, the fixed sampling position A is "missing", the fixed sampling position B and the fixed sampling position C are "valid", the system reads the four types of ion values of the fixed sampling position B and the fixed sampling position C at t1, calculates the mean value and fills it into the fixed sampling position A, marks it as "backfilling", and sets the continuous missing count of the fixed sampling position A to 1; in the fixed time sampling window t2, the fixed sampling position A is "missing" again, and since the continuous missing count reaches 2, the fixed sampling position A is excluded from the time continuity check and the comparison at this time, and only enters the intra-layer statistics of the spatial consistency check at this time in the form of placeholder; in the fixed time sampling window t3, the four types of ion readings of the fixed sampling position A are "valid", the system clears the continuous missing count of the fixed sampling position A, cancels the exclusion mark, and the fixed sampling position A is restored to the full participation state. The above process ensures that both occasional missing in a single window and continuous missing can be repaired and protected in a fixed time sampling window, respectively, and the robustness of the time continuity check, the spatial consistency check and the subsequent reference interval comparison is maintained.

[0057] In some embodiments of the present application, the time continuity check is based on the change direction and change amplitude of the copper ion concentration data, the zinc ion concentration data, the sulfate ion concentration data and the chloride ion concentration data of the same fixed sampling position in three consecutive fixed time sampling windows, when the direction alternates and the change amplitude is lower than the preset micro-amplitude threshold, the linear extrapolation value of the previous fixed time sampling window and the next fixed time sampling window of the fixed sampling position is used to replace the concentration data of the middle fixed time sampling window; when the direction alternates for the second time and the change amplitude is lower than the preset micro-amplitude threshold, the subsequent concentration data of the fixed sampling position in the comparison is counted according to the preset weight reduction coefficient.

[0058] Specifically, a time series buffer is established for each fixed sampling position, and the copper ion concentration data, zinc ion concentration data, sulfate ion concentration data and chloride ion concentration data are sequentially written in the fixed time sampling window in order, and a "direction alternation count" is maintained separately for the fixed sampling position. The time continuity verification is performed in a three-window sliding manner, and the window group is the previous fixed time sampling window, the current fixed time sampling window and the next fixed time sampling window. The change direction and change amplitude of the four types of ions at the same fixed sampling position are calculated for the adjacent two windows, the change direction is taken as two types of rising or falling, and the change amplitude is the absolute value of the difference corresponding to the fixed time sampling window interval. The micro-amplitude threshold is determined by the short-term fluctuation statistics of the verified copper ion concentration data, verified zinc ion concentration data, verified sulfate ion concentration data and verified chloride ion concentration data in the initialization sampling window or verified engineering constant, and remains unchanged in the current collection period.

[0059] When the same fixed sampling position appears direction alternation and the change amplitude of any ion in the four types of ions in the three windows is lower than the micro-amplitude threshold, it is determined that the current fixed time sampling window of the fixed sampling position is affected by the micro-amplitude disturbance, and the trend given by the previous fixed time sampling window and the next fixed time sampling window is needed to replace the current fixed time sampling window. The replacement value is determined according to the extension value of the line connecting the previous fixed time sampling window and the next fixed time sampling window at the current time, and the four fields of copper ion concentration data, zinc ion concentration data, sulfate ion concentration data and chloride ion concentration data are replaced respectively, and the data state of the current fixed time sampling window is marked as "time continuity replacement". If the previous fixed time sampling window or the next fixed time sampling window is missing, backfilled once or rejected, the replacement is not performed, and only the current fixed time sampling window is counted in the preset weight reduction coefficient in the current comparison.

[0060] When the same fixed sampling position satisfies the condition of "direction alternation and change amplitude lower than micro-amplitude threshold" for the second time, the direction alternation count is increased by one and the weight reduction duration processing is triggered, that is, in the remaining fixed time sampling window of the current collection period, the verified copper ion concentration data, verified zinc ion concentration data, verified sulfate ion concentration data and verified chloride ion concentration data of the fixed sampling position are uniformly counted in the reference interval comparison, deviation level generation and state label set determination according to the preset weight reduction coefficient, but the original record and the time continuity replacement record are reserved for tracing. If the subsequent three three-window groups do not appear direction alternation or the change amplitude is not lower than the micro-amplitude threshold, the direction alternation count is automatically cleared and the weight reduction is removed.

[0061] The boundary and exception are handled according to the following principles. The three-window group located at the beginning or end of the sequence and lacking the previous fixed time sampling window or the next fixed time sampling window does not participate in replacement, only participates in the recording of direction and amplitude, and is counted in the current comparison with light weight. When the same fixed sampling position is in the same fixed time sampling window and is judged as an outlier fixed sampling position due to spatial consistency check and has been uniformly weighted, the time continuity check only records and does not superimpose the weight. The connection of backfilling once is that if the current fixed time sampling window is backfilled once, the time continuity check is still executed as usual, but does not trigger replacement, but can only trigger weight. All replacement and weight events are written into the log, including fixed sampling position number, three-window timestamp, direction and amplitude of four types of ions, whether to replace, whether to weight and weight coefficient; the micro-amplitude threshold, the direction alternation count and the weight state are automatically reset to the next acquisition cycle.

[0062] In some embodiments of the present application, the spatial consistency check is based on the relative deviation between the same layer fixed sampling positions in the same fixed time sampling window. The deviation of the same layer fixed sampling positions from the median value in the layer is sorted and the single fixed sampling position with the largest deviation is removed as an outlier fixed sampling position. When the relative deviation direction of the upper layer fixed sampling position set and the lower layer fixed sampling position set is opposite and the concentration difference between the electrode adjacent area fixed sampling position set and the main body area fixed sampling position set increases, the removal of the outlier fixed sampling position is cancelled, and all fixed sampling positions in the fixed time sampling window are uniformly counted according to the preset weight coefficient.

[0063] Specifically, in the same fixed time sampling window, first, the fixed sampling positions with data status marked as "valid" or "time continuity replacement" are screened out in the upper fixed sampling position set, the middle fixed sampling position set, the lower fixed sampling position set and the electrode adjacent area fixed sampling position set respectively, and the fixed sampling positions with data status marked as "missing", "backfill once" or having been eliminated are discarded. The median values of the copper ion concentration data, the zinc ion concentration data, the sulfate ion concentration data and the chloride ion concentration data in each layer are calculated respectively. For each fixed sampling position in the same layer, the absolute deviations of the four types of ions relative to the median value of the corresponding layer are calculated respectively, and the maximum of the absolute deviations of the four types of ions is taken as the layer internal deviation degree of the fixed sampling position in the layer; the greater the layer internal deviation degree is, the more abnormal the fixed sampling position is. At the same time, the layer internal deviation direction is determined: the sign of the type of ion that produces the layer internal deviation degree (positive if higher than the median value of the layer, and negative if lower than the median value of the layer) is taken as the layer internal deviation direction of the fixed sampling position. All fixed sampling positions in the same layer are sorted in descending order of layer internal deviation degree, and the single fixed sampling position with the largest layer internal deviation degree is selected as the outlier fixed sampling position, and its data status in the fixed time sampling window is marked as "spatial consistency elimination", and it is no longer included in any layer internal statistics and subsequent comparison in the fixed time sampling window. If there are parallel maximums, the copper ion concentration data deviation absolute value, the zinc ion concentration data deviation absolute value, the sulfate ion concentration data deviation absolute value and the chloride ion concentration data deviation absolute value are compared in turn until a unique determination is made; if still cannot be distinguished, the fixed sampling position with smaller number is selected. If there are less than two valid fixed sampling positions in a layer in the fixed time sampling window, the layer does not perform layer internal deviation calculation, and does not select the outlier fixed sampling position, and only participates in the spatial consistency check as "insufficient number" in the hierarchical weight reduction.

[0064] After the selection of the fixed sampling position of each layer is completed, it is determined whether to trigger the "cancellation of the rejection of the fixed sampling position of the outlier and the uniform weight reduction". First, the relative deviation direction of the upper fixed sampling position set and the lower fixed sampling position set is compared: the difference between the median value of the upper fixed sampling position set and the median value of the middle fixed sampling position set is taken as the criterion of the relative deviation direction of the upper layer, and the difference between the median value of the lower fixed sampling position set and the median value of the middle fixed sampling position set is taken as the criterion of the lower layer; when the dominant ion (i.e. the ion that produces a large interlayer difference) is positive in the upper layer and negative in the lower layer, or negative in the upper layer and positive in the lower layer, it is determined that the relative deviation direction of the upper fixed sampling position set and the lower fixed sampling position set is opposite. Then, the concentration difference between the electrode adjacent area fixed sampling position set and the main area fixed sampling position set is calculated: the median value of the electrode adjacent area fixed sampling position set and the median value of the main area fixed sampling position set (the main area fixed sampling position set is combined by the upper fixed sampling position set, the middle fixed sampling position set and the lower fixed sampling position set) are compared, and the maximum absolute difference in the four types of ions is taken as the concentration difference index of the fixed time sampling window; the concentration difference index of the fixed time sampling window is compared with the concentration difference index of the previous fixed time sampling window, if it shows an expanding trend, it is determined that the concentration difference between the electrode adjacent area fixed sampling position set and the main area fixed sampling position set increases. Only when the above two conditions are met, the "spatial consistency rejection" of the marked outlier fixed sampling position in the fixed time sampling window is cancelled, the participation qualification of the fixed time sampling window is restored, and all fixed sampling positions in the fixed time sampling window are uniformly counted by the preset weight reduction coefficient for subsequent comparison and judgment; if any condition is not met, the "spatial consistency rejection" of the outlier fixed sampling position is maintained, and the remaining fixed sampling positions are counted according to the original weight.

[0065] In the implementation process, the intra-layer median value and the intra-layer deviation degree only take effect within the fixed time sampling window and are not used across windows; once the uniform counting by the preset weight reduction coefficient is triggered, it is only effective for the fixed time sampling window and does not change the default weight of the next fixed time sampling window. In order to ensure traceability, the intra-layer median value, the outlier fixed sampling position number, the intra-layer deviation degree and direction of the outlier fixed sampling position, whether to trigger the uniform counting by the preset weight reduction coefficient, and the concentration difference index of the electrode adjacent area fixed sampling position set and the main area fixed sampling position set and its change direction relative to the previous fixed time sampling window are recorded in each fixed time sampling window; when the number of effective fixed sampling positions is insufficient to cause the non-execution of the part of the rule, the reason is recorded and the hierarchical weight reduction is performed to avoid the bias of the spatial consistency verification conclusion caused by the occasional missing measurement.

[0066] In some embodiments of the present application, the establishment of the reference interval includes initialization sampling window and sliding update: the initialization sampling window remains uncompensated, and the upper and lower limits of the verified copper ion concentration data, the verified zinc ion concentration data, the verified sulfate ion concentration data and the verified chloride ion concentration data are determined as the initialization reference interval; during operation, the verified copper ion concentration data, the verified zinc ion concentration data, the verified sulfate ion concentration data and the verified chloride ion concentration data of the last several fixed time sampling windows are used to update the sliding reference interval, and the sliding reference interval is frozen in the main compensation execution section and the setting verification section of the segmented compensation path.

[0067] Specifically, the start and end time of the initialization sampling window and the number of fixed time sampling windows are defined, the initialization sampling window remains uncompensated, specifically, the copper salt solution addition rate setting data, the zinc salt solution addition rate setting data, the water dilution amount setting data, the circulation flow rate setting data and the stirring speed setting data are frozen, and no automatic or manual formula change is performed; if the process safety requires a small amplitude of maintenance operation, it is recorded as a maintenance action and marked with a time stamp so that the corresponding fixed time sampling window is excluded when the reference interval is calculated. Before the end of the initialization sampling window, the verified copper ion concentration data, the verified zinc ion concentration data, the verified sulfate ion concentration data and the verified chloride ion concentration data are aggregated according to the fixed time sampling window, and a data list is established ion by ion, which only contains records with valid data state marks or time continuity replacement, and does not contain missing, backfilling or spatial consistency excluded records.

[0068] The determination of the initialization reference interval is carried out ion by ion. The concentration data of the verified copper ion, the verified zinc ion, the verified sulfate ion and the verified chloride ion are calculated for the concentration trend and the robust dispersion, and the upper and lower limits are given accordingly, which cover the normal fluctuations in the initialization sampling window but are not too wide; preferably, the quantile range method or the symmetric band method composed of the median level and the robust dispersion is used, and the specific threshold is taken from the process verification record and stored in the form of parameters to avoid writing dead constants during operation. In order to prevent occasional abnormality from widening the interval, if the single window abnormality proportion exceeds the preset proportion, the window is ignored when generating the upper and lower limits of the ion. After the initialization reference interval is generated, the version number, the time stamp and the fixed time sampling window list used for calculation are recorded to ensure subsequent traceability.

[0069] The sliding reference interval is constructed during operation. First, the length of the sliding window and the update step are set, for example, taking the last several fixed time sampling windows as samples, and trying to update once every time the new window ends; each time the update is performed, the data state markers in the recent samples are extracted as valid or time continuity replacement records, the central tendency and robust dispersion are recalculated, and new upper and lower bounds are generated. To avoid frequent fluctuations of the sliding reference interval due to short-term disturbances, minimum residence time and minimum change amplitude rules are introduced: the sliding reference interval is maintained for at least several fixed time sampling windows since the last update, and only when the difference between the new upper or lower bound and the current value exceeds a predetermined percentage will the update be accepted; if the condition is not met, the current sliding reference interval is used. If there are not enough valid records in the recent samples or the spatial consistency check triggers uniform weight reduction in most windows, the update is delayed and recorded as an update failure event.

[0070] The main compensation execution section and the setting verification section of the segmented compensation path freeze the sliding reference interval. The meaning of freezing is to suspend the recalculation of the upper and lower bounds, and to maintain the sliding reference interval at the time of entering the main compensation execution section unchanged, so as to avoid "compensation while drifting". The starting condition of freezing is the starting time of the first section of the main compensation execution section, and the ending condition is that the setting verification section passes the shutdown criterion or reaches the maximum freezing time limit; if the setting verification section does not pass and the maximum freezing time limit has been reached, only a single small update is allowed according to the conservative strategy, and the parameter change record of this update is recorded. If the checked sulfate ion concentration data and the checked chloride ion concentration data continue to rise and the ratio change trajectory consistency check shows that the direction is opposite, the temporary lower limit of the checked copper ion concentration data and the checked zinc ion concentration data is allowed to be protected by limiting the upper limit of the temporary lower limit, to prevent the target from being relaxed incorrectly when the impurity pressure increases.

[0071] To ensure the mutual independence and coordination of different ion reference intervals, the checked copper ion concentration data reference interval, the checked zinc ion concentration data reference interval, the checked sulfate ion concentration data reference interval, and the checked chloride ion concentration data reference interval are output respectively at each generation or update, along with the interval validity period, the sample window number used, and the window number excluded. In the generation of the state tag set, the reference interval at the freezing time is always used as a reference, and the success or failure of any compensation action is determined only by the frozen reference, to avoid false positives caused by target movement.

[0072] The degradation strategy is executed in the boundary case. When the number of valid records verified within the initialization sampling window is lower than the minimum sample threshold, the initialization reference interval is not directly generated, but the initialization sampling window is extended until the threshold is met; if it cannot be extended due to production rhythm, the verified conservative interval is used as a temporary initialization reference interval and marked as temporary, and automatically replaced after the subsequent sample meets the threshold. For the sliding reference interval, if the update fails continuously for multiple times, the update step is doubled and a full integrity check is triggered, and after confirming that the sampling system and the verification link are fault-free, the default step is restored.

[0073] In terms of version management and audit, each generation, update, freezing and unfreezing of the initialization reference interval and the sliding reference interval is written into the log, and the log includes the timestamp, version number, upper and lower bounds of each ion, sample window list, rejection reason statistics, whether to trigger unified weight reduction, whether in the main compensation execution segment or the setting verification segment, and operator notes. The determination of any state label set and the intensity decision of any segmented compensation path refer to the version number of the effective reference interval at that time, ensuring one-to-one correspondence when reviewing.

[0074] In some embodiments of the present application, the ratio change trajectory consistency verification takes the ratio change trajectory between the copper ion concentration data and the zinc ion concentration data and the ratio change trajectory of the copper ion concentration data and the zinc ion concentration data relative to the total of the sulfate ion concentration data and the chloride ion concentration data as the basis, extracts the ratio reference interval in the initialization sampling window, updates the ratio reference interval in the running process with the recent several fixed time sampling windows, and freezes the ratio reference interval in the main compensation execution segment and the setting verification segment of the segmented compensation path; when any ratio change trajectory deviates from the ratio reference interval in two or more consecutive fixed time sampling windows and the sulfate ion concentration data or the chloride ion concentration data continuously rises in the same fixed time sampling window, it is recorded as direction deviation and the weight is increased in the deviation level determination.

[0075] Specifically, the consistency check object of the ratio change trajectory is determined as two trajectories: one is the ratio change trajectory between the copper ion concentration data and the zinc ion concentration data, and the other is the ratio change trajectory of the copper ion concentration data and the zinc ion concentration data relative to the total of the sulfate ion concentration data and the chloride ion concentration data. In each fixed time sampling window, after the upper, middle and lower fixed sampling position sets are subjected to the intra-layer spatial consistency check, the intra-layer median values of the checked copper ion concentration data, the checked zinc ion concentration data, the checked sulfate ion concentration data and the checked chloride ion concentration data are obtained respectively; the upper, middle and lower fixed sampling position sets are combined into a main zone fixed sampling position set, and the three-layer median values in the fixed time sampling window are subjected to median operation again to obtain the representative values of the checked copper ion concentration data, the checked zinc ion concentration data, the checked sulfate ion concentration data and the checked chloride ion concentration data of the main zone fixed sampling position set; the representative values form the ratio change trajectory node between the copper ion concentration data and the zinc ion concentration data, and the ratio change trajectory node of the copper ion concentration data and the zinc ion concentration data relative to the total of the sulfate ion concentration data and the chloride ion concentration data. The electrode adjacent zone fixed sampling position set is only used for directional review in the fixed time sampling window, and does not directly participate in the calculation of the ratio change trajectory node, unless the main zone fixed sampling position set has insufficient valid records, in which case the electrode adjacent zone fixed sampling position set is supplemented and the source change is marked in the log.

[0076] In the initialization sampling window, no compensation is maintained, and the records with the data state markers of missing, backfilling once and spatial consistency rejection are removed, only the records with the data state markers of valid and time continuity replacement are retained, and the above two ratio change trajectories are formed window by window. The centralized trend and robust dispersion of the ratio change trajectory between the copper ion concentration data and the zinc ion concentration data and the ratio change trajectory of the copper ion concentration data and the zinc ion concentration data relative to the total of the sulfate ion concentration data and the chloride ion concentration data are counted respectively, and the upper and lower limits are determined as the initialization ratio reference interval; if the unified weight reduction or the main zone fixed sampling position set has insufficient valid records is triggered in a single fixed time sampling window, the fixed time sampling window is not included in the calculation of the initialization ratio reference interval. After the initialization ratio reference interval is calculated, a version number is generated, the list of fixed time sampling windows involved and the rejection reasons are recorded, and are used as the basis for subsequent deviation level determination and state tag set determination.

[0077] In the running process, the length of the sliding window and the update step are set, and the ratio change trajectory between the copper ion concentration data and the zinc ion concentration data and the ratio change trajectory of the copper ion concentration data and the zinc ion concentration data relative to the total of the sulfate ion concentration data and the chloride ion concentration data are updated. At the end of each new fixed time sampling window, if the number of valid records in the recent sample meets the threshold and no large-scale unified weight reduction occurs, the new ratio reference interval is generated by recalculating the upper and lower bounds of the recent sample; if the change amount of the new upper and lower bounds relative to the current ratio reference interval is less than the minimum change amplitude, or the ratio reference interval has not reached the minimum residence time since the last update, the existing ratio reference interval is maintained unchanged. The ratio reference interval is frozen when entering the main compensation execution section and the setting verification section of the segmented compensation path, and all recalculation is suspended during the freezing period. Only one limited update is allowed in the case that the longest freezing time limit is reached and the setting verification fails, and the parameter change record of this limited update is recorded. If the verified sulfate ion concentration data and the verified chloride ion concentration data are continuously rising and cause significant pulling of the ratio change trajectory, only the weight in the deviation level determination is allowed to be increased, and the upper and lower bounds of the ratio reference interval are not allowed to be relaxed.

[0078] In the deviation identification, continuity and concomitance are used as trigger conditions. The ratio reference interval is compared between the ratio change trajectory between the copper ion concentration data and the zinc ion concentration data and the ratio change trajectory of the copper ion concentration data and the zinc ion concentration data relative to the total of the sulfate ion concentration data and the chloride ion concentration data. If any ratio change trajectory falls out of the corresponding upper and lower bounds in two or more consecutive fixed time sampling windows, and the verified sulfate ion concentration data or the verified chloride ion concentration data continuously rises in the same fixed time sampling window, the ratio change trajectory is marked as direction deviation, which is counted in the deviation level determination according to a preset weight increase coefficient, and provides strong trigger basis for the impurity rising interference state label in the state label set. If only single window deviation occurs without meeting the condition of two consecutive windows and without the continuous rising of the verified sulfate ion concentration data or the verified chloride ion concentration data, it is counted as mild deviation and is counted according to the mild weight. If the main area fixed sampling position set has insufficient valid records in a certain fixed time sampling window, the ratio change trajectory node of the fixed time sampling window does not participate in the deviation statistics, and the deviation identification is postponed to the next fixed time sampling window.

[0079] In the abnormality and boundary processing, when the representative value required for forming the ratio change trajectory node is from the time continuity replacement and the fixed time sampling window triggers the unified weight reduction at the same time, the ratio change trajectory node is only used for direction recording and does not participate in the ratio reference interval update and the direction deviation count; when the continuous multiple windows are in this situation, the sliding update is suspended and an update failure event is output once. The generation, update and freezing events of all ratio reference intervals, the generation and release events of all direction deviations are written into the log, the log includes the fixed time sampling window timestamp, the ratio reference interval version number, the values of the two ratio change trajectories in the fixed time sampling window, whether it is out of bounds, whether it meets the continuity condition, the verified sulfate ion concentration data and the verified chloride ion concentration data, the accompanying change direction and the weight increase coefficient in the deviation level judgment, ensuring that the basis for each judgment and each compensation decision can be restored at the time of subsequent audit.

[0080] In some embodiments of the present application, the state tag set includes a single ion deficiency state tag, a double ion coupling deficiency state tag, an impurity rising interference state tag and a spatial distribution imbalance state tag, wherein: the single ion deficiency state tag corresponds to the verified copper ion concentration data or the verified zinc ion concentration data falling out of the corresponding reference interval in two or more consecutive fixed time sampling windows; the double ion coupling deficiency state tag corresponds to the verified copper ion concentration data and the verified zinc ion concentration data falling out of the corresponding reference interval at the same fixed time sampling window; the impurity rising interference state tag corresponds to the verified sulfate ion concentration data or the verified chloride ion concentration data rising in two or more consecutive fixed time sampling windows and causing the ratio change trajectory to fall out of the ratio reference interval; the spatial distribution imbalance state tag corresponds to the spatial difference degree of multiple fixed sampling positions in the same fixed time sampling window expanding and the concentration difference between the electrode adjacent area fixed sampling position set and the main body area fixed sampling position set increasing; when the double ion coupling deficiency state tag and the impurity rising interference state tag are both true, the path corresponding to the impurity rising interference state tag is preferentially executed.

[0081] Specifically, the state tag set is uniformly judged at the end of each fixed time sampling window, and the input is the verified copper ion concentration data, the verified zinc ion concentration data, the verified sulfate ion concentration data, the verified chloride ion concentration data, the reference interval, the ratio reference interval, the spatial difference degree index, and the concentration difference index of the electrode adjacent area fixed sampling position set and the main body area fixed sampling position set. The system maintains a continuous counter, an effective flag, a trigger timestamp and a release timestamp for each fixed sampling position and each state tag. The continuous counter is only accumulated when the data state flag is valid or the time continuity replacement and the spatial consistency check are not uniformly reduced, and is suspended but not cleared when the data state flag is missing, backfilled once or uniformly reduced.

[0082] The single-ion deficiency state label is implemented as follows: at the same fixed sampling position, track the windowed slope of the verified copper ion concentration data and the verified zinc ion concentration data respectively, and determine the condition that the verified copper ion concentration data or the verified zinc ion concentration data simultaneously satisfy "the slope is in the downward direction and is lower than the lower limit of the corresponding reference interval" in two or more consecutive fixed time sampling windows. When the condition is met, the single-ion deficiency state label in the corresponding metal ion direction is set to be effective, and the triggered fixed sampling position, fixed time sampling window, and reference interval lower limit out-of-bound amplitude are recorded for subsequent starting strength estimation of the segmented compensation path. The release condition is that the verified copper ion concentration data or the verified zinc ion ion concentration data returns to the reference interval in two consecutive fixed time sampling windows, and the slope of the second window is not in the downward direction; when the condition is met, the single-ion deficiency state label counter at the fixed sampling position is cleared but the last triggering log is retained.

[0083] The double-ion coupling deficiency state label is implemented as follows: at the same fixed sampling position, the verified copper ion concentration data and the verified zinc ion concentration data are subjected to window-consistent consistency determination, and the time deviation is allowed to be equal to the synchronization tolerance of the fixed time sampling window, the determination condition is that both are in the downward direction and simultaneously lower than the lower limit of the respective reference interval in the same fixed time sampling window, and the same trend is maintained or not improved to the reference interval in the subsequent fixed time sampling window. When the condition is met, it is set to be effective and the joint out-of-bound amplitude of the two and the smaller one are recorded. The release condition is that both return to the reference interval in two adjacent fixed time sampling windows and at least one of the slopes turns to the non-downward direction. If the verified sulfate ion concentration data or the verified chloride ion concentration data continuously rises during the effective period of the double-ion coupling deficiency state label and is accompanied by a ratio change trajectory falling out of the ratio reference interval, the double-ion coupling deficiency state label remains recorded but does not directly drive the segmented compensation path of salt addition, and whether compensation in the metal ion direction is still needed is evaluated after the execution of the corresponding path of the impurity rising interference state label is completed.

[0084] The realization of the impurity rising interference state label is: tracking the monotonicity of the verified sulfate ion concentration data and the verified chloride ion concentration data at the same fixed sampling position and its relationship with the ratio reference interval, and the judgment condition is that the verified sulfate ion concentration data or the verified chloride ion concentration data rises in two or more consecutive fixed time sampling windows, and the ratio change trajectory between the copper ion concentration data and the zinc ion concentration data or the ratio change trajectory of the copper ion concentration data and the zinc ion concentration data relative to the total ratio of the sulfate ion concentration data and the chloride ion concentration data falls out of the corresponding ratio reference interval in the same two fixed time sampling windows. When the condition is met, it is effective, and the rising weight coefficient with the opposite direction is written into the deviation level judgment to increase the weight of the fixed sampling position. The release condition is that the verified sulfate ion concentration data and the verified chloride ion concentration data no longer rise in adjacent two fixed time sampling windows, and at least one ratio change trajectory returns to the ratio reference interval; if the direction deviates during the frozen ratio reference interval, the impurity rising interference state label is kept effective and the adjustment of the water dilution amount setting data and the circulation flow setting data is preferentially triggered in the segmented compensation path.

[0085] The realization of the spatial distribution imbalance state label is: first calculating the in-layer median value in the same fixed time sampling window and obtaining the in-layer deviation degree, and then calculating the concentration difference index of the three-layer combined median value of the main area fixed sampling position set and the median value of the electrode adjacent area fixed sampling position set, and the judgment condition is that the in-layer deviation degree of multiple fixed sampling positions in the same fixed time sampling window is significantly larger than that in the previous fixed time sampling window, and the concentration difference index between the electrode adjacent area fixed sampling position set and the main area fixed sampling position set is larger than that in the previous fixed time sampling window. When the condition is met, it is effective and records the occurrence layer, the occurrence side and the concentration difference index increment, which is used to improve the priority of the stirring speed setting data and the circulation flow setting data in the segmented compensation path; the release condition is that the in-layer deviation degree converges in two consecutive fixed time sampling windows and the concentration difference index no longer increases or falls back to the historical stable interval.

[0086] The rule of priority execution of the impurity rising interference state label corresponding path is realized by the "inhibition flag" and the "sequence lock" when the double ion coupling insufficient state label and the impurity rising interference state label are established at the same time. The inhibition flag is set in the first fixed time sampling window when the impurity rising interference state label takes effect, so that the salt-related segmented compensation path cannot increase the strength of the copper salt solution addition rate setting data and the zinc salt solution addition rate setting data before the inhibition flag is released; the sequence lock requires the adjustment of the water dilution amount setting data and the circulation flow rate setting data to be executed first and at least one fixed time sampling window to be observed. If the verified sulfate ion concentration data and the verified chloride ion concentration data stop rising and at least one ratio change trajectory returns to the ratio reference interval, the inhibition flag is automatically released and the double ion coupling insufficient state label is re-judged whether it still needs subsequent salt compensation.

[0087] To prevent false triggering, the judgment of all state label sets introduces double thresholds of minimum change amplitude and minimum duration window number, and the threshold is not relaxed during the freezing period of the reference interval and the ratio reference interval. The log system records the triggering or release of each state label, the fixed sampling position number involved, the reference interval out-of-bound amplitude, the ratio reference interval out-of-bound trajectory, the spatial difference degree and the concentration difference index, the weight increase or decrease coefficient, and whether it is affected by the unified weight decrease in each fixed time sampling window. This can ensure that the generation of the state label set is traceable, reviewable, and corresponds to the starting intensity, sequence and inter-segment retention condition of the segmented compensation path.

[0088] In some embodiments of the present application, the segmented compensation path includes a pilot small dose test segment, a main compensation execution segment and a setting verification segment: in the pilot small dose test segment, the copper salt solution addition rate setting data and the zinc salt solution addition rate setting data are adjusted in small amplitude in sequence, and the last fixed time sampling window without compensation is taken as the baseline to calculate the rising sensitivity and determine the main compensation execution sequence; in the main compensation execution segment, multi-segment addition is implemented according to the main compensation execution sequence, and at the end of each compensation segment, the compensation intensity is maintained or reduced by a preset proportion according to the inter-segment retention condition; in the setting verification segment, when the verified copper ion concentration data and the verified zinc ion concentration data return to the reference interval and the verified sulfate ion concentration data and the verified chloride ion concentration data no longer rise and the spatial difference degree no longer expands, the segmented compensation path is ended.

[0089] Specifically, the precondition for entering the segmented compensation path is that the deviation level is the second level and there is at least a single-ion deficiency state label or a double-ion coupling deficiency state label in the state label set; if the impurity rising interference state label is effective, the adjustment of the water dilution amount setting data and the circulation flow rate setting data is performed first until the ratio change trajectory returns to the ratio reference interval or stops rising, and then the segmented compensation related to salt addition can be entered. The reference interval and the ratio reference interval are frozen when entering the segmented compensation path, and the latest fixed time sampling window without compensation is taken as the baseline window. The verified copper ion concentration data, verified zinc ion concentration data, verified sulfate ion concentration data, and verified chloride ion concentration data of the baseline window are recorded, as well as the spatial difference.

[0090] The pilot small dose test section sequentially adjusts the copper salt solution addition rate setting data and the zinc salt solution addition rate setting data in small increments, with each small increment lasting for one to two fixed time sampling windows, and an observation window of the same length is set after each small increment. At the end of each observation window, the change direction of the recovery sensitivity, the stable time, and the spatial balance degree based on the baseline window are calculated respectively. The one with higher recovery sensitivity and shorter stable time and without deteriorating spatial balance degree is determined as the first in the main compensation execution order, and the other is the second. If the spatial distribution imbalance state label is effective during the pilot small dose test section, the salt addition is suspended, the stirring speed setting data and the circulation flow rate setting data are fine-tuned first until the spatial difference degree no longer expands, and then the remaining steps of the pilot small dose test section are resumed. At the end of the pilot small dose test section, the main compensation execution order, the starting intensity and the upper limit of the maximum cumulative intensity of the two types of salt addition are determined, and the adjustment amount during the pilot small dose test section is counted into the cumulative amount.

[0091] The main compensation execution section implements multi-section dosing according to the main compensation execution sequence, each compensation section containing two consecutive fixed time sampling window intervals of execution sub-window and observation sub-window; the execution sub-window has fixed proportion increment adjustment of the starting intensity to increase the copper salt solution addition rate setting data or the zinc salt solution addition rate setting data, the observation sub-window does not change the setting, and only monitors the verified copper ion concentration data, the verified zinc ion concentration data, the verified sulfate ion concentration data and the verified chloride ion concentration data, and the spatial difference. The inter-section retention condition is that any two of the recovery amplitude, the stable time and the spatial balance degree are improved at the same time; when the inter-section retention condition is met, the current intensity is maintained or the intensity is slightly increased by a fixed proportion in the next compensation section; when the inter-section retention condition is not met, the intensity is reduced by a preset proportion in the next compensation section or a fine adjustment of the water dilution setting data and the circulation flow setting data is inserted between two sections; when the observation sub-window has continuous rising of the verified sulfate ion concentration data or the verified chloride ion concentration data and the ratio change trajectory falls out of the ratio reference interval, the subsequent salt addition is immediately suspended and the path of the water dilution setting data and the circulation flow setting data is entered, until the ratio change trajectory recovers. The main compensation execution section sets the maximum cumulative intensity upper limit and the single-section maximum intensity upper limit for the two types of salt addition respectively; when any of the upper limits is reached and the inter-section retention condition is still not met, the salt addition is stopped and only the spatial balance degree is converged by the stirring speed setting data and the circulation flow setting data. If the spatial distribution imbalance state label appears again in the main compensation execution section and the spatial difference increases compared with the last observation sub-window, the conclusion of this section is recorded as not meeting the inter-section retention condition, and the stirring speed setting data and the circulation flow setting data are adjusted in the next section.

[0092] The setting verification section maintains the current setting without increasing the copper salt solution addition rate setting data and the zinc salt solution addition rate setting data, and continuously observes a plurality of fixed time sampling windows; the end condition of the setting verification section is that the verified copper ion concentration data and the verified zinc ion concentration data return to the reference interval at the same time and do not exceed the boundary again in at least two consecutive fixed time sampling windows, and the verified sulfate ion concentration data and the verified chloride ion concentration data do not rise and the spatial difference does not expand relative to the value when entering the setting verification section. If any condition in the setting verification section is broken, return to the main compensation execution section and restart a section with degraded intensity, while maintaining the frozen reference interval and the frozen ratio reference interval until the setting verification section is successful or the longest freezing time limit is reached. After the setting verification section, the frozen state is released, the baseline window is updated to the latest uncompensated window, and the setting record is written for subsequent period reuse of the starting intensity and the main compensation execution sequence.

[0093] The abnormality and boundary handling is performed in the following manner. If any execution sub-window has data status marked as missing or uniform down-weighting leading to indeterminacy of observation sub-window indicator, the compensation segment is not counted into inter-segment retention condition, the overall intensity is not increased and an observation sub-window is extended; if two consecutive segments are indeterminate, the segmentation compensation path is suspended and a sampling integrity check is triggered. If the set maximum cumulative intensity upper limit is reached or a reverse shock occurs (the verified copper ion concentration data and the verified zinc ion concentration data cross the upper limit of the reference interval and then cross the interval again in two consecutive fixed time sampling windows), an intensity rollback is performed and the setting verification segment is directly entered.

[0094] In some embodiments of the present application, the inter-segment retention condition is composed of three indicators: the recovery amplitude, the stable time and the spatial balance degree. When any two indicators are improved at the same time, the current compensation intensity is retained, otherwise the compensation intensity is reduced by a preset proportion in the next compensation segment; the recovery amplitude is the net increment of the verified copper ion concentration data and the verified zinc ion concentration data at the start and end time of the compensation segment, the stable time is the duration that the verified copper ion concentration data and the verified zinc ion concentration data remain within the reference interval after the end of the compensation segment, and the spatial balance degree is the degree of decline of the relative deviation between the same layer fixed sampling positions in the same fixed time sampling window.

[0095] Specifically, at the end of each compensation section, the starting time of the compensation section is taken as the starting time of the compensation section, the end time of the observation sub-window of the compensation section is taken as the end time of the compensation section, and the three indicators of the recovery amplitude, the stable time and the spatial balance degree are calculated in turn under the premise of the frozen reference interval and the frozen ratio reference interval, and the compensation intensity of the next compensation section is determined accordingly. The recovery amplitude is based on the net increment of the verified copper ion concentration data and the verified zinc ion concentration data, and the net increment is defined as the representative value at the end time of the compensation section minus the representative value at the starting time of the compensation section, and the representative value is the median representative of the fixed sampling position set in the fixed time sampling window after spatial consistency verification. In order to avoid false judgment caused by single ion high, the smaller one of the net increment of the verified copper ion concentration data and the net increment of the verified zinc ion concentration data is taken as the recovery amplitude of the compensation section, and it is required to be not less than the minimum distinguishable change threshold, and less than the threshold is regarded as not improved. The stable time starts timing after the end of the compensation section, and the number of continuous windows in which the verified copper ion concentration data and the verified zinc ion concentration data are simultaneously located in the respective reference intervals is counted. If either ion goes out of the range, the timing is interrupted and restarted after the out-of-range is removed. In order to suppress the influence of occasional jumps, the stable time needs to reach the minimum continuous window number to be considered improved, and if the stable time is insufficient, it is considered not improved. The spatial balance degree takes the relative deviation between the fixed sampling positions of the same layer in the same fixed time sampling window as the measurement. First, record the baseline of the layer deviation degree of each layer at the starting time of the compensation section, then record the present value of the layer deviation degree of each layer at the end time of the compensation section, and compare the "degree of decline of the present value relative to the baseline". When the layer deviation degree of at least two layers appears to decline, or the overall deviation degree after the combination of the fixed sampling position set of the main body area and the fixed sampling position set of the electrode adjacent area decreases relative to the baseline and the concentration difference between the fixed sampling position set of the main body area and the fixed sampling position set of the electrode adjacent area no longer expands, it is determined that the spatial balance degree is improved. If the number of effective fixed sampling positions is insufficient or the layer deviation degree is not determined due to the unified weight reduction of the window, the window is not counted in the determination, and the majority of the determinable windows is taken as the criterion. The improvement of the three indicators is determined by introducing a minimum change threshold, which is derived from the robust dispersion of the initialization sampling window or the verified engineering parameter, and the threshold is fixed in the current collection period.

[0096] When any two of the back-up amplitude, the stability time and the space balance degree are improved at the same time, the next compensation section retains the current compensation intensity; when all three are improved and the impurity rising interference state label and the space distribution imbalance state label are not triggered, the compensation intensity is allowed to be increased by a small increment in the next compensation section, but not more than the upper limit of the single segment maximum intensity and the maximum cumulative intensity; when less than two are improved, the compensation intensity is reduced by a preset proportion in the next compensation section, or the salt is added after the cooperative fine tuning of the dilution amount setting data, the circulation flow setting data and the stirring speed setting data is inserted first; when the observed sub-window of the verified sulfate ion concentration data or the verified chloride ion concentration data continuously rises and the ratio change trajectory falls out of the ratio reference interval, regardless of the results of the three indicators, it is directly considered that the inter-segment retention condition is not met, the salt is suspended and the disposal in the impurity direction is entered. If any indicator cannot be determined due to missing, backfilling or uniform weight reduction, the indicator is marked as "not improved", and when the unidentifiable state appears for two consecutive sections, the overall enters the conservative path, that is, the compensation intensity is reduced and the fine tuning of the mixed and mass transfer related setting data is preferentially executed.

[0097] In some embodiments of the present application, the priority resolution and cooperative adjustment of the segmented compensation path include: when there is an impurity rising interference state label, first adjusting the water dilution amount setting data and the circulation flow setting data, and then adjusting the copper salt solution addition rate setting data and the zinc salt solution addition rate setting data; when there is a space distribution imbalance state label and at the same time there is a single ion deficiency state label, first adjusting the stirring speed setting data and the circulation flow setting data, and then performing segmented compensation of the copper salt solution addition rate setting data or the zinc salt solution addition rate setting data in the corresponding metal ion direction.

[0098] Specifically, after entering the segmented compensation path, the execution order queue is generated according to the state label set, and the inhibition flag and the order lock are set. When the impurity rising interference state label is effective, the zinc salt solution addition rate setting data and the copper salt solution addition rate setting data are placed in the inhibition flag, and only the adjustment of the dilution amount setting data and the circulation flow rate setting data is allowed. The dilution amount setting data and the circulation flow rate setting data are increased or decreased in small steps, and each change lasts for one to two fixed time sampling windows as execution sub-windows, and then an equal length observation sub-window is set, only the position of the verified sulfate ion concentration data, the verified chloride ion concentration data and the two ratio change trajectories relative to the ratio reference interval is monitored, and whether the spatial difference degree is expanded. After two fixed time sampling windows meet the condition that "the verified sulfate ion concentration data and the verified chloride ion concentration data no longer rise and at least one ratio change trajectory returns to the ratio reference interval", the inhibition flag and the order lock are automatically released, the dilution amount setting data and the circulation flow rate setting data are kept at the last effective value, and the pilot small dose test section of the copper salt solution addition rate setting data and the zinc salt solution addition rate setting data can be started; if the ratio change trajectory falls out of the ratio reference interval again or the spatial difference degree expands in the observation sub-window, the last increment of the dilution amount setting data and the circulation flow rate setting data is withdrawn and the observation sub-window is extended, until the release condition is met or the preset change upper limit is reached, and then the conservative stay is entered.

[0099] When the spatial distribution imbalance state label and the single ion deficiency state label exist at the same time, the order lock points to the stirring speed setting data and the circulation flow rate setting data first, and the copper salt solution addition rate setting data or the zinc salt solution addition rate setting data is suspended until the order lock is released. The stirring speed setting data and the circulation flow rate setting data also use the small step adjustment mode of "execution sub-window + observation sub-window", and the observation criterion is that the in-layer deviation of at least two levels decreases compared with when entering this section, and the concentration difference between the electrode adjacent area fixed sampling position set and the main body area fixed sampling position set no longer increases. The order lock is released after two fixed time sampling windows meet the criterion, and the corresponding pilot small dose test section is entered according to the direction of the metal ion pointed by the single ion deficiency state label; if the continuous multiple windows do not meet the standard or trigger the unified weight reduction, which leads to indeterminacy, a small adjustment of the dilution amount setting data is inserted first to reduce the local ion strength, and then the fine tuning of the stirring speed setting data and the circulation flow rate setting data is continued; if the improvement is still not achieved after reaching the preset change upper limit, the conservative mixing and circulation settings are maintained and only the minimum amplitude of the metal direction segmented compensation is allowed, and the strength is immediately withdrawn if the inter-segment retention condition is not met.

[0100] When the impurity rising interference state label and the spatial distribution imbalance state label are effective at the same time, the priority is: the make-up water dilution amount setting data and the circulating flow rate setting data, the stirring speed setting data, the copper salt solution addition rate setting data and the zinc salt solution addition rate setting data. In implementation, the copper salt solution addition rate setting data and the zinc salt solution addition rate setting data are simultaneously locked, and are unlocked in turn only after the "ratio change trajectory returns to the ratio reference interval and the spatial difference degree no longer expands" for two consecutive fixed time sampling windows; the unlocking sequence follows the rising sensitivity measured in the pilot small dose test section, and when any observation sub-window appears again in the direction opposite to or the spatial difference degree expands, the locking is immediately restored and the liquid side or the mixed side setting data of the previous step is returned.

[0101] To avoid coupling amplification, the copper salt solution addition rate setting data and the zinc salt solution addition rate setting data cannot be increased at the same time in any execution sub-window, and the make-up water dilution amount setting data, the circulating flow rate setting data and the stirring speed setting data cannot be adjusted in the same direction at the same time. Only one setting data is changed at a time, and after the change, the influence on the verified copper ion concentration data, the verified zinc ion concentration data, the verified sulfate ion concentration data, the verified chloride ion concentration data and the spatial difference degree must be evaluated by an observation sub-window. The reference interval and the ratio reference interval remain frozen during the entire priority resolution and collaborative adjustment, and do not move the target due to short-term improvement.

Claims

1. A method for real-time compensation of electrolyte concentration during copper-zinc electrowinning, characterized in that, include: Copper ion concentration data, zinc ion concentration data, sulfate ion concentration data and chloride ion concentration data are collected synchronously at fixed time sampling windows in the upper layer fixed sampling location set, middle layer fixed sampling location set, lower layer fixed sampling location set and electrode adjacent area fixed sampling location set to form concentration data arranged by position and time; Based on the variation relationship of the same fixed sampling position in adjacent fixed time sampling windows and the relative deviation between fixed sampling positions in the same layer within the same fixed time sampling window, the concentration data is checked for temporal continuity and spatial consistency. Based on the ratio change relationship between metal ions and anions, the concentration data is checked for consistency of ratio change trajectory, and the checked concentration data is obtained. Establish a reference interval and compare the verified concentration data with the reference interval to generate a set of deviation levels and status labels; The segmented compensation path is executed according to the status label set. The set data for copper salt solution addition rate, zinc salt solution addition rate, water dilution amount, circulation flow rate and stirring speed are sequentially adjusted until the copper ion concentration data and zinc ion concentration data meet the reference range and the sulfate ion concentration data and chloride ion concentration data are in the stable range.

2. The method for real-time compensation of electrolyte concentration during copper-zinc electrowinning according to claim 1, characterized in that, At least two fixed sampling locations are set in each of the upper, middle, and lower fixed sampling location sets and the electrode adjacent area fixed sampling location set. Copper ion concentration data, zinc ion concentration data, sulfate ion concentration data, and chloride ion concentration data are recorded synchronously in the same fixed time sampling window. When a single fixed sampling location has missing concentration data in a single fixed time sampling window, it is filled once with the average concentration data of two adjacent fixed sampling locations in the same fixed time sampling window. When the same fixed sampling location has missing concentration data in two or more consecutive fixed time sampling windows, the fixed sampling location is removed from the current time continuity check and the current comparison, and only participates in the intra-layer statistics of the current spatial consistency check.

3. The method for real-time compensation of electrolyte concentration during copper-zinc electrowinning according to claim 2, characterized in that, The time continuity verification is based on the direction and magnitude of change of copper ion concentration data, zinc ion concentration data, sulfate ion concentration data and chloride ion concentration data at the same fixed sampling location in three consecutive fixed time sampling windows. When alternating directions occur and the magnitude of change is lower than the preset micro-threshold, the concentration data of the intermediate fixed time sampling window is replaced by the linear extrapolation value of the previous fixed time sampling window and the next fixed time sampling window at the same fixed sampling location. When alternating directions occur for the second time at the same fixed sampling location and the magnitude of change is lower than the preset micro-threshold, the subsequent concentration data of the fixed sampling location in the current comparison are included according to the preset weighting coefficient.

4. The method for real-time compensation of electrolyte concentration during copper-zinc electrowinning according to claim 3, characterized in that, Spatial consistency verification is based on the relative deviation between fixed sampling positions in the same layer within the same fixed time sampling window. The deviations of the fixed sampling positions in the same layer relative to the median value of that layer are sorted and the single fixed sampling position with the largest deviation is removed as an outlier fixed sampling position. When the relative deviation directions of the upper layer fixed sampling position set and the lower layer fixed sampling position set are opposite and the concentration difference between the fixed sampling position set in the electrode adjacent area and the fixed sampling position set in the main area increases, the removal of outlier fixed sampling positions is canceled, and all fixed sampling positions in that fixed time sampling window are uniformly included according to the preset weighting coefficient.

5. The method for real-time compensation of electrolyte concentration during copper-zinc electrowinning according to claim 4, characterized in that, The establishment of the reference interval includes initializing the sampling window and sliding update: the initial sampling window remains uncompensated, and the upper and lower bounds are determined by the verified copper ion concentration data, verified zinc ion concentration data, verified sulfate ion concentration data and verified chloride ion concentration data, respectively, as the initial reference interval. During operation, the sliding reference interval is updated with the verified copper ion concentration data, verified zinc ion concentration data, verified sulfate ion concentration data, and verified chloride ion concentration data from the most recent fixed time sampling windows, and the sliding reference interval is frozen in the main compensation execution segment and the tuning verification segment of the segmented compensation path.

6. The method for real-time compensation of electrolyte concentration during copper-zinc electrowinning according to claim 5, characterized in that, The consistency verification of the ratio change trajectory is based on the ratio change trajectory between copper ion concentration data and zinc ion concentration data, as well as the ratio change trajectory of copper ion concentration data and zinc ion concentration data relative to the sum of sulfate ion concentration data and chloride ion concentration data. The ratio reference interval is extracted in the initial sampling window, updated in the sampling window of the most recent fixed time during the operation, and frozen in the main compensation execution segment and the tuning verification segment of the segmented compensation path. When any ratio change trajectory deviates from the ratio reference range in two or more consecutive fixed-time sampling windows, and the sulfate ion concentration data or chloride ion concentration data rises continuously within the same fixed-time sampling window, it is recorded as a directional deviation and its weight is increased in the deviation level determination.

7. The method for real-time compensation of electrolyte concentration during copper-zinc electrowinning according to claim 6, characterized in that, The status label set includes single-ion deficiency status labels, dual-ion coupling deficiency status labels, impurity rise interference status labels, and spatial distribution imbalance status labels. Specifically: a single-ion deficiency status label corresponds to a verified copper ion concentration or a verified zinc ion concentration that decreases and falls outside the corresponding reference interval in two or more consecutive fixed-time sampling windows; a dual-ion coupling deficiency status label corresponds to verified copper ion concentration and verified zinc ion concentration that decrease synchronously and fall outside the corresponding reference interval in the same fixed-time sampling window; an impurity rise interference status label corresponds to verified sulfate ion concentration or verified chloride ion concentration that increases in two or more consecutive fixed-time sampling windows, causing the ratio change trajectory to fall outside the ratio reference interval; and a spatial distribution imbalance status label corresponds to an increase in the spatial difference between multiple fixed sampling locations within the same fixed-time sampling window, and an increase in the concentration difference between the set of fixed sampling locations in the electrode proximity area and the set of fixed sampling locations in the main body area. When both the dual-ion coupling deficiency status label and the impurity rise interference status label are established simultaneously, the path corresponding to the impurity rise interference status label is executed first.

8. The method for real-time compensation of electrolyte concentration during copper-zinc electrowinning according to claim 7, characterized in that, The segmented compensation path includes a pilot small-dose test segment, a main compensation execution segment, and a tuning and verification segment. In the pilot small-dose test segment, the set data for the addition rate of copper salt solution and zinc salt solution are adjusted slightly in sequence. The most recent uncompensated fixed-time sampling window is used as the baseline to calculate the recovery sensitivity and determine the main compensation execution order. In the main compensation execution segment, multiple additions are performed according to the main compensation execution order. At the end of each compensation segment, the compensation intensity is maintained or reduced according to a preset ratio based on the inter-segment retention conditions. In the tuning and verification segment, the segmented compensation path ends when the verified copper ion concentration data and the verified zinc ion concentration data return to the reference range, and the verified sulfate ion concentration data and the verified chloride ion concentration data no longer increase and the spatial difference no longer expands.

9. The method for real-time compensation of electrolyte concentration during copper-zinc electrowinning according to claim 8, characterized in that, The inter-segment retention conditions consist of three indicators: recovery magnitude, stabilization time, and spatial balance. The current compensation intensity is retained when any two of these indicators improve simultaneously; otherwise, the compensation intensity is reduced by a preset ratio in the next compensation segment. The recovery magnitude is the net increment of the verified copper ion concentration data and the verified zinc ion concentration data at the start and end times of the compensation segment. The stabilization time is the duration for which the verified copper ion concentration data and the verified zinc ion concentration data remain within the reference range after the end of the compensation segment. The spatial balance is the degree of decrease in the relative deviation between fixed sampling positions in the same layer within the same fixed time sampling window.

10. The method for real-time compensation of electrolyte concentration during copper-zinc electrowinning according to claim 9, characterized in that, The priority resolution and coordinated adjustment of the segmented compensation path include: when there is an impurity rise interference status label, first adjust the water dilution setting data and circulation flow setting data, and then adjust the copper salt solution addition rate setting data and zinc salt solution addition rate setting data; when there is a spatial distribution imbalance status label and a single ion deficiency status label at the same time, first adjust the stirring speed setting data and circulation flow setting data, and then perform segmented compensation of the copper salt solution addition rate setting data or zinc salt solution addition rate setting data corresponding to the metal ion direction.

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