Integrated treatment system for mancozeb production wastewater with integrated manganese and zinc recovery function

Abstract

The present application relates to the field of industrial wastewater treatment and resource recycling, in particular to a maneb-zinc production wastewater integrated treatment system with integrated manganese-zinc recovery function; the system comprises parameter acquisition and mapping, frequency control breakage, isoelectric focusing separation and in-situ acidification closed loop modules; the system combines the dynamic solution of the pulse control parameters with the inflow flow and conductivity; the asymmetric high-frequency pulse electric field is used to destroy the coordination bond in the wastewater to release the target metal ions, and the anode potential is limited to prevent the manganese ions from being deeply oxidized; then a continuous spatial pH gradient field is constructed to drive the zinc and manganese ions to form micro-flocs in a specific pH range and be segmented and intercepted; finally, the intercepted micro-flocs are dissolved in-situ by using the self-produced acid solution of the bipolar membrane to realize the closed loop output; the present application discards the traditional chemical oxidation and mixed precipitation, effectively overcomes the problems of unstable breakage and membrane interface fouling by using the spatial continuous gradient, and realizes the high-purity segmented recovery and continuous reuse of manganese and zinc.

Description

Technical Field

[0001] This invention relates to the field of industrial wastewater treatment and resource recovery, specifically to an integrated treatment system for wastewater from the production of manganese and zinc by Dassen, which integrates manganese and zinc recovery functions. Background Technology

[0002] The production process of manganese zinc generates wastewater containing manganese complexes, zinc complexes, and organic complex residues. Traditional treatment methods often use chemical oxidation, alkali precipitation, and neutralization to remove the metal components. Although these methods can reduce the metal content and organic load in the wastewater to some extent, the release of complexed metal ions is difficult, and different metals are easily mixed and precipitated, resulting in low purity of the recovered liquid. Furthermore, the released manganese ions are easily further oxidized into solid products that are difficult to recover during the treatment process. With the increasing demand for continuous production and resource recycling in workshops, the treatment of wastewater from manganese zinc production gradually needs to take into account continuous operation, metal separation, and recycling. However, existing technologies are prone to problems such as unstable complex breaking effect, difficulty in metal segmentation and recovery, and easy scaling and clogging on the membrane surface or separation interface when operating conditions exceed the set threshold, resulting in low system operation stability and target metal recycling efficiency. Summary of the Invention

[0003] The purpose of this invention is to provide an integrated treatment system for manganese and zinc production wastewater with integrated manganese and zinc recovery functions. This system aims to solve the problems in existing technologies, such as unstable complex-breaking effects when faced with fluctuating influent, easy mixing and precipitation of different metals leading to low recovery purity, easy further oxidation of released manganese ions into solid products, and easy scaling at the separation interface. Specifically, the technical solution of this invention is as follows: An integrated wastewater treatment system for manganese and zinc production, incorporating manganese and zinc recovery capabilities, includes: The parameter acquisition and mapping module is used to acquire the initial fluid parameters of wastewater containing complexed metals and calculate and generate pulse control parameters. The frequency-controlled complex-breaking module is used to introduce the wastewater containing complexed metal into a frequency-controlled complex-breaking zone equipped with an anode and a cathode, and apply an asymmetric high-frequency pulse electric field based on the pulse control parameters to break the coordination bonds in the wastewater containing complexed metal, thereby generating a complex-breaking fluid containing free target metal ions and degraded small organic molecules. The isoelectric focusing separation module is used to introduce the complex-breaking fluid into the bipolar film isoelectric focusing region, establish a continuous spatial acid-base gradient field under the action of the applied DC electric field, drive the free target metal ions to migrate and form metal micro flocs in the corresponding acid-base range, and retain them in the micro floc collection cavity connected to the bipolar film isoelectric focusing region. The in-situ acidification closed-loop module includes an acid reflux pipeline connecting the acid-producing side of the bipolar isoelectric focusing region and the micro-floc collection chamber. The acid-producing side is formed by the aggregation of hydrogen ions dissociated from the bipolar membrane inside the bipolar isoelectric focusing region. It is used to dissolve the retained metal micro-flocs with acid to generate a metal salt solution and output it.

[0004] Preferably, the initial fluid parameters include influent flow rate data and conductivity data; the parameter acquisition and mapping module obtains the matching pulse control parameters based on the influent flow rate data and the conductivity data through a preset grading mapping logic table; wherein, the pulse control parameters include the pulse electric field duty cycle.

[0005] Preferably, the anode in the frequency-controlled complex-breaking zone is an anode coated with ruthenium-iridium boron-doped diamond; the frequency-controlled complex-breaking module sets the frequency of the asymmetric high-frequency pulse electric field to the resonant frequency corresponding to the polarization response frequency range of the coordination bonds in the complexed metal wastewater.

[0006] Preferably, the free target metal ion includes manganese ions; the frequency-controlled network breaking module limits the polarization potential generated by the anode during operation to a level lower than or equal to a preset potential threshold, the preset potential threshold being lower than the oxidation potential threshold of the manganese ions; the frequency-controlled network breaking module limits the polarization potential of the anode below the preset potential threshold through a voltage limiting circuit.

[0007] Preferably, the bipolar membrane isoelectric focusing region is composed of a multi-chamber microchannel formed by alternating bipolar membranes and monovalent anion selective exchange membranes; the isoelectric focusing separation module constructs the continuous spatial pH gradient field by controlling the flow of dissociated water introduced on both sides of the bipolar membrane.

[0008] Preferably, the pH range corresponding to the continuous spatial pH gradient field includes, in order of pH value, a first pH range, a second pH range, and a non-precipitation range; The free-state target metal ions include a first target metal ion and a second target metal ion; the complex-breaking fluid also includes non-target ions; If the first target metal ion enters the first pH range and reaches the first precipitation pH critical condition corresponding to its nucleation critical state, a first metal micro-floc is formed and retained; if the second target metal ion enters the second pH range and reaches the second precipitation pH critical condition corresponding to its nucleation critical state, a second metal micro-floc is formed and retained; if the second target metal ion does not reach the second precipitation pH critical condition corresponding to its nucleation critical state, it continues to migrate in the continuous spatial pH gradient field; if the non-target ion enters the non-precipitation range, it remains in a free state and is discharged.

[0009] Preferably, the first target metal ion is zinc ion, and the first metal flocculent is zinc hydroxide; the second target metal ion is manganese ion, and the second metal flocculent is manganese hydroxide.

[0010] Preferably, the degrading organic molecules carry a negative charge; the isoelectric focusing separation module, under the combined action of the DC electric field and the fluid shear force generated by the complex-breaking fluid in the multi-chamber microchannel, drives the degrading organic molecules to accumulate on the surface of the monovalent anion selective exchange membrane, forming a dynamic competitive repulsion layer; the isoelectric focusing separation module, based on the DC electric field and the fluid shear force, maintains the local enrichment concentration of the degrading organic molecules on the membrane surface between 50 mg / L and 150 mg / L.

[0011] Preferably, the in-situ acidification closed-loop module includes a reflux output terminal for outputting the metal salt solution.

[0012] Preferably, the preset potential threshold is 0.8V to 1.1V.

[0013] The present invention has the following beneficial effects: 1. This invention, by sequentially setting a parameter acquisition and mapping module, a frequency-controlled complex-breaking module, an isoelectric focusing separation module, and an in-situ acidification closed-loop module, transforms the treatment process of wastewater containing complexed metals from the traditional chemical oxidation and mixing neutralization method into a continuous treatment process combining electric field complex breaking, spatial migration, segmented interception, and in-situ acidification recovery. This enables the release of manganese and zinc ions while maintaining their original valence state, segmented recovery, and closed-loop reuse, reducing the probability of mixed precipitation and improving the purity of the recovered liquid. 2. Based on influent flow rate data and conductivity data, this invention calculates pulse control parameters in real time through a preset grading mapping logic table, and adaptively adjusts at least the duty cycle of the pulse electric field. This can transform influent fluctuations into quantifiable electric field control inputs, ensuring that wastewater under different flow loads and ion intensities maintains a relatively stable complex breaking intensity. This avoids problems of insufficient complex breaking or overtreatment under fixed parameter conditions, and improves the stability of continuous operation. Attached Figure Description

[0014] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be conventionally introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Figure 1 This is a schematic diagram of the integrated treatment system for wastewater from the production of manganese and zinc, which integrates manganese and zinc recovery functions according to the present invention. Detailed Implementation

[0015] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0016] Example 1: Please see Figure 1 The integrated treatment system for wastewater from the production of manganese and zinc, which integrates manganese and zinc recovery functions, includes: a parameter acquisition and mapping module, used to acquire the initial fluid parameters of the wastewater containing complexed metals and calculate and generate pulse control parameters; The frequency-controlled complex-breaking module is used to introduce wastewater containing complexed metals into the frequency-controlled complex-breaking zone. Based on pulse control parameters, an asymmetric high-frequency pulsed electric field is applied to the frequency-controlled complex-breaking zone through the anode and cathode set in the zone to break the coordination bonds in the wastewater containing complexed metals, generating a complex-breaking fluid containing free target metal ions and degraded small organic molecules. The frequency-controlled complex-breaking module limits the polarization potential of the anode to below or equal to a preset potential threshold. The isoelectric focusing separation module is used to introduce the complex-breaking fluid into the bipolar film isoelectric focusing region. The bipolar film isoelectric focusing region is connected to the frequency-controlled complex-breaking region through a pipeline. Under the action of a DC electric field, a continuous spatial acid-base gradient field is established in the bipolar film isoelectric focusing region, which drives the migration of free target metal ions and forms metal micro-flocs in the corresponding acid-base range. The metal micro-flocs are then intercepted in the micro-floc collection chamber connected to the bipolar film isoelectric focusing region. The in-situ acidification closed-loop module includes an acid reflux pipeline connecting the acid-producing side of the bipolar isoelectric focusing region and the micro-floc collection chamber. The acid-producing side is formed by the aggregation of hydrogen ions dissociated from the bipolar membrane inside the bipolar isoelectric focusing region. It is used to dissolve the retained metal micro-flocs with acid to generate a metal salt solution and output it.

[0017] This embodiment provides a continuous treatment system for manganese and zinc production wastewater with integrated manganese and zinc recovery function; specifically, the system is arranged between the mother liquor recovery end and the comprehensive wastewater buffer tank in the manganese and zinc production workshop, and is used to treat wastewater containing manganese-amine complex, zinc-amine complex and dithiocarbamate-derived organic matter, and directly outputs metal salt solution that can be returned to the front-end synthesis section. Specifically, the system includes, in sequence along the wastewater flow direction, a parameter acquisition and mapping module, a frequency-controlled complex breaking module, an isoelectric focusing separation module, and an in-situ acidification closed-loop module. The wastewater first enters the buffer inlet manifold, and a flow meter, conductivity meter, and temperature compensation unit are installed at the rear end of the manifold. The parameter acquisition and mapping module reads the real-time flow rate and conductivity, and provides pulse control parameters accordingly. These pulse control parameters are used to determine at least the duty cycle of the asymmetric high-frequency pulse electric field, the duration of the pulse group, and the pulse interval time, so that the fluid entering the frequency-controlled complex breaking zone can maintain a repeatable complex breaking intensity under different ion loads. The frequency-controlled complex breaking zone can be set as a plate-type flow reaction chamber, with the anode and cathode arranged in parallel inside the chamber, forming a narrow gap flow channel between the two electrodes; wastewater enters tangentially from the inlet of the flow channel and passes through the electrode gap under the combined action of laminar flow and local micro eddies; at this time, the pulse power supply applies an asymmetric high-frequency pulse electric field to this zone; asymmetry means that the duration of the forward pulse, the duration of the reverse relaxation, or the peak amplitude of the two are different, so that the coordination bonds are continuously subjected to alternating traction but the anode is avoided from being in a high polarization state for a long time. Based on this, high frequency specifically refers to the frequency range of the pulsed electric field being set from 10kHz to 50kHz; in this way, the chelate rings originally coated with metal ions are preferentially weakened and broken, releasing the free target metal ions; at the same time, some organic complex residues are cleaved into negatively charged degraded organic small molecules. To further illustrate its working principle, specific fluid treatment parameters are provided here; assuming that the volumetric flow rate of wastewater entering the reaction chamber at a certain moment is... Electrical conductivity is After mapping, pulse working group A is obtained; under this working group, the duration of the positive pulse is The duration of the reverse relaxation is ; If the initial molar concentrations of manganese complex and zinc complex in the wastewater are respectively and After one pulse group, the release rates of free manganese ions and zinc ions reached 70% and 80%, respectively. The remaining incompletely dissociated complexed particles continued to be subjected to the field in subsequent pulse groups. That is, the system is configured such that the system does not completely dissociate in one go, but gradually converts the complexed metal into mobile free ions according to the electric field window. During the frequency-controlled complex breaking process, the polarization potential is constrained by an upper limit, which is lower than the oxidation potential threshold of the target metal ion. For example, when the target metal ion is manganese ion, its oxidation potential threshold is 1.23V. To ensure that deep oxidation does not occur, a hardware-level limit is implemented through a voltage limiting circuit to maintain it between 0.8V and 1.1V. The beneficial effect is that although the system applies enough energy to weaken the coordination structure, it does not allow the anode to enter the range that would further oxidize manganese ions into high-valence insoluble products, thus overcoming the technical defect in traditional oxidation methods where released manganese ions are prone to secondary oxidation to form solid precipitates. After the complex is broken, the fluid enters the bipolar membrane isoelectric focusing region directly through the pipeline. Under the action of a DC electric field, hydrogen ions and hydroxide ions generated by the dissociation of water by the bipolar membrane establish a continuous spatial acid-base gradient in multiple adjacent microcells. Free metal ions traverse the microcells of different acid-base levels laterally or obliquely under the combined action of electromigration and fluid carrying. When a certain metal ion enters its acid-base range suitable for the formation of micro-flocs, local nucleation occurs and micron-sized metal micro-flocs are formed. Since the size of these micro-flocs is larger than the pore size standard of the retention medium, they will be screened, blocked, or retained on the retention side, while the remaining ions and soluble impurities that are still in a free state continue to migrate or are discharged with the liquid flow. As an example at the microscopic level, assume that the isoelectric focusing region is divided into three continuous micro-regions along the flow direction: the first micro-region, corresponding to the pre-transition section of the non-precipitation zone; the second micro-region, corresponding to the first pH range; and the third micro-region, corresponding to the second pH range. Specifically, the pH value of the pre-transition section of the first micro-region is controlled below 7.5, the pH value of the second micro-region is controlled between 7.5 and 8.5, and the pH value of the third micro-region is controlled between 9.0 and 10.5. If the mass concentration ratio of free zinc ions to manganese ions entering the zone is within a preset range, most of the zinc ions can form hydroxide micro-flocs in the second micro-zone and be collected by the first interception side of the micro-floc collection chamber. However, because manganese ions have a higher pH threshold required to form micro-flocs, they continue to migrate to the third micro-zone to form another type of micro-flocs and are collected by the second interception side of the micro-floc collection chamber. Through the spatial sequential distribution, the two metal ions that were originally mixed are separated into different collection channels. The in-situ acidification closed-loop module is set after each interception side; the acid solution formed by the bipolar membrane dissociation water is not discharged as waste liquid, but is introduced into the corresponding micro-floc collection chamber through the acid return pipeline; the collected metal micro-flocs are redissolved in acid, converted into metal salt solution, and then sent to the storage tank or directly back to the production system through the output pipeline; since the acid source comes from inside the system, no new external acid is introduced, so the source of impurities in the recovered liquid is small, which facilitates subsequent reuse; Furthermore, in terms of abnormal operating condition control, three types of abnormalities may occur during continuous operation. If the conductivity of the influent jumps to or reaches the upper limit of the preset conductivity within the preset time period, resulting in an abnormal increase in current density under pulse action, the parameter acquisition and mapping module will prioritize reducing the duty cycle and shortening the duration of the positive pulse to avoid excessive increase in anode potential. If the complex breaking is insufficient and the proportion of free metal ions in the isoelectric focusing zone is lower than or equal to the preset minimum concentration, the system will automatically extend the residence time in the complex breaking zone or reduce the influent flow rate to compensate for the decrease in downstream interception. If the pressure difference on a certain interception side continues to rise, it indicates that the micro-flocs are accumulating too quickly. In this case, the in-situ acidification closed-loop module will first start the acid flushing backflow on that side to convert the intercepted micro-flocs into a solution before restoring normal separation, thus avoiding local blockage. For example, during the continuous production period of concentrated mother liquor replacement in the manganese-zinc synthesis workshop, the front-end washing mother liquor and equipment flushing liquid are mixed and enter the comprehensive wastewater buffer tank. This batch of wastewater has a high content of complexed manganese and complexed zinc, and is accompanied by residual amines and sulfur-containing organic matter. After the wastewater is pumped into this system at a constant flow rate, migratory manganese and zinc ions are first released in the frequency-controlled complex breaking zone, and then different metal micro-flocs are generated in stages in the bipolar membrane isoelectric focusing zone. Finally, the acid solution generated by in-situ dissociation is used to convert them into manganese salt solution and zinc salt solution respectively. At the end of the concentrated mother liquor replacement period, the workshop can directly incorporate the obtained recovered liquid into the batching section of the next day to reduce the amount of external raw materials to be added. This embodiment transforms the static mixing process that originally relied on chemical oxidation and alkaline precipitation into a continuous physicochemical separation process based on electric field breaking, spatial migration and in-situ acidification recovery, thereby achieving the release of the target metal while maintaining its original valence state, segmented retention and closed-loop reuse.

[0018] Example 2: The initial fluid parameters include influent flow rate data and conductivity data. The parameter acquisition and mapping module obtains the matching pulse control parameters based on the influent flow rate data and conductivity data through a preset tiered mapping logic table that uses the influent flow rate data and conductivity data as matching indices. Among them, the pulse control parameters include the pulse electric field duty cycle.

[0019] This embodiment provides a parameter mapping mechanism for fluctuating influent conditions. Specifically, in actual workshop operation, the mixing ratio of centrifugal mother liquor, floor flushing liquid, and equipment switching discharge is not constant. If fixed pulse electric field parameters are still used, there will be problems such as insufficient network breaking and unreasonable energy distribution at certain times. Therefore, a dual-variable mapping method based on flow rate and conductivity is introduced at the influent end to determine the pulse electric field duty cycle in real time. Specifically, the influent flow rate reflects the volumetric load of liquid entering the reaction chamber per unit time, and the conductivity reflects the total amount of migratable ions in the liquid and the strength of the solution's electrical properties. The mapping function is not limited to a single form of expression and can employ table lookup, piecewise linear, two-dimensional interpolation, or an empirical fitting model embedded in the parameter acquisition and mapping module. Its system logic configuration is as follows: under the dynamic constraints of increased influent flow rate leading to a shorter residence time and increased conductivity leading to a stronger electric field response, a duty cycle suitable for the current wastewater state is provided. To further illustrate this mapping mechanism, the following parameter classification and mapping examples are provided; it is assumed that the system pre-establishes three flow ranges including low flow range F1, medium flow range F2 and high flow range F3, and three conductivity ranges including low conductivity range C1, medium conductivity range C2 and high conductivity range C3; Specifically, the low flow rate zone F1 corresponds to a volumetric flow rate less than or equal to Q1, the medium flow rate zone F2 corresponds to a volumetric flow rate greater than Q1 and less than or equal to Q2, and the high flow rate zone F3 corresponds to a volumetric flow rate greater than Q2; the low conductivity zone C1 corresponds to a conductivity less than or equal to E1, the medium conductivity zone C2 corresponds to a conductivity greater than E1 and less than or equal to E2, and the high conductivity zone C3 corresponds to a conductivity greater than E2. Q1, Q2, E1, and E2 are all constants preset based on the actual front-end process. The parameter acquisition and mapping module embeds a historical data statistical model, which calculates and calibrates the critical thresholds for each zone based on the joint probability density function of historical influent conductivity and flow rate. The preset constants are obtained through statistical distribution analysis of historical influent flow rate and historical conductivity under different production cycles of the front-end process. The parameter acquisition and mapping module internally forms a 3×3 mapping table: when the wastewater is in the low flow rate zone F1 and the low conductivity zone C1, the duty cycle is 30%; when it is in the medium flow rate zone F2 and the medium conductivity zone C2, the duty cycle is 45%; when it is in the high flow rate zone F3 and the high conductivity zone C3, the duty cycle is 60%. For example, if the flow rate falls in the medium flow rate zone F2 and the conductivity falls in the high conductivity zone C3 in the first 30 minutes after the start of the concentrated replacement period of the mother liquor, the system will not directly apply the fixed parameters, but will select the duty cycle corresponding to F2 and C3 from the mapping table, such as 52%. In this way, even if the wastewater composition varies in different shifts and different rinsing stages on the same production line, the frequency-controlled complex breaking zone can still maintain a similar complex breaking effect. Furthermore, time smoothing can be incorporated into the mapping process; if the flow rate jumps from the medium flow rate region F2 to the high flow rate region F3 within two adjacent sampling periods, while the conductivity remains in the medium conductivity region C2, the parameter acquisition and mapping module does not need to instantaneously increase the duty cycle from 45% to 55%, but rather through a short-term ramp-up process, for example, first increasing to 48%, and then increasing to 52% in the next sampling period; this can suppress frequent power supply jitter and reduce the impact on the electrode surface; Furthermore, in terms of abnormal operating condition control, if the sensor signal is abnormal, such as the flow signal being disconnected or the conductivity reading continuously exceeding the range, the parameter acquisition and mapping module enters the protection mapping mode. At this time, the average value of the most recent stable period can be used as a temporary input, or the system can be switched to a conservative duty cycle, such as fixed in the range of 35% to 40%, to ensure that the system does not completely shut down due to a single sensor failure. If the abnormality continues for more than the preset time, the flow of the front-end buffer tank will be reduced and a maintenance prompt will be issued. For example, in the same manganese zinc wastewater recovery unit, the regular production shift is mainly for equipment cleaning and drainage, with a high flow rate and medium conductivity; the concentrated replacement period of the mother liquor is mainly for the replacement and drainage of the reaction mother liquor, with a low flow rate and high conductivity. If both shifts use the same duty cycle, the regular production shift is prone to insufficient residence time, while the concentrated replacement period of the mother liquor may result in overtreatment. After adopting the above mapping method, the duty cycle of the regular production shift can be automatically increased to compensate for the shorter residence time, while the duty cycle of the concentrated replacement period of the mother liquor is maintained at a medium level, so that the entire treatment chain remains stable. This mechanism transforms influent fluctuations into quantifiable electric field control inputs, thereby achieving adaptive matching of the network breakdown intensity under different wastewater loads and avoiding the coexistence of overtreatment and undertreatment.

[0020] Example 3: The anode in the frequency-controlled complex breaking zone is an anode coated with ruthenium-iridium boron-doped diamond; the frequency-controlled complex breaking module anchors the frequency of the asymmetric high-frequency pulse electric field to the resonant frequency corresponding to the polarization response frequency range of the coordination bonds in the complexed metal wastewater.

[0021] The frequency-controlled network breaking module locks the polarization potential of the anode below the potential threshold through hardware limiting; among which, the free target metal ions include manganese ions; This embodiment provides a complex-breaking enhancement mechanism for strongly complexed structures containing easily oxidizable manganese ions. Specifically, based solely on adjusting the duty cycle according to flow rate and conductivity, there remains a technical defect that needs to be addressed: if the anode material is ordinary and the pulse frequency deviates from the coordination bond response range, the system may have to rely on higher voltage or longer energizing time to achieve complex breaking, which increases the risk of manganese ion oxidation. Therefore, this embodiment further limits the anode structure, frequency anchoring method, and potential limiting method. Specifically, the anode in the frequency-controlled osmosis breaking zone is a composite anode coated with ruthenium-iridium-doped diamond. This type of anode combines the stability of the conductive framework, surface electrochemical activity, and resistance to organic pollution. When faced with residual sulfur-containing organic matter and amine complexing agents in mancozeb wastewater, its surface is not prone to forming a continuous insulating passivation layer, thus making it suitable for operation under long-cycle pulse conditions. The cathode can be a corrosion-resistant metal plate or a conductive composite plate to form a stable slit electric field with the anode. In this application, frequency anchoring means that the system does not arbitrarily set the asymmetric pulse frequency, but selects it around the response range of the dominant coordination bond in the target wastewater. For manganese-amine complexation and zinc-amine complexation, one or more preferred frequency windows can be obtained through experimental calibration first, and the frequency window most suitable for the current water quality can be selected during operation. For example, the frequency-controlled complex breaking module stores three candidate frequency groups: f1, f2, and f3. If it is found that f2 has the highest downstream ion release rate and the most stable anode potential during the trial operation, then f2 will be used as the main operating frequency. When the composition of the influent changes, it is also possible to switch between the three frequency groups instead of starting the search from zero. To further illustrate the technical effect of frequency anchoring, the following quantitative example of the dissociation process is provided; assuming the initial concentration of manganese complex in a specific batch of wastewater is C1; if frequency group f1 deviating from the response range is used, the dissociation rate after one treatment cycle is only 41.6%; if frequency group f2, which is closer to the resonant response, is used, the dissociation rate after the same treatment cycle can reach 75.0%; the total duration of electric field energization is the same in both cases, but the latter has a stronger directional effect on the coordination bonds, so it is not necessary to compensate for the efficiency difference by raising the potential; More importantly, the polarization potential is locked below a preset threshold through hardware limiting. This hardware limiting can be achieved by analog limiting circuits, comparator cutoff units, fast gate control modules, or a pulse source host computer and slave computer working together. Its operating logic is as follows: once the sampling circuit detects that the polarization potential has reached near the preset upper limit threshold, the limiting unit immediately compresses the pulse peak or terminates the positive pulse in advance, so that the anode cannot cross the high-valence oxidation potential range that would lead to further oxidation of manganese ions. In this way, even if there is a sudden increase in conductivity, bubble adhesion, or local concentration polarization, the manganese ions will not be converted into high-valence insoluble substances that are difficult to recover due to control lag. To further illustrate, assume the preset potential threshold is E1, the oxidation threshold of manganese ions is E2, and E1 is lower than E2. When the system operates under normal conditions, the polarization potential fluctuates periodically below E1. If the theoretical peak value tends towards E2 due to an increase in the influent conductivity at a certain moment, the limiting unit will cut off the positive pulse when the potential approaches E1. Thus, although the complex breaking energy decreases slightly in this cycle, manganese still remains in the divalent state and can continue to dissociate and migrate in subsequent cycles. It can be seen that this implementation does not require chemical treatment of the generated high-valent manganese oxides through reducing agents, but directly suppresses the generation of high-valent manganese through potential hardware limiting. Furthermore, in terms of abnormal operating condition control, if long-term monitoring reveals a decrease in the rupture rate while the potential never reaches the limiting threshold, it is first determined that the anode surface activity has decreased or the frequency window has shifted. At this time, a short-term self-cleaning step can be triggered, or the system can switch back between candidate frequency groups. If the limiting action is too frequent, it indicates that the current influent conditions exceed the preset treatment window. The system can then link the front-end buffer tank to dilute the influent or temporarily reduce the treatment throughput. For example, when the manganese zinc production line was running continuously for three days, the proportion of waste liquid from the front-end reactor cleaning increased, and the content of amine complexing agents in the wastewater was higher than the conventional value. If ordinary titanium-based anodes and unlocked general pulse frequencies are still used, the voltage is often increased to maintain the complex breaking, which easily leads to manganese oxidation. After adopting this embodiment, the composite anode can still maintain high surface activity when the organic load increases. The frequency control complex breaking module switches to a frequency group more suitable for this batch of wastewater, and the hardware limiter keeps the polarization potential continuously limited to the upper limit of anode polarization, so that manganese ions remain in a recyclable state. This mechanism addresses the contradiction that breaking the network requires sufficient energy while manganese cannot be oxidized, through a synergistic approach involving material selection, frequency anchoring, and hardware limiting. This allows manganese ions to be released while maintaining their original valence state and to operate stably and continuously.

[0022] Example 4: The bipolar membrane isoelectric focusing region consists of a multi-chamber microchannel formed by alternating bipolar membranes and monovalent anion selective exchange membranes; the isoelectric focusing separation module constructs a continuous spatial pH gradient field by controlling the dissociated water flow on both sides of the bipolar membrane.

[0023] This embodiment provides a multi-chamber microchannel mechanism for stabilizing the construction of a spatial pH gradient. Specifically, given that free manganese and zinc ions can be released relatively stably upstream, if only a single precipitation tank or ordinary membrane chamber is used downstream, the acid-base environment distribution will be disordered and lack gradient restriction, easily leading to the problem of the two metals mixing and precipitating in the same area. Therefore, this embodiment further adopts a multi-chamber microchannel structure with alternating bipolar membranes and monovalent anion selective exchange membranes, so that the pH is no longer controlled at a single point, but forms a gradient field that changes continuously along space. Specifically, the multi-chamber microchannel may include several separation units arranged in series or parallel. In each separation unit, a bipolar membrane is responsible for dissociating water into hydrogen ions and hydroxide ions, while a monovalent anion selective exchange membrane controls the transmembrane migration path of specific ions and inhibits unwanted reverse migration. By setting dissociated water flows on both sides of the bipolar membrane and adjusting their flow rate, pressure, and circulation rate, the generation rate of acid or alkali in each microchamber can be controlled, thereby forming a continuous acid-base gradient that gradually transitions from the acidic side to the alkaline side. As an example, assume the region contains four adjacent microchambers, denoted as M1, M2, M3, and M4. After controlling the dissociated water flow, the pH of M1 is close to weakly acidic, M2 is close to neutral, M3 is slightly alkaline, and M4 is relatively strong alkaline. Free metal ions in the broken-complex fluid do not immediately precipitate after entering from the inlet, but gradually migrate through M1 to M4. Thus, if a metal ion is suitable for forming microflocs in M3, it will mainly be retained within that microchamber region; if another metal ion is suitable for forming microflocs in M4, it will continue to advance to M4. Spatial position thus becomes the separation dimension. Furthermore, the dissociated water flow not only affects the pH level but also the smoothness of the gradient. If the rate of change of the pH gradient between M2 and M3 exceeds the preset smoothing threshold, metal ions may suddenly nucleate at the boundary, forming large particle deposits, which is not conducive to continuous retention. By appropriately adjusting the dissociated water flow, a smoother gradient can be formed between M2 and M4, and metal ions gradually reach the nucleation conditions during migration, forming micro-flocs with more uniform particle size. Furthermore, regarding abnormal operating condition control, if a pH drift is detected in a microcell during operation, for example, if M3 becomes too acidic, causing a reduction in the microflocs that should form there, the dissociation water supply to the corresponding bipolar membrane side should be increased first; if the drift still does not recover, check whether there is a local leak or a decrease in ion selectivity in the monovalent selective membrane; if multiple microcells drift simultaneously, it indicates a systemic abnormality in the total dissociation water supply or DC field strength. In this case, the system can be switched to a low-flux steady-state mode to first maintain the safety of the membrane module and then gradually restore the gradient distribution. For example, during the stable operation phase of the same manganese zinc production line, the zinc content in the recovered liquid is slightly higher than that in the concentrated replacement period of the mother liquor. After the mixed ion flow after complex breaking enters the multi-chamber microchannel, it remains soluble in the front microchamber. When it enters the middle microchamber, zinc-like micro-flocs begin to form and are retained. The remaining manganese ions continue to migrate downstream and complete deposition in the rear microchamber, which is more alkaline. Since the pH of each microchamber is shaped in real time by the dissociated water flow, even if the feed water ratio fluctuates, the separation position can still be kept within the expected window. This step decomposes the originally difficult-to-control overall acid-base environment into a continuous gradient field of multiple tunable micro-chambers, thereby achieving the sequential precipitation and stable retention of different metal ions in space.

[0024] Example 5: The pH ranges corresponding to the continuous spatial pH gradient field include, in order of pH value, a first pH range, a second pH range, and a non-precipitation range; the free target metal ions include a first target metal ion and a second target metal ion; when the isoelectric focusing separation module drives the migration of the free target metal ions, it is configured as follows: if the first target metal ion enters the first pH range and reaches the first precipitation pH critical condition corresponding to its nucleation critical state, a first metal micro-floc is formed and retained; if the second target metal ion enters the second pH range and reaches the second precipitation pH critical condition corresponding to its nucleation critical state, a second metal micro-floc is formed and retained; if a non-target ion enters the non-precipitation range, it remains in a free state and is discharged.

[0025] The first target metal ion is zinc ion, and the first metal micro-floc is zinc hydroxide; the second target metal ion is manganese ion, and the second metal micro-floc is manganese hydroxide. This embodiment provides a mechanism for segmented isoelectric focusing separation in a continuous gradient field. Specifically, simply constructing a continuous pH gradient is insufficient to guarantee high-purity recovery, because in addition to zinc and manganese ions, actual wastewater may also contain sodium ions, sulfate ions, and a small amount of impurity ions. If the functions of different intervals are not further divided, the precipitation region of the target metal may overlap with the impurity migration region. Therefore, this embodiment clearly divides the gradient field into a first pH interval, a second pH interval, and a non-precipitation interval. Specifically, the first pH range is used to preferentially reach the conditions for the formation of the first metal flocs by the first target metal ions; the second pH range is used to further reach the conditions for the formation of the second metal flocs by the second target metal ions; the non-precipitation range is used to allow ions that do not need to be recovered to remain in a dissolved state and eventually be discharged; for manganese zinc production wastewater, the first target metal ion can be selected as zinc ions, corresponding to the formation of zinc hydroxide flocs; the second target metal ion can be selected as manganese ions, corresponding to the formation of manganese hydroxide flocs; As an example, suppose that the fluid entering the isoelectric focusing zone after the complex is broken contains zinc ions, manganese ions, and sodium ions as impurities at the initial concentration. The fluid first passes through the first pH zone A, where most of the zinc ions reach the solubility product constant for the formation of zinc hydroxide and are retained. The manganese ions and sodium ions that have not reached the isoelectric point continue to migrate along the flow channel. Subsequently, the fluid enters the second pH zone B, where some manganese ions reach the critical concentration condition for the formation of manganese hydroxide micro-flocs and are retained. Sodium ions do not form precipitates throughout the process and eventually enter the non-precipitation zone C and are discharged. In this way, zone A mainly collects zinc, zone B mainly collects manganese, and zone C serves as a discharge channel for non-target ions. In this application, the precipitation pH threshold refers to the critical state in which the target metal ions react with hydroxide ions in a corresponding local acidic or alkaline environment to facilitate nucleation, aggregation, and retention. In other words, the system utilizes the difference in the order in which different metals form hydroxide microflocs under different acidic or alkaline conditions, and amplifies this difference into a separation effect through spatial migration. Specifically, for the first target metal ion, zinc ions, the local pH critical nucleation window corresponding to the first precipitation pH critical condition is 7.5 to 8.5; for the second target metal ion, manganese ions, the local pH critical nucleation window corresponding to the second precipitation pH critical condition is 9.0 to 10.5. Furthermore, regarding the control of abnormal operating conditions, if the boundary between the first and second pH ranges is too close, causing cross-precipitation of zinc and manganese, this can be corrected by reducing the degree of alkalization at the end of the first pH range or lengthening the transition section between the two ranges. If non-target ions participate in co-precipitation prematurely outside the non-precipitation range, it indicates that the concentration of impurities introduced after upstream complex breaking or the degree of local supersaturation is too high. In this case, co-precipitation can be weakened by reducing the unit flux, increasing the shear rate, or increasing the number of transition microchambers. For example, after a full line rinsing in the manganese-zinc plant, the zinc-to-manganese mass ratio in the wastewater is close to 1:1. After the complex-breaking fluid enters the multi-chamber microchannel, fine white zinc hydroxide microflocs first appear in the first pH range at the front end and are collected by the corresponding interception chamber; light-colored manganese hydroxide microflocs then appear in the second pH range at the rear end and are collected separately; while sodium ions and some soluble anions in the system background electrolyte are discharged along the non-precipitation path; the system thus outputs two separate sources of recovery liquid. The system utilizes the difference in the order in which zinc ions and manganese ions form micro-flocs under local acidic or alkaline conditions to achieve spatial sequential separation, thereby improving the purity of the recovered liquid and reducing the burden of subsequent reprocessing.

[0026] Example 6: The degraded organic small molecules carry a negative charge; under the combined action of a DC electric field and the fluid shear force of the complex-breaking fluid, the isoelectric focusing separation module drives the degraded organic small molecules to accumulate on the surface of the monovalent anion selective exchange membrane, forming a dynamic competitive repulsion layer with a concentration higher than or equal to the preset anti-fouling concentration threshold; wherein, the dynamic competitive repulsion layer is used to inhibit the scaling of metal ions on the membrane surface.

[0027] This embodiment provides a mechanism for inhibiting membrane fouling using degraded organic small molecules. Specifically, in the aforementioned segmented precipitation scheme, although zinc and manganese can be separated, with the extension of continuous operation time, metal ions may still prematurely deposit near the membrane surface due to local concentration polarization, thus causing fouling. Existing conventional treatment methods usually involve increasing the frequency of chemical cleaning or adding scale inhibitors, but this will introduce additional chemical agents into the system, reducing the purity of the recovered liquid. Therefore, this embodiment further utilizes the negatively charged degraded organic small molecules generated in the upstream complex-breaking stage to construct a dynamic competitive repulsion layer on the membrane surface; the anti-fouling concentration threshold is a preset calibrated local mass concentration. Specifically, after upstream frequency-controlled complex breaking, some large molecular organic complex residues are broken down into negatively charged small molecular acids or small molecular organic anions. After entering the isoelectric focusing region, these small molecules migrate directionally under the influence of a DC electric field and spread along the membrane surface under the influence of shear flow in the flow channel. When their local concentration on the surface of the monovalent anion selective exchange membrane reaches or exceeds the preset anti-fouling concentration threshold, an enriched layer in a dynamic adsorption-desorption equilibrium state is formed. This enriched layer preferentially occupies the mass transfer boundary layer position near the membrane surface, making it difficult for metal ions to directly adhere to the membrane surface and nucleate, thereby reducing the probability of inorganic fouling. As an example, suppose that metal ions near the surface of a certain membrane segment exhibit concentration polarization. Without the participation of organic small molecules, local high concentrations of zinc ions may form local nucleation conditions near the membrane surface, resulting in fouling. After introducing negatively charged small molecules, the local mass concentration of organic small molecules near the membrane surface reaches a preset threshold and preferentially occupies active sites in the mass transfer boundary layer. This physically repels zinc ions that would normally adhere to the membrane surface and traps them in the outer flow layer. Due to shear disturbance in the outer flow layer, these zinc ions are carried back to the bulk fluid, thereby reducing the probability of them forming adhesive fouling on the membrane surface. The competition here is reflected in the competition for sites in the vicinity of the membrane surface, and the dynamics are reflected in the fact that the enriched layer is constantly renewed with the flow, rather than forming a permanent covering membrane layer. Furthermore, the anti-fouling concentration threshold is configured to a local enrichment level that reduces the nucleation rate on the membrane surface. For example, the anti-fouling concentration threshold is set to a local concentration of negatively charged degrading organic small molecules on the membrane surface that is 3 to 5 times the concentration of the bulk solution, or a local mass concentration that is 50 mg / L to 150 mg / L. The system can indirectly determine whether the enrichment layer has been established by the transmembrane pressure difference growth rate, membrane resistance change, or metal flux change in the retrieval zone. If it is determined that the enrichment layer has not been established, the shear flow rate can be appropriately increased or the DC field strength can be finely adjusted to promote the migration of negatively charged small molecules to the membrane surface. Specifically, the system collects the transmembrane pressure difference signal through the control module and inputs it to the proportional-integral-derivative controller to dynamically adjust the frequency of the feed water variable frequency pump to change the shear flow rate in the flow channel, thereby locking the local enrichment mass concentration in a closed loop within the preset range of 50 mg / L to 150 mg / L. Furthermore, in terms of abnormal operating condition control, if there are too few negatively charged small molecules and an effective repulsion layer cannot be formed, the system can switch to a periodic low-intensity backwashing mode to prevent the initial thin scale from solidifying; if there are too many negatively charged small molecules, which may cause the organic coating on the membrane surface to thicken, the system can control it to be in a dynamic renewal rather than static accumulation state by increasing the transverse rinsing flow rate or temporarily reducing the DC field strength; in other words, the enriched layer needs to be maintained within a window that is sufficient to repel metal but not enough to clog the membrane surface. For example, on the seventh day of continuous operation of the manganese-zinc wastewater recovery line, the membrane module typically enters the high-risk scaling period of conventional processes. However, since this system has already broken down the residual macromolecular organic matter into negatively charged small molecule acids upstream, these small molecules, along with the complex-breaking fluid, enter the isoelectric focusing region and preferentially spread on the surface of the monovalent selective membrane under the combined action of the DC electric field and the flow channel shear. The operation records show that although zinc and manganese continue to precipitate in stages downstream, the increase in membrane pressure difference is significantly slowed down, and the shutdown cleaning cycle is significantly longer than when this mechanism is not used. This mechanism transforms degraded organic molecules, which were originally considered potential pollutants, into antifouling resources on the membrane surface, thereby inhibiting the early nucleation and fixed deposition of metal ions on the membrane surface and improving the stability of continuous operation.

[0028] Example 7: The in-situ acidification closed-loop module includes a reflux output terminal for outputting the metal salt solution to external synthesis process equipment; This embodiment provides a closed-loop reuse mechanism that directly incorporates the recovered liquid into the front-end synthesis process. Specifically, if the micro-floc acidification and metal salt solution are only completed within the system, but the recovered liquid still needs to be transported or transferred elsewhere, it will increase the storage and transportation links and the risk of contamination, and also weaken the process synergy and integration between the system and the production line. Therefore, this embodiment sets up a reflux output end so that the metal salt solution formed by in-situ acidification can be directly transported to external synthesis process equipment. Specifically, each metal micro-floc collection chamber in the in-situ acidification closed-loop module is connected to the corresponding acidification dissolution chamber. After the acid solution output from the bipolar membrane acid production side enters the dissolution chamber, it converts the zinc hydroxide micro-flocs and manganese hydroxide micro-flocs into reusable zinc salt solutions and manganese salt solutions, respectively. After each solution is tested for online concentration, conductivity, or density, if it reaches the target parameter threshold range set by the front-end synthesis section, it is sent to the corresponding batching tank, complexing reactor, or salt replenishment tank through the reflux output end. As an example at the microscopic level, suppose that at a certain time, the first interception side collects zinc hydroxide micro-flocs equivalent to a preset first mass concentration, and the second interception side collects manganese hydroxide micro-flocs equivalent to a preset second mass concentration; after in-situ acidification, the former forms zinc salt solution A, and the latter forms manganese salt solution B; if the concentration of A reaches the lower limit of reuse, the reflux valve of A is opened and it is transported to the zinc salt replenishment tank; if B has not yet reached the lower limit of reuse, it continues to be circulated and concentrated in the dissolution chamber or merged with the subsequent batch of recovered liquid, and is output after reaching the standard; in this way, reuse is not unconditionally continuous, but is constrained by the reuse window; Furthermore, the reflux output can be connected to the production execution system or the local interlock control system; when the synthesis process equipment is in the allowable receiving state, the reflux output is turned on; when the synthesis process equipment is under maintenance, cleaning or suspended feeding state, the recovered liquid is temporarily stored in the intermediate buffer tank to avoid accidental delivery; in this way, a controllable closed loop is formed between the wastewater recovery chain and the front-end production chain, rather than a hard connection. Furthermore, regarding abnormal operating condition control, if a batch of recovered liquid contains excessive impurities, such as high turbidity or conductivity deviating from the requirements of the upstream application, the recovered liquid will not be directly sent back to the synthesis process, but will be sent back to the front end of the system for reprocessing or sent to a separate purification unit; if the upstream process cannot receive the recovered liquid for a short period of time, but the downstream recovered liquid continues to be generated, the system can reduce the processing throughput in conjunction with the buffer tank when the liquid level rises to the upper limit, prioritizing overall stability; if an abnormal increase in pressure is detected in the return pipeline, it indicates that there may be crystallization, blockage, or valve malfunction. At this time, the return will be stopped and the circulation insulation or flushing procedure will be initiated. For example, during the daily operation of the manganese zinc production line, a certain amount of zinc salt and manganese salt needs to be added at the end of the regular production shift to maintain the reaction ratio of the next batch. At the same time, the wastewater treated during the centralized replacement period of the mother liquor has been separated and acidified in situ by this system to obtain zinc salt solution and manganese salt solution that meet the conditions for reuse. After confirming that the front-end batching tank has the receiving conditions, the control system opens the reflux output end and quantitatively sends the recovered liquid to the corresponding replenishment point. In this way, the metal components in the wastewater of the previous cycle directly become the raw materials required for the production of the next cycle, realizing the closed loop of materials within the workshop. This mechanism advances end-of-pipe recycling from the completion of treatment to the completion of process reuse, thereby enabling the direct recycling of the target metal salt solution within the same production system, thus improving the continuous operation stability of the treatment system and the closed-loop processing capability of materials.

[0029] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention in any other way. Any person skilled in the art may make changes or modifications to the above-disclosed technical content to create equivalent embodiments that can be applied to other fields. However, any conventional modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the protection scope of the present invention.

Claims

1. An integrated wastewater treatment system for manganese and zinc production with integrated manganese and zinc recovery function, characterized in that, include: The parameter acquisition and mapping module is used to acquire the initial fluid parameters of wastewater containing complexed metals and calculate and generate pulse control parameters. The frequency-controlled complex-breaking module is used to introduce the wastewater containing complexed metal into a frequency-controlled complex-breaking zone equipped with an anode and a cathode, and apply an asymmetric high-frequency pulse electric field based on the pulse control parameters to break the coordination bonds in the wastewater containing complexed metal, thereby generating a complex-breaking fluid containing free target metal ions and degraded small organic molecules. The isoelectric focusing separation module is used to introduce the complex-breaking fluid into the bipolar film isoelectric focusing region, establish a continuous spatial acid-base gradient field under the action of the applied DC electric field, drive the free target metal ions to migrate and form metal micro flocs in the corresponding acid-base range, and retain them in the micro floc collection cavity connected to the bipolar film isoelectric focusing region. The in-situ acidification closed-loop module includes an acid reflux pipeline connecting the acid-producing side of the bipolar isoelectric focusing region and the micro-floc collection chamber. The acid-producing side is formed by the aggregation of hydrogen ions dissociated from the bipolar membrane inside the bipolar isoelectric focusing region. It is used to dissolve the retained metal micro-flocs with acid to generate a metal salt solution and output it.

2. The integrated wastewater treatment system for manganese-zinc production with integrated manganese-zinc recovery function as described in claim 1, characterized in that, The initial fluid parameters include influent flow rate data and conductivity data; the parameter acquisition and mapping module obtains the matching pulse control parameters based on the influent flow rate data and conductivity data through a preset grading mapping logic table; wherein, the pulse control parameters include the pulse electric field duty cycle.

3. The integrated wastewater treatment system for manganese-zinc production with integrated manganese-zinc recovery function as described in claim 1, characterized in that, The anode in the frequency-controlled complex-breaking zone is an anode coated with ruthenium-iridium boron-doped diamond; the frequency-controlled complex-breaking module sets the frequency of the asymmetric high-frequency pulse electric field to the resonant frequency corresponding to the polarization response frequency range of the coordination bonds in the complexed metal wastewater.

4. The integrated wastewater treatment system for manganese-zinc production with integrated manganese-zinc recovery function as described in claim 1, characterized in that, The free target metal ions include manganese ions; the frequency-controlled network breaking module limits the polarization potential generated by the anode during operation to a level lower than or equal to a preset potential threshold, which is lower than the oxidation potential threshold of the manganese ions; the frequency-controlled network breaking module limits the polarization potential of the anode to the preset potential threshold through a voltage limiting circuit.

5. The integrated wastewater treatment system for manganese-zinc production with integrated manganese-zinc recovery function as described in claim 1, characterized in that, The bipolar membrane isoelectric focusing region is composed of a multi-chamber microchannel formed by alternating bipolar membranes and monovalent anion selective exchange membranes; the isoelectric focusing separation module constructs the continuous spatial acid-base gradient field by controlling the flow of dissociated water introduced on both sides of the bipolar membrane.

6. The integrated wastewater treatment system for manganese-zinc production with integrated manganese-zinc recovery function as described in claim 5, characterized in that, The acid-base intervals corresponding to the continuous spatial acid-base gradient field include, in order of acid-base value, a first acid-base interval, a second acid-base interval, and a non-precipitation interval. The free-state target metal ions include a first target metal ion and a second target metal ion; the complex-breaking fluid also includes non-target ions; If the first target metal ion enters the first acid-base range and reaches the first precipitation pH critical condition corresponding to its nucleation critical state, then the first metal micro-flocs are formed and retained. If the second target metal ion enters the second pH range and reaches the second precipitation pH critical condition corresponding to its nucleation critical state, then the second metal micro-flocs are formed and retained. If the second target metal ion does not reach the second precipitation pH critical condition corresponding to its nucleation critical state, it will continue to migrate in the continuous spatial acid-base gradient field. If the non-target ion enters the non-precipitation zone, it remains in a free state and is discharged.

7. The integrated wastewater treatment system for manganese-zinc production with integrated manganese-zinc recovery function as described in claim 6, characterized in that, The first target metal ion is zinc ion, and the first metal flocculent is zinc hydroxide; the second target metal ion is manganese ion, and the second metal flocculent is manganese hydroxide.

8. The integrated wastewater treatment system for manganese-zinc production with integrated manganese-zinc recovery function as described in claim 5, characterized in that, The degraded organic molecules carry a negative charge; under the combined action of the DC electric field and the fluid shear force generated by the complex-breaking fluid in the multi-chamber microchannel, the isoelectric focusing separation module drives the degraded organic molecules to accumulate on the surface of the monovalent anion selective exchange membrane, forming a dynamic competitive repulsion layer; based on the DC electric field and the fluid shear force, the isoelectric focusing separation module maintains the local enrichment concentration of the degraded organic molecules on the membrane surface between 50 mg / L and 150 mg / L.

9. The integrated wastewater treatment system for manganese-zinc production with integrated manganese-zinc recovery function as described in claim 1, characterized in that, The in-situ acidification closed-loop module includes a reflux output terminal for outputting the metal salt solution.

10. The integrated wastewater treatment system for manganese-zinc production with integrated manganese-zinc recovery function according to claim 4, characterized in that, The preset potential threshold is 0.8V to 1.1V.

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