Electrolyte recycling system and method
By using a zoned circulation system and a high-performance electrolyte recycling and reuse system, the problems of low current efficiency and electrode contamination in electrolysis devices have been solved. This system enables efficient regeneration of electrolyte and recovery of copper resources, reduces energy consumption, and is suitable for industrial applications.
Patent Information
- Application Number
- CN202511882051.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-15
- Publication Date
- 2026-02-13
AI Technical Summary
In existing technologies, electrolysis devices suffer from problems such as low current efficiency, easy passivation or contamination of electrode surfaces, easy damage to cation exchange membranes, failure to recover heat, and lack of real-time monitoring of key parameters, resulting in poor electrolyte regeneration and high operating costs.
An electrolyte recycling and reuse system using partitioned circulation and high-performance materials includes independent positive and negative electrode storage tanks and circulation pumps, combined with highly catalytically active boron-doped diamond thin film electrodes and titanium sheet electrodes coated with nano-nickel-cobalt alloy, and equipped with multi-parameter sensors and a main controller to achieve efficient regeneration of electrolyte and recovery of copper resources.
It improves electrolysis efficiency, extends the service life of electrodes and ion membranes, reduces system energy consumption, and enables automated and precise industrial applications.
Smart Images
Figure CN121519084A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of electrolyte recycling and regeneration technology, specifically to an electrolyte recycling and reuse system and method. Background Technology
[0002] In PCB manufacturing, the sodium persulfate-sulfuric acid micro-etching solution contains sulfuric acid, sodium persulfate, copper sulfate, and sodium sulfate. Its core micro-etching reaction is: Cu + S₂O₈ 2- → Cu 2+ + 2SO4 2- The process essentially involves persulfate oxidizing copper, reducing itself back to sulfate. To regenerate the waste liquid, traditional methods employ electrochemical oxidation, using BDD electrode material at the anode. Through electrocatalytic oxidation, the sulfate ions (SO42-) in the solution are removed. 2- ) is converted into persulfate (S2O8) 2- Its electrolysis reaction mechanism is as follows: ①H2O - e - → ·OH + H + ; ②2SO4 2- + 2·OH + 2H + → S2O8 2- + 2H2O; The cathode is made of pure titanium or titanium alloy and is used to selectively reduce and precipitate copper accumulated in the micro-etching waste liquid. The reaction equation is as follows: Cu 2+ + 2e - → Cu; However, existing technologies have the following problems in practical applications: (1) In traditional electrolysis devices, the electrolyte flow distribution in the anode and cathode regions is uneven, resulting in low current efficiency and easy passivation or contamination of the electrode surface, which affects the regeneration effect. (2) Cation exchange membranes are easily contaminated and structurally damaged during use, which leads to a decrease in ion selectivity and a shortened service life; (3) The heat generated during the electrolysis process was not effectively recovered, resulting in energy waste and high system operating costs; (4) The lack of real-time monitoring and intelligent control of key parameters such as electrolyte concentration, pH, and redox potential makes it difficult to achieve stable and efficient continuous operation. Summary of the Invention
[0003] To address the shortcomings of existing technologies, this invention provides an electrolyte recycling system and method, solving the problems mentioned in the background. This invention achieves efficient regeneration of micro-etched waste liquid and simultaneous recovery of copper resources, improving electrolysis efficiency; through zoned circulation and the application of high-performance materials, it significantly extends the service life of electrodes and ion membranes; the heat recovery system reduces system operating energy consumption; and the intelligent control system enables automated and precise operation of the device, reducing manual intervention and making it suitable for industrial applications.
[0004] An electrolyte recycling system includes an electrolysis cylinder, a positive electrode liquid storage cylinder, a negative electrode liquid storage cylinder, a positive electrode liquid circulation pump, and a negative electrode liquid circulation pump. The electrolysis cylinder has a positive electrode electrolysis frame in the middle and a negative electrode electrolysis frame on the outside of the positive electrode electrolysis frame. The positive electrode electrolysis frame is connected to the rear of the positive electrode liquid storage tank through the positive electrode liquid outlet pipe, and the front of the positive electrode liquid storage tank is connected to the positive electrode electrolysis frame through the positive electrode liquid inlet pipe. The positive electrode liquid circulation pump is installed on the positive electrode liquid inlet pipe and is used to transport the positive electrode liquid in the positive electrode liquid storage tank to the positive electrode electrolysis frame through the positive electrode liquid inlet pipe. The negative electrode electrolysis frame is connected to the rear of the negative electrode liquid storage tank through the negative electrode liquid outlet pipe. The front of the negative electrode liquid storage tank is connected to the negative electrode electrolysis frame through the negative electrode liquid inlet pipe. The negative electrode liquid circulation pump is installed on the negative electrode liquid inlet pipe and is used to transport the negative electrode liquid in the negative electrode liquid storage tank to the negative electrode electrolysis frame through the negative electrode liquid inlet pipe. It also includes a control system, which forms a telecommunication connection with each electronic component to coordinate the cooperation of the various components.
[0005] Preferably, the positive electrode electrolysis frame includes a positive electrode frame body, which is fastened together by a plurality of titanium screws. The positive electrode frame body is hollow in the middle to form a positive electrode electrolysis region. A boron diamond electrode is provided in the positive electrode electrolysis region. A cation membrane is also provided on both sides of the positive electrode frame body. The bottom of the positive electrode frame is provided with a positive electrode liquid inlet pipe. The upper port of the positive electrode liquid inlet pipe is connected to the positive electrode liquid inlet pipe through an adapter. The positive electrode liquid inlet pipe is provided with several liquid outlets. The positive electrode liquid inlet pipe delivers positive electrode liquid to the bottom of the positive electrode electrolysis zone through the liquid outlets.
[0006] Preferably, the positive electrode frame is made of polyvinylidene fluoride or reinforced polypropylene; the boron diamond electrode is made of boron-doped diamond film, the boron diamond electrode has multiple liquid passage holes, and the boron diamond electrode is connected to the pulse power supply.
[0007] Preferably, the cation exchange membrane comprises a polyethylene cation exchange membrane, wherein the side of the polyethylene cation exchange membrane in contact with the positive electrolyte is provided with a sulfonated polyether ether ketone layer, and the side of the polyethylene cation exchange membrane in contact with the negative electrolyte is provided with a polymer layer containing nitrogen-containing coordinating groups.
[0008] Preferably, the negative electrode frame includes a negative electrode frame body, which is disposed around the positive electrode electrolysis frame. The area between the negative electrode frame body and the positive electrode frame is defined as the negative electrode electrolysis region, and a titanium sheet electrode is disposed in the negative electrode electrolysis region. The bottom of the negative electrode frame is provided with a negative electrode inlet pipe. The inlet end of the negative electrode inlet pipe is connected to the negative electrode liquid inlet pipe through an adapter. The negative electrode inlet pipe is provided with several outlets. The negative electrode inlet pipe delivers negative electrode liquid to the bottom of the negative electrode electrolysis zone through the outlets.
[0009] Preferably, the titanium sheet electrode is coated with a nano-nickel-cobalt alloy coating, the titanium sheet electrode is arranged in a grid pattern, and the titanium sheet electrode is connected to a pulse power supply.
[0010] Preferably, both the positive electrode liquid storage tank and the negative electrode liquid storage tank are equipped with filter bag frames, and filter bags are fitted inside the filter bag frames. The port of the positive electrode liquid outlet pipe or the negative electrode liquid outlet pipe is located inside the filter bag. The filter bag adopts a graded filter bag structure, with its outer layer being a fiber filter bag with a pore size of 3-6μm and its outer layer being a large-pore filter screen with an inner diameter of 30-70μm.
[0011] Preferably, the control system includes a main controller, a pH sensor, a redox potential sensor, a differential pressure sensor, and a flow sensor. The pH sensor and the redox potential sensor are both installed in the positive electrode liquid storage tank and the negative electrode liquid storage tank. The differential pressure sensor is installed on both the inner and outer sides of the positive electrode electrolysis frame. The flow sensor is installed on the positive electrode liquid inlet pipe and the negative electrode liquid inlet pipe. The main controller is connected to the pH sensor, redox potential sensor, differential pressure sensor and flow sensor via telecommunications. The main controller is located inside the control box, and a touch screen is provided on the outer surface of the control box. An audible and visual alarm is provided on the upper surface of the control box.
[0012] An electrolyte recycling method, applied to the electrolyte recycling system described in any one of the above claims, includes the following steps: S1. Inject the PCB micro-etching waste liquid to be treated into the positive electrode liquid storage tank and the negative electrode liquid storage tank of the system. Then, start the initialization program through the touch screen of the control system. The main controller performs self-test and calibration on the pH and oxidation-reduction potential sensors to confirm that each execution unit, including the positive electrode liquid circulation pump, the negative electrode liquid circulation pump, the pulse power supply, etc., is in standby mode. S2. Start the positive electrode liquid circulation pump and the negative electrode liquid circulation pump to pump the positive electrode liquid and the negative electrode liquid into the corresponding areas of the electrolysis tank through the positive electrode liquid inlet pipe and the negative electrode liquid inlet pipe, respectively. The electrolyte flow path is as follows: Positive electrode circuit: Positive electrode liquid storage tank → Positive electrode liquid circulation pump → Positive electrode liquid inlet pipe → Positive electrode liquid inlet pipe → Positive electrode electrolysis zone → Positive electrode liquid outlet pipe → Filter bag in positive electrode liquid storage tank → Circulation completed; Negative electrode circuit: Negative electrode liquid storage tank → Negative electrode liquid circulation pump → Negative electrode liquid inlet pipe → Negative electrode liquid inlet pipe → Negative electrode electrolysis zone → Negative electrode liquid outlet pipe → Filter bag in negative electrode liquid storage tank → Circulation completed; The reflux electrolyte first passes through a large-pore filter screen of 30-70μm in the inner layer of the filter bag to intercept larger particles, and then passes through a precision fiber filter bag of 3-6μm in the outer layer to remove fine suspended matter and impurities, effectively preventing the electrodes and ion membrane from clogging. S3. The main controller starts the pulse power supply and applies pulse voltage to the boron diamond electrode and the titanium sheet electrode. Within the positive electrode region: Under the excitation of a pulsed electric field, the boron-doped diamond thin-film electrode efficiently catalyzes the generation of hydroxyl radicals from water molecules; the hydroxyl radicals react with sulfate (SO4) in the solution. 2- A reaction occurs, re-oxidizing it to persulfate (S₂O₈). 2- To achieve the regeneration of micro-etched components, the reaction formula is: 2SO4 2- + 2·OH + 2H + →S2O8 2- + 2H2O; Within the negative electrode electrolysis zone: a mesh-like titanium electrode coated with a nano-nickel-cobalt alloy layer selectively reduces copper ions (Cu) in the solution under a pulsed electric field. 2+ This causes it to precipitate as metallic copper and adhere to the electrode surface. The reaction formula is: Cu 2+ + 2e - → Cu; S4. Throughout the entire cyclic electrolysis process, the control system monitors the key chemical parameters of the electrolyte in the two storage tanks in real time through pH sensors, redox potential sensors, differential pressure sensors, and flow sensors; the main controller adjusts the current density and frequency of the pulse power supply according to the redox potential value; and dynamically adjusts the system operating parameters by triggering an audible and visual alarm when the differential pressure is abnormal, ensuring that the entire process is in the optimal state. S5. When the main controller determines from sensor data that the persulfate concentration in the positive electrode solution has reached the target regeneration standard and the copper deposition on the negative electrode has reached a certain thickness, the system prompts that regeneration is complete, stops the circulation pump and pulse power supply, and discharges the regenerated micro-etching solution from the positive electrode solution storage tank for reuse; then the grid-shaped titanium sheet electrode in the negative electrode electrolysis area can be removed for copper stripping to recover high-purity metallic copper; the system can prompt to replace the filter bag based on the pressure difference across the filter bag or the running time to complete maintenance.
[0013] Compared with the prior art, the present invention has the following beneficial effects: 1. The electrolyte recycling system of the present invention, by setting up independent positive and negative electrode liquid storage tanks and circulation pumps, combined with the partitioned structure of the positive electrode electrolysis frame and the outer negative electrode electrolysis frame, realizes independent circulation and precise control of anolyte and catholyte, effectively avoids cross-contamination, and improves electrolysis efficiency and electrode stability. 2. The electrolyte recycling system of this invention uses a boron-doped diamond thin film electrode as the positive electrode, which has high catalytic activity and anti-pollution performance; the negative electrode uses a grid-shaped titanium sheet electrode coated with a nano-nickel-cobalt alloy coating to enhance conductivity and reaction area; the cation membrane uses a polyethylene-based composite material, with a sulfonated polyether ether ketone layer and a nitrogen-containing coordination group polymer layer on both sides, which significantly improves ion selectivity, chemical corrosion resistance and mechanical strength. 3. The electrolyte recycling system of the present invention is equipped with multi-parameter sensors such as pH, redox potential, pressure difference, flow rate, etc., and a main controller to monitor and automatically adjust the electrolysis process in real time, ensuring that the system operates under optimal conditions, improving the quality of the regenerated liquid and the stability of the device operation. 4. The electrolyte recycling and reuse system of this invention achieves efficient regeneration of micro-etched waste liquid and simultaneous recovery of copper resources, resulting in a significant improvement in electrolysis efficiency. On the other hand, the intelligent control system enables automated and precise operation of the system, reducing manual intervention and making it suitable for industrial applications. Attached Figure Description
[0014] Figure 1 This is a schematic diagram of the overall structure of the electrolyte recycling and reuse system of the present invention; Figure 2 This is an internal structural diagram of the electrolyte recycling and reuse system of the present invention; Figure 3 This is a structural diagram of the electrolysis cylinder in the electrolyte recycling system of the present invention; Figure 4 This is a structural diagram of the control box of the electrolyte recycling and reuse system of the present invention.
[0015] In the diagram: 1. Electrolysis cylinder; 101. Positive electrode frame; 102. Positive electrode electrolysis zone; 103. Boron diamond electrode; 105. Negative electrode electrolysis frame; 106. Negative electrode electrolysis zone; 107. Cation membrane; 108. Separator plate; 109. Overflow port; 110. Electrode mounting slot; 111. Titanium sheet electrode; 112. Liquid separation zone; 2. Positive electrode liquid storage cylinder; 3. Negative electrode liquid storage cylinder; 4. Positive electrode liquid circulation pump; 5. Negative electrode liquid circulation pump; 6. Positive electrode liquid outlet pipe; 7. Positive electrode liquid inlet pipe; 8. Negative electrode liquid outlet pipe; 9. Negative electrode liquid inlet pipe; 10. Filter bag frame; 11. Control box; 12. Audible and visual alarm; 13. Touch screen. Detailed Implementation
[0016] To enable those skilled in the art to better understand the technical solution of the present invention, the product of the present invention will be further described in detail below with reference to embodiments and accompanying drawings.
[0017] It should be noted that when an element is referred to as being "fixed to" another element, it can be directly attached to the other element or there may be an intervening element; when an element is referred to as being "connected to" another element, it can be directly connected to the other element or there may be an intervening element. The terms "vertical," "horizontal," "left," "right," and similar expressions used herein are for illustrative purposes only and do not represent the only possible implementation.
[0018] like Figure 1 and Figure 2 As shown, an electrolyte recycling system includes an electrolytic cylinder 1, a positive electrode liquid storage cylinder 2, a negative electrode liquid storage cylinder 3, a positive electrode liquid circulation pump 4, and a negative electrode liquid circulation pump 5. A positive electrode electrolysis frame is located in the middle of the electrolytic cylinder 1, and a negative electrode electrolysis frame 105 is located on the outer side of the positive electrode electrolysis frame. The positive electrode electrolysis frame is connected to the rear of the positive electrode liquid storage cylinder via a positive electrode liquid outlet pipe 6. The front of the positive electrode liquid storage cylinder 2 is connected to the positive electrode electrolysis frame via a positive electrode liquid inlet pipe 7. The positive electrode liquid circulation pump 4 is installed on the positive electrode liquid inlet pipe 7 and is used to circulate the electrolyte in the positive electrode liquid storage cylinder 2. The positive electrode liquid is transported into the positive electrode electrolysis frame through the positive electrode liquid inlet pipe 7; the negative electrode electrolysis frame 105 is connected to the rear of the negative electrode liquid storage tank through the negative electrode liquid outlet pipe 8, and the front of the negative electrode liquid storage tank 3 is connected to the negative electrode electrolysis frame 105 through the negative electrode liquid inlet pipe 9. The negative electrode liquid circulation pump 5 is installed on the negative electrode liquid inlet pipe 9 and is used to transport the negative electrode liquid in the negative electrode liquid storage tank 3 into the negative electrode electrolysis frame 105 through the negative electrode liquid inlet pipe 9; it also includes a control system, which forms a telecommunication connection with each electronic component to coordinate the cooperation of each component.
[0019] It should be noted that: In this invention, a partition plate 108 is inserted into the electrolysis cylinder 1, and the two sides of the partition plate 108 form a sealed arrangement with the inner side of the electrolysis cylinder 1. The partition plate 108 divides the electrolysis cylinder 1 into a front electrolysis zone and a rear liquid separation zone 112. A positive electrode electrolysis frame is provided in the middle of the electrolysis zone, and the positive electrode electrolysis frame is independently separated to form a positive electrode electrolysis zone 102. The two sides of the positive electrode electrolysis zone 102 form a negative electrode electrolysis zone 106. The positive electrode liquid inlet pipe includes a positive electrode liquid inlet first pipe and a positive electrode liquid inlet second pipe. One end of the positive electrode liquid inlet first pipe is inserted into the positive electrode liquid inlet. Inside the electrode liquid storage tank 2, one end is fixedly connected to the inlet of the positive electrode liquid circulation pump 4. One end of the positive electrode liquid inlet pipe is fixedly connected to the outlet of the positive electrode liquid circulation pump 4, and the other end extends to the upper port of the positive electrode electrolysis zone 102, so that the positive electrode liquid can be transported into the positive electrode electrolysis zone 102 through the positive electrode liquid inlet pipe. One end of the positive electrode liquid outlet pipe is fixedly connected to the outlet of the positive electrode electrolysis zone 102, and the other end extends into the filter bag frame 10 inserted in the positive electrode storage tank, so that the positive electrode liquid flowing out of the positive electrode electrolysis zone 102 is filtered through the filter bag in the filter bag frame 10 before flowing out. Similarly, the negative electrode inlet pipe includes a negative electrode inlet pipe 1 and a negative electrode inlet pipe 2. One end of the negative electrode inlet pipe 1 is inserted into the negative electrode liquid storage tank 3, and the other end is fixedly connected to the inlet of the negative electrode liquid circulation pump 5. One end of the negative electrode inlet pipe 2 is fixedly connected to the outlet of the negative electrode liquid circulation pump 5, and the other end extends to the upper port of the positive electrode electrolysis zone 102, so that the negative electrode liquid can be transported to the negative electrode electrolysis zone 106 through the negative electrode inlet pipe. The partition plate 108 is provided with an overflow port 109 corresponding to the negative electrode electrolysis zone 106. The negative electrode liquid in the upper part of the negative electrode electrolysis zone 106 will flow into the liquid distribution zone 112 through the overflow port 109. One end of the negative electrode outlet pipe is fixedly connected to the outlet of the liquid distribution zone 112, and the other end extends into the filter bag frame 10 inserted in the negative electrode storage tank, so that the negative electrode liquid flowing out of the negative electrode electrolysis zone 106 is filtered by the filter bag in the filter bag frame 10 before flowing out.In this invention, the positive electrode solution of the micro-etching waste liquid to be regenerated is placed in the positive electrode solution storage tank 2, and the negative electrode solution is placed in the negative electrode solution storage tank 3. The positive electrode solution circulation pump 4 and the negative electrode solution circulation pump 5 are started, and the positive electrode solution is transported to the positive electrode frame through the positive electrode solution inlet pipe 7. After reacting with the electrodes in the positive electrode frame, it flows back to the positive electrode solution storage tank 2 through the positive electrode solution outlet pipe 6. Through this repeated circulation of the solution, the reduced persulfate ions (S₂O₈²⁻) in the positive electrode solution in the positive electrode solution storage tank 2 reaches the standard for positive electrode solutions in PCB micro-etching liquid, thus completing the reduction and recovery of the positive electrode solution in a single batch of micro-etching waste liquid. The solution is reused in the PCB micro-etching solution for recycling. Similarly, by activating the negative electrode liquid circulation pump 5, the negative electrode liquid is transported to the negative electrode frame through the negative electrode liquid inlet pipe 9. After reacting with the electrodes in the negative electrode frame, it flows back to the negative electrode liquid storage tank 3 through the negative electrode liquid outlet pipe 8. Through this repeated circulation of the solution, the copper accumulated in the micro-etching waste liquid in the negative electrode liquid storage tank 3 is reduced and precipitated, thus meeting the standard of negative electrode liquid in PCB micro-etching solution. This completes the reduction and recovery of negative electrode liquid in a single batch of micro-etching waste liquid, allowing it to be reused in the PCB micro-etching solution for recycling. This invention provides a regeneration system that does not interfere with each other through the two chemical principles of positive electrode oxidation regeneration and negative electrode reduction copper precipitation, ensuring the preservation of copper ions (Cu). 2+ It can migrate directionally from the positive electrode region to the negative electrode region according to process requirements, thereby being reduced and recovered at the cathode, realizing the targeted recycling and reuse of resources; moreover, through physical isolation and independent circulation, this invention greatly reduces problems such as composition fluctuations, increased side reactions, and electrode poisoning caused by cross-contamination of electrolyte, laying a structural foundation for the long-term, stable, and continuous operation of the system.
[0020] like Figures 1 to 3As shown, the positive electrode electrolysis frame includes a positive electrode frame 101, which is fastened together by several titanium screws. A hollow central portion of the positive electrode frame forms a positive electrode electrolysis zone 102. A boron diamond electrode 103 is disposed within the positive electrode electrolysis zone 102. A cation exchange membrane 107 is also disposed on both sides of the positive electrode frame 101. A positive electrode inlet pipe is located at the bottom of the positive electrode frame 101. The upper end of the positive electrode inlet pipe is connected to a positive electrode liquid inlet pipe 7 via an adapter. The positive electrode inlet pipe has several outlets, through which positive electrode liquid is supplied to the bottom of the positive electrode electrolysis zone 102. The positive electrode frame 101 is made of polyvinylidene fluoride or reinforced polypropylene. The boron diamond electrode 103 is made of boron-doped diamond film and has multiple liquid passage holes. The boron diamond electrode 103 is connected to a pulse power supply. The cation exchange membrane 107 includes a polyethylene cation exchange membrane. The side of the polyethylene cation exchange membrane in contact with the positive electrolyte is provided with a sulfonated polyether ether ketone layer, and the side of the polyethylene cation exchange membrane in contact with the negative electrolyte is provided with a polymer layer containing nitrogen-containing coordinating groups.
[0021] It should be noted that in this invention, the positive electrode frame 101 is made of polyvinylidene fluoride or reinforced polypropylene. These two materials not only have the ability to resist corrosion from strong acids and strong oxidizing media, but are also excellent electrical insulators, which can effectively prevent current from short-circuiting through the frame itself. The front and rear sides of the positive electrode frame 101 are sealed and fitted to the partition plate 108 and the front plate of the electrolysis cylinder 1. Electrode mounting slots 110 are provided on the front and rear side plates of the positive electrode frame 101, and corresponding electrode mounting slots 110 are also provided at the positions of the front and rear plates of the electrolysis cylinder 1. The boron diamond electrode 103 is fixed to the electrode rod by bolts. The two ends of the electrode rod are engaged in the electrode mounting slots 110, so that the boron diamond electrode 103 hangs downward in the middle of the positive electrode electrolysis zone 102. The left and right side plates of the positive electrode frame 101 separate the positive electrode electrolysis zone 102 and the negative electrode electrolysis zone 106. The left and right side plates are arranged in a grid pattern. The left and right side plates and the front and rear sides are fastened with titanium screws and sealing rings to form a sealed cavity. Its bottom is connected to the bottom plate by a durable seal. The cation exchange membrane 107 is sealed and glued to the inside of the left and right side panels using an adhesive with strong acid and strong oxidizing properties. It is pressed into the membrane mounting grooves on both sides of the frame by an additional PVDF membrane pressure plate and another set of titanium screws. The grooves are also equipped with sealing gaskets. The titanium screws are made of pure titanium of TA2 grade or higher, and their surfaces are anodized to form a denser oxide film. The contact surfaces between the titanium screws and the frame are equipped with fluororubber O-rings to ensure the sealing between the titanium screws and the frame. This forms a rigid, sealed reaction chamber. Its core function is to completely isolate the strongly oxidizing positive electrolyte from the external environment and the negative electrode area, providing a safe and stable sealed space for the efficient electrochemical reaction inside. The boron-doped diamond film is precisely perforated using laser technology to form a uniform array of liquid-passing pores with a pore size of 0.5-2 mm and a pore density of 10-20 pores / cm². This boron-doped diamond film exhibits excellent oxygen evolution overpotential and introduces specific catalytic active centers, making it easier for water molecules to be catalyzed to generate hydroxyl radicals on its surface. This effectively inhibits the oxygen evolution side reaction. Furthermore, the liquid-passing pores disrupt the laminar boundary layer on the electrode surface, forcing the electrolyte to generate micro-turbulence as it flows across the electrode surface, greatly enhancing the reaction of SO4. 2- and product S2O8 2-The mass transfer efficiency is improved. The pulse power supply is set with a turn-on time of 1ms, a turn-off time of 2ms, and a peak current density of 100mA / cm². This allows the pulse power supply to establish a strong electric field to drive the reaction instantaneously during the turn-on period, while the double layer of the electrode interface discharges during the turn-off period, which helps to desorb intermediate products and prevents the electrode surface from being covered by a passivation layer. The cation membrane 107 is a composite cation membrane 107, with a high mechanical strength polyethylene cation exchange membrane as the supporting substrate. On the side facing the positive electrode liquid, a layer of sulfonated polyether ether ketone is laminated using a casting film deposition technology, so that the sulfonic acid groups of the sulfonated polyether ether ketone provide a highly efficient proton H+ conduction channel. On the side facing the negative electrode liquid, a polymer layer containing pyridine or imidazole groups is grafted using ultraviolet light grafting technology. These nitrogen-containing groups are beneficial to Cu. 2+ With specific coordination capabilities, H+ ions, due to their small hydrated ionic radius, can rapidly migrate through the sulfonated polyether ether ketone layer under potential difference, maintaining charge balance; nitrogen-containing coordinating groups support Cu 2+ The coordination effect essentially constructs a selective channel with a lower energy barrier, enabling Cu to... 2+ The migration rate is much higher than that of other cations such as Na. + K + Meanwhile, this dense layer effectively prevents large molecular organic impurities and colloidal particles from approaching and contaminating the polyethylene-based cation exchange membrane. The upper port of the positive electrode inlet pipe is connected to the positive electrode liquid inlet pipe 7 via an adapter. The positive electrode inlet pipe extends along the side wall of the positive electrode frame 101 to the bottom surface of the frame. The section of the positive electrode inlet pipe at the bottom of the frame has several outlets, allowing the positive electrode liquid to flow from the bottom of the frame into the positive electrode electrolysis zone 102. This allows the positive electrode liquid in the positive electrode electrolysis zone 102 to circulate, and the inflow of positive electrode liquid from the bottom also provides a certain degree of liquid tumbling and stirring in the positive electrode area, further enhancing the fluid turbulence of the entire positive electrode electrolysis zone 102 and ensuring uniform concentration of reactants on the electrode surface. In this invention, by combining liquid tumbling and stirring, fluid through-hole and pulse electrolysis, the liquid tumbling and stirring can quickly renew the reactant layer on the electrode surface during the pulse interval, preparing for the arrival of the next pulse. This ensures that the electrode surface is always in an ideal state with high reactant concentration, fast product detachment and fresh active sites, thereby pushing the current efficiency and reaction rate to a level that is difficult to achieve with traditional technologies.
[0022] like Figures 1 to 3As shown, the negative electrode frame includes a negative electrode frame body, which is disposed around the positive electrode electrolysis frame. The area between the negative electrode frame body and the positive electrode frame is designated as the negative electrode electrolysis zone 106, and a titanium sheet electrode 111 is disposed within the negative electrode electrolysis zone 106. A negative electrode inlet pipe is provided at the bottom of the negative electrode frame body. The inlet end of the negative electrode inlet pipe is connected to the negative electrode liquid inlet pipe 9 via an adapter. The negative electrode inlet pipe has several outlets, and the negative electrode liquid is supplied to the bottom of the negative electrode electrolysis zone 106 through the outlets. The surface of the titanium sheet electrode 111 is coated with a nano-nickel-cobalt alloy coating. The titanium sheet electrode 111 is arranged in a grid pattern and is connected to a pulse power supply.
[0023] It should be noted that in this invention, the negative electrode frame is the electrolysis cylinder 1 body, including the front and rear side plates and left and right side plates of the electrolysis cylinder 1, which are made of polyvinylidene fluoride or reinforced polypropylene to ensure the overall corrosion resistance and electrical insulation. The partition plate 108 is provided with an overflow hole corresponding to the negative electrode electrolysis area 106. The overflow hole is located lower than the upper end face of the positive electrode frame 101, so that the negative electrode electrolysis area 106 and the liquid distribution area 112 at the rear of the electrolysis cylinder 1 are connected. This allows the solution on the negative electrode electrolysis area 106 to flow into the liquid distribution area 112 at the rear of the electrolysis cylinder 1 through the overflow hole. The negative electrode inlet pipe is connected to the negative electrode area and is used to transport the negative electrode liquid into the negative electrode electrolysis area 106. One end of the negative electrode outlet pipe is connected to the liquid distribution area 112 and is used to circulate the negative electrode liquid flowing into the liquid distribution area 112 through the overflow hole back into the negative electrode liquid storage frame. The partition plate 108 and the front side plate are provided with electrode mounting slots 110 at corresponding positions. The titanium sheet electrode 111 is fixed on the electrode suspension arm, and both ends of the electrode suspension arm are engaged in the electrode mounting slots 110, so that the titanium sheet electrode 111 is suspended in the negative electrode electrolysis area 106. The titanium sheet electrode 111 is made of TA1 grade pure titanium plate, which is made into a grid of rhomboid or hexagonal holes by precision laser cutting or expansion stretching process. The opening ratio of the grid is designed to be 40%-60%, that is, the hole area accounts for 40%-60% of the total area, so as to achieve the best balance between specific surface area and mechanical strength. The nano-nickel-cobalt alloy coating is first formed by sandblasting and acid etching of a titanium substrate, followed by pulse electrodeposition of a 5-15 μm thick nickel-cobalt alloy nanocrystalline coating under specific electrolyte and process parameters. The molar ratio of nickel to cobalt is controlled at 7:3 to obtain higher catalytic activity and good copper adhesion strength. The nano-nickel-cobalt alloy coating has hydrogen evolution inhibition and copper deposition catalytic effects. Its high hydrogen evolution overpotential forces electrons to be preferentially used for the reduction of Cu²⁺. At the same time, its nanocrystalline structure provides a large number of uniformly energetic nucleation sites, which promotes the rapid formation of a dense and smooth coating in an island-like growth mode, rather than a loose powder. The negative electrode inlet pipe is made of PVDF material, installed inside the bottom plate of the cylinder, and extends into the negative electrode area 106. The inlet end of the negative electrode inlet pipe is connected to the negative electrode liquid inlet pipe through an adapter, so that the negative electrode liquid can enter from the bottom of the negative electrode electrolysis area 106. On the one hand, the negative electrode liquid that has been reduced in the upper part can flow from the overflow port 109 into the liquid distribution area 112. On the other hand, the injected negative electrode liquid can also play an auxiliary stirring role, thereby promoting mass transfer.The pulsed power supply is applied to the negative electrode. On the one hand, during the pulse interval, the Cu²⁺ concentration near the electrode interface is restored, avoiding concentration polarization and dendrite growth caused by ion depletion. On the other hand, applying a short, low-amplitude reverse pulse every certain period of operation can selectively break up and peel off any tiny dendrite tips that may form without affecting the dense copper plating, thus achieving an online polishing effect and obtaining a smoother and denser deposition layer.
[0024] like Figure 2 As shown, both the positive electrode liquid storage tank 2 and the negative electrode liquid storage tank 3 are equipped with filter bag frames 10, and filter bags are fitted inside the filter bag frames 10. The ports of the positive electrode liquid outlet pipe 6 or the negative electrode liquid outlet pipe 8 are located inside the filter bags. The filter bags adopt a graded filter bag structure, with an outer layer of fiber filter bags with a pore size of 3-6μm and an inner layer of large-pore filter screens with a pore size of 30-70μm.
[0025] It should be noted that in this invention, the bottom of the filter bag frame 10 is fixed to the bottom of the positive electrode liquid storage tank 2 and the negative electrode liquid storage tank 3 by fasteners or welding, and is located on the side of the positive electrode liquid storage tank 2 and the negative electrode liquid storage tank 3 near the liquid outlet; the filter bag is fitted inside the filter bag frame 10, and its upper port is sealed and fixed to the top of the filter bag frame 10 by elastic straps, clamps or clips, ensuring that all liquids must pass through two layers of filter media before entering the internal clean liquid area; the inner large-pore filter screen is made of polyester PET or stainless steel. The monofilament filter screen woven from 316L steel wire has a pore size of 30-70μm, preferably 50μm. This pore size can effectively intercept larger particles from the electrolysis zone, such as fragments of detached trace electrode coatings, coarse particles of deposited copper, and accidental impurities in the pipeline. The outer fiber filter bag is a deep filtration filter bag made of polypropylene PP meltblown or needle-punched nonwoven fabric with a pore size of 3-6μm, preferably 5μm. This pore size can capture fine suspended solids, colloids, bacterial growth clusters, and micro-precipitates produced by chemical reactions. In this invention, the inner large-pore filter screen is fitted inside the outer small-pore fiber filter bag, and then both are fitted together in the filter bag frame 10. The outlet end of the positive or negative electrode liquid outlet pipe is inserted into the filter bag. The liquid flowing out from the positive or negative electrode liquid outlet pipe first passes through the inner large-pore filter screen, then through the small-pore fiber filter bag, and then flows out into the positive or negative electrode storage tank.
[0026] like Figure 2 and Figure 4As shown, the control system includes a main controller, a pH sensor, a redox potential sensor, a differential pressure sensor, and a flow sensor. The pH sensor and the redox potential sensor are installed in the positive electrode liquid storage tank and the negative electrode liquid storage tank, respectively. The differential pressure sensor is installed on both the inner and outer sides of the positive electrode electrolysis frame, and the flow sensor is installed on the positive electrode liquid inlet pipe 7 and the negative electrode liquid inlet pipe 9. The main controller is electrically connected to the pH sensor, the redox potential sensor, the differential pressure sensor, and the flow sensor. The main controller is located in the control box 11, and a touch screen 13 is provided on the outer surface of the control box 11. An audible and visual alarm 12 is provided on the upper surface of the control box 11.
[0027] It should be noted that in this invention, the main controller is primarily used to acquire digital signals from all sensors in real time and process and judge them according to a preset algorithm; the redox potential sensor is used to monitor the overall redox potential of the solution. In the sulfuric acid-sodium persulfate system, the ORP value is related to the persulfate ion (S₂O₈). 2- Concentration is highly positively correlated; therefore, the ORP value can directly, online, and sensitively reflect the regeneration progress. The pH sensor monitors the pH value in real time, and the main controller adjusts the system based on the real-time data from the pH sensor to ensure the reaction proceeds within the optimal pH window. This prevents the aggravation of side reactions such as chlorine evolution or damage to electrodes and membranes caused by pH runaway, ensuring reaction selectivity and component lifespan. The differential pressure sensor uses a ceramic diaphragm differential pressure transmitter, which can accurately measure the minute pressure difference ΔP across the cation exchange membrane 107 in real time. A continuous increase in the pressure difference ΔP is the most direct and sensitive indicator of membrane fouling or blockage. The differential pressure sensor enables the system to have predictive maintenance capabilities, triggering alarms or automatic cleaning programs before membrane performance deteriorates significantly, avoiding sudden shutdowns. The flow sensor uses an electromagnetic flow meter to accurately measure the electrolyte circulation flow rate. The main controller uses flow rate as a key control variable to ensure sufficient mass transfer rate on the electrode surface. The interlocked control of flow rate and current density avoids problems such as electrode dry burning due to insufficient flow or energy waste due to excessive flow.
[0028] An electrolyte recycling method, applied to any of the electrolyte recycling systems described above, includes the following steps: S1. Inject the PCB micro-etching waste liquid to be treated into the positive electrode liquid storage tank 2 and negative electrode liquid storage tank 3 of the system. Then, start the initialization program through the touch screen 13 of the control system. The main controller performs self-test and calibration on the pH and oxidation-reduction potential sensors to confirm that each execution unit, including the positive electrode liquid circulation pump 4, the negative electrode liquid circulation pump 5, the pulse power supply, etc., is in standby mode. S2. Start the positive electrode liquid circulation pump 4 and the negative electrode liquid circulation pump 5 to pump the positive electrode liquid and the negative electrode liquid into the corresponding areas of the electrolysis cylinder 1 through the positive electrode liquid inlet pipe 7 and the negative electrode liquid inlet pipe 9, respectively. The electrolyte flow path is as follows: Positive electrode circuit: Positive electrode liquid storage tank 2 → Positive electrode liquid circulation pump 4 → Positive electrode liquid inlet pipe 7 → Positive electrode liquid inlet pipe → Positive electrode electrolysis zone 102 → Positive electrode liquid outlet pipe 6 → Filter bag in positive electrode liquid storage tank 2 → Circulation completed; Negative electrode circuit: Negative electrode liquid storage tank 3 → Negative electrode liquid circulation pump 5 → Negative electrode liquid inlet pipe 9 → Negative electrode liquid inlet pipe → Negative electrode electrolysis zone 106 → Negative electrode liquid outlet pipe 8 → Filter bag in negative electrode liquid storage tank 3 → Circulation completed; The reflux electrolyte first passes through the outer 30-70μm large-pore filter screen of the filter bag to intercept larger particles, and then passes through the inner 3-6μm precision fiber filter bag to remove fine suspended matter and impurities, effectively preventing the electrodes and ion membrane from clogging. S3. The main controller starts the pulse power supply and applies pulse voltage to the boron diamond electrode 103 and the titanium sheet electrode 111. Within the positive electrode region: Under the excitation of a pulsed electric field, the boron-doped diamond thin-film electrode efficiently catalyzes the generation of hydroxyl radicals from water molecules; the hydroxyl radicals react with sulfate (SO4) in the solution. 2- A reaction occurs, re-oxidizing it to persulfate (S₂O₈). 2- To achieve the regeneration of micro-etched components, the reaction formula is: 2SO4 2- +2·OH + 2H + →S2O8 2- + 2H2O; Within the negative electrode electrolysis zone 106: a mesh-like titanium sheet electrode 111, coated with a nano-nickel-cobalt alloy layer, selectively reduces copper ions (Cu) in the solution under a pulsed electric field. 2+ This causes it to precipitate as metallic copper and adhere to the electrode surface. The reaction formula is: Cu 2+ +2e - →Cu; S4. Throughout the entire cyclic electrolysis process, the control system monitors the key chemical parameters of the electrolyte in the two storage tanks in real time through pH sensors, redox potential sensors, differential pressure sensors, and flow sensors; the main controller adjusts the current density and frequency of the pulse power supply according to the redox potential value; and dynamically adjusts the system operating parameters by triggering the audible and visual alarm 12 when the differential pressure is abnormal, ensuring that the entire process is in the optimal state. S5. When the main controller determines from the sensor data that the persulfate concentration in the positive electrode liquid has reached the target regeneration standard and the copper deposition on the negative electrode has reached a certain thickness, the system prompts that the regeneration is complete, stops the circulation pump and pulse power supply, and discharges the regenerated micro-etching solution from the positive electrode liquid storage tank 2 for reuse; then the grid-shaped titanium sheet electrode 111 of the negative electrode electrolysis zone 106 can be removed for copper stripping to recover high-purity metallic copper; the system can prompt the replacement of the filter bag based on the pressure difference on both sides of the filter bag or the running time to complete the maintenance.
[0029] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Anyone skilled in the art can readily implement the present invention based on the accompanying drawings and the above description. However, any modifications, alterations, and variations made by those skilled in the art without departing from the scope of the present invention using the disclosed technical content are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and variations made to the above embodiments based on the essential technology of the present invention are still considered part of the technical solution of the present invention.
Claims
1. An electrolyte recycling system, characterized by: Including electrolytic cylinder (1), positive electrode liquid storage cylinder (2), negative electrode liquid storage cylinder (3), positive electrode liquid circulating pump (4) and negative electrode liquid circulating pump (5), the middle part of the electrolytic cylinder (1) is provided with positive electrode electrolytic frame, the outer side of the positive electrode electrolytic frame is provided with negative electrode electrolytic frame (105); The positive electrode electrolytic frame is communicated with the rear part of the positive electrode liquid storage cylinder through the positive electrode liquid outlet pipe (6), the front part of the positive electrode liquid storage cylinder (2) is communicated with the positive electrode electrolytic frame through the positive electrode liquid inlet pipe (7), the positive electrode liquid circulating pump (4) is installed on the positive electrode liquid inlet pipe (7), and is used for conveying the positive electrode liquid in the positive electrode liquid storage cylinder (2) into the positive electrode electrolytic frame through the positive electrode liquid inlet pipe (7); The negative electrode electrolytic frame (105) is communicated with the rear part of the negative electrode liquid storage cylinder through the negative electrode liquid outlet pipe (8), the front part of the negative electrode liquid storage cylinder (3) is communicated with the negative electrode electrolytic frame (105) through the negative electrode liquid inlet pipe (9), and the negative electrode liquid circulating pump (5) is installed on the negative electrode liquid inlet pipe (9) and is used for conveying the negative electrode liquid in the negative electrode liquid storage cylinder (3) into the negative electrode electrolytic frame (105) through the negative electrode liquid inlet pipe (9); It also includes a control system, the control system is connected with each electronic component, and is used for coordinating each component.
2. The electrolyte recycling system of claim 1, wherein: The positive electrode electrolytic frame includes a positive electrode frame body (101), a plurality of titanium screws are fastened and connected on the positive electrode frame body (101), the middle part of the positive electrode frame is hollowly arranged to form a positive electrode electrolysis area (102), a boron diamond electrode (103) is arranged in the positive electrode electrolysis area (102), and cation membranes (107) are further arranged on the two sides of the positive electrode frame body (101). A positive electrode liquid inlet pipe is arranged at the bottom of the positive electrode frame body (101), the upper end of the positive electrode liquid inlet pipe is butted with the positive electrode liquid inlet pipe (7) through an adapter, a plurality of liquid outlet openings are arranged on the positive electrode liquid inlet pipe, and the positive electrode liquid inlet pipe is used for conveying the positive electrode liquid to the bottom of the positive electrode electrolysis area (102) through the liquid outlet openings.
3. The electrolyte recycling system of claim 2, wherein: The positive electrode frame body (101) is processed by polyvinylidene fluoride or reinforced polypropylene; the boron diamond electrode (103) is a boron-doped diamond film, a plurality of liquid passing holes are arranged in the boron diamond electrode (103), and the boron diamond electrode (103) is connected with an impulse power supply.
4. The electrolyte recycling system of claim 2, wherein: The cation membrane (107) includes a polyvinyl cation exchange membrane, a sulfonated polyether ether ketone layer is arranged on the side of the polyvinyl cation exchange membrane in contact with the positive electrode electrolyte, and a polymer layer containing a nitrogen coordination group is arranged on the side of the polyvinyl cation exchange membrane in contact with the negative electrode electrolyte.
5. The electrolyte recycling system of claim 1, wherein: The negative electrode frame includes a negative electrode frame body, the negative electrode frame body is arranged outside the positive electrode electrolytic frame, the area between the negative electrode frame body and the positive electrode frame is arranged as a negative electrode electrolysis area (106), and a titanium sheet electrode (111) is arranged in the negative electrode electrolysis area (106). A negative electrode liquid inlet pipe is arranged at the bottom of the negative electrode frame body, the inlet end of the negative electrode liquid inlet pipe is butted with the negative electrode liquid inlet pipe (9) through an adapter, a plurality of liquid outlet openings are arranged on the negative electrode liquid inlet pipe, and the negative electrode liquid inlet pipe is used for conveying the negative electrode liquid to the bottom of the negative electrode electrolysis area (106) through the liquid outlet openings.
6. The electrolyte recycling system of claim 5, wherein: The titanium sheet electrode (111) is coated with a layer of nanometer nickel-cobalt alloy coating, the titanium sheet electrode (111) is arranged in a grid shape, and the titanium sheet electrode (111) is connected with the pulse power supply.
7. The electrolyte recycling system of claim 1, wherein: The positive electrolyte storage tank (2) and the negative electrolyte storage tank (3) are both provided with filter bag frames (10), the filter bag frames (10) are sleeved with filter bags, and the ports of the positive electrolyte outlet pipe (6) or the negative electrolyte outlet pipe (8) are located in the filter bags. The filter bag adopts a hierarchical filter bag structure, the outer layer is a fiber filter bag with a pore size of 3-6 μm, and the inner layer is a large-pore filter screen with a pore size of 30-70 μm.
8. The electrolyte recycling system of claim 1, wherein: The control system comprises a main controller, a pH sensor, a redox potential sensor, a differential pressure sensor and a flow sensor, the pH sensor and the redox potential sensor are both installed in the positive electrolyte storage tank and the negative electrolyte storage tank, the differential pressure sensor is installed on the two sides of the positive electrolysis frame, and the flow sensor is installed on the positive electrolyte inlet pipe (7) and the negative electrolyte inlet pipe (9). The main controller is in electrical connection with the pH sensor, the redox potential sensor, the differential pressure sensor and the flow sensor. The main controller is arranged in the control box (11), the outer surface of the control box (11) is provided with a touch screen (13), and the upper end surface of the control box (11) is provided with an audible and visual alarm (12).
9. An electrolyte recycling method, characterized by: The electrolyte recycling system is applied to the electrolyte recycling system of any one of the preceding claims 1-8, and comprises the following steps: S1, injecting the PCB micro-etching waste liquid to be treated into the positive electrolyte storage tank (2) and the negative electrolyte storage tank (3) of the system, then starting the initialization program through the touch screen (13) of the control system, and performing self-checking and calibration on the pH and redox potential sensors by the main controller, to confirm that each execution unit including the positive electrolyte circulating pump (4), the negative electrolyte circulating pump (5) and the pulse power supply is in standby state; S2, starting the positive electrolyte circulating pump (4) and the negative electrolyte circulating pump (5), pumping the positive electrolyte and the negative electrolyte into the corresponding areas of the electrolysis tank (1) through the positive electrolyte inlet pipe (7) and the negative electrolyte inlet pipe (9) respectively, and the electrolyte flow path is as follows: Positive electrode loop: positive electrolyte storage tank (2) → positive electrolyte circulating pump (4) → positive electrolyte inlet pipe (7) → positive electrolyte inlet pipe → positive electrolysis area (102) → positive electrolyte outlet pipe (6) → filter bag in the positive electrolyte storage tank (2) → complete circulation; Negative electrode loop: negative electrolyte storage tank (3) → negative electrolyte circulating pump (5) → negative electrolyte inlet pipe (9) → negative electrolyte inlet pipe → negative electrolysis area (106) → negative electrolyte outlet pipe (8) → filter bag in the negative electrolyte storage tank (3) → complete circulation; The backflow electrolyte is first intercepted by the large-pore filter screen with a pore size of 30-70 μm in the inner layer of the filter bag, and then removed by the precision fiber filter bag with a pore size of 3-6 μm in the outer layer, so that the electrode and the ion membrane are effectively prevented from being blocked; S3, the main controller starts the pulse power supply, and applies pulse voltage to the boron diamond electrode (103) and the titanium sheet electrode (111). In the positive electrode area: boron-doped diamond thin film electrode under the excitation of pulse electric field, efficient catalysis of water molecules to produce hydroxyl radicals; hydroxyl radicals and sulfate SO4 2- in the solution react to re-oxidize it to persulfate S2O8 2- , to achieve the regeneration of micro-etching components, the reaction is as follows: 2SO4 2- + 2·OH + 2H + →S2O8 2- + 2H2O; Within the negative electrode electrolysis region (106): a mesh-like titanium sheet electrode (111) coated with a nano-nickel-cobalt alloy layer selectively reduces copper ions (Cu) in the solution under a pulsed electric field. 2+ This causes it to precipitate as metallic copper and adhere to the electrode surface. The reaction formula is: Cu 2+ + 2e - → Cu; S4、In the whole cycle electrolysis process, the control system monitors the key chemical indicators of the electrolyte in the two storage tanks in real time through the pH sensor, redox potential sensor, pressure difference sensor and flow sensor; the main controller adjusts the current density and frequency of the pulse power supply according to the redox potential value; when the pressure difference is abnormal, the audible and light alarm (12) is triggered to alarm and other dynamic adjustment system operating parameters to ensure that the whole process is in the optimal state; S5、When the main controller judges that the concentration of persulfate in the positive electrolyte has reached the target regeneration standard according to the sensor data, and the negative copper deposition reaches a certain thickness, the system prompts that the regeneration is completed, stops the circulating pump and the pulse power supply, and discharges the regenerated micro-etching liquid from the positive electrolyte storage tank (2) for reuse; Then the grid-shaped titanium sheet electrode (111) in the negative electrolysis area (106) can be taken out for copper stripping treatment to recover high-purity copper; The system can prompt to replace the filter bag according to the pressure difference or running time of the filter bag to complete the maintenance.