Method and device for optimizing insoluble anode copper plating process combined with electrolytic copper dissolving

Abstract

The invention discloses an insoluble anode copper plating process optimization method and device combined with electrolytic copper dissolving, the method adopts two processes of acidic electrolytic copper dissolving and insoluble anode copper electroplating of acidic copper sulfate as production combination, and a solution with higher sulfuric acid concentration is obtained from part of electrolytic catholyte and / or electroplating anolyte by adopting a copper removal agent; and the method is used for adjusting the sulfuric acid concentration of an electrolyte and / or a solution in an electroplating bath, and improving the problem that an electrolytic separator is damaged due to the fact that copper ions in a cathode bath area of the copper-dissolving electrolytic bath are accumulated due to ion leakage in the operation process and spongy copper is electrically separated out on the cathode of the electrolytic bath.

Description

A method and device for optimizing insoluble anode copper plating process combined with electrolytic copper dissolution Technical Field

[0001] The present invention relates to a process technology and equipment for electroplating copper with an insoluble anode, and in particular to an optimization method and device for the insoluble anode copper plating process combined with electrolytic copper dissolution. Background Art

[0002] The most common existing acid copper sulfate electroplating process uses an aqueous solution composed mainly of copper sulfate and sulfuric acid as the plating solution, i.e., an acid copper sulfate electroplating solution, which may also contain other electroplating additives. During the electroplating process, copper ions in the plating solution are electrolytically reduced to metallic copper at the cathode. As copper is electroplated, the copper ion concentration in the plating solution decreases and the sulfuric acid concentration increases. Therefore, existing acid copper sulfate electroplating processes are mainly divided into two types: soluble anode and insoluble anode processes. Different methods are used to replenish the copper source during the electroplating process, and the dissolved copper source is used to stabilize the sulfuric acid in the plating solution.

[0003] The soluble anode copper plating process involves the gradual dissolution of the anode during the electrochemical reaction. A common soluble anode material is phosphor copper. During the electroplating process, the copper metal at the anode dissolves into copper ions, replenishing the copper ions in the plating solution. However, the use of phosphor copper anodes is prone to problems such as anode polarization and uneven current distribution, resulting in unstable coating quality. Furthermore, phosphor copper is expensive, and its production and use generate harmful phosphorus-containing wastewater, which can be extremely harmful to organs such as the liver. To ensure that the wastewater meets discharge standards, additional treatment costs for the electroplating wastewater must be added.

[0004] An insoluble anode copper plating process refers to a copper plating process in which the anode undergoes minimal or no dissolution during the electroplating reaction. Common insoluble anodes include titanium coated with precious metal oxides, conductive graphite, platinum, and lead alloys. In existing copper plating technologies, copper oxide is typically used to supplement the plating solution in acidic insoluble anode copper plating processes. This copper oxide reacts with sulfuric acid in the plating solution to replenish lost copper ions, while also consuming an equivalent amount of sulfuric acid. In particular, in the circuit board production process, the industry prefers to use copper oxide to supplement insoluble anode acidic copper plating production lines to achieve a uniform and smooth coating, eliminate phosphorus compound contamination in the wastewater, and reduce labor intensity.

[0005] Patent application number 201980055803.8 proposes using an electrolytic cell to dissolve copper through acidic electrolysis to form an insoluble anode copper plating solution as a copper source. One preferred solution is to form a controllable circulation flow system between the electrolytic cell and the solution in the electroplating tank on the electroplating production line, and use an acid balance electrolysis system to adjust the sulfuric acid concentration in the plating solution to ensure smooth copper electroplating operations. Specifically, an anion exchange membrane is used to separate the electrolytic cell into an electrolytic anode region and an electrolytic cathode region, and a metal containing copper is used as the electrolytic anode, and a conductor is used as the electrolytic cathode. At the same time, an acid-balanced cathode region is separated from the electrolytic anode region, and the acid-balanced cathode region is separated by a diaphragm facing the electrolytic cathode region. An acid-balanced cathode is set in the acid-balanced cathode region, and an acid-balanced anode is set in the electrolytic cathode region. During the electrolysis process, hydrogen is generated at the acid-balanced cathode, and oxygen and hydrogen ions are generated at the acid-balanced anode. Sulfate ions in the electrolytic anolyte are affected by the electric field attraction of the acid-balanced anode and pass through the anion exchange membrane into the electrolytic cathode region, combining with hydrogen ions generated by water electrolysis to form sulfuric acid, thereby increasing the sulfate concentration of the electrolytic cathode solution. However, the use of an acid-balanced electrolysis system requires the additional addition of acid-balanced electrodes, acid-balanced power supplies, and separators, which greatly increases the equipment cost. In addition, the excess hydrogen released at the cathode during acid-balanced electrolysis is highly flammable and explosive, requiring safe handling of the hazardous hydrogen source. Consequently, this patented process suffers from the disadvantages of large equipment investment, high power consumption, and the generation of a large amount of hazardous hydrogen.

[0006] Furthermore, in actual use, separators rarely achieve the ideal 100% barrier efficiency for specific ions or molecules, and the assembly structure of electrolytic cell separators results in gaps. Therefore, for electrolytic cells or electroplating cells with ion-selective diaphragms, bipolar membranes, or reverse osmosis membrane separators, a certain amount of ion interpenetration and migration still occurs between the cathodic and anodic regions. For example, when an anion exchange membrane is used as the separator in a copper electrolysis cell, the anode of the cell is metallic copper, the electrolytic anolyte is a mixture of sulfuric acid and copper sulfate, and the cathode is stainless steel, the electrolytic catholyte is sulfuric acid. During the copper electrolysis process, sulfate anions in the cathode region rapidly migrate through the anion exchange membrane into the anode region due to the electric field force, where hydrogen is electrolyzed. The metallic copper at the anode dissolves and combines with sulfate to form copper sulfate. Although most of the copper ions are trapped in the anode region, a small amount of copper ions can still seep into the cathode region of the copper electrolysis cell. As the electrolytic copper dissolution proceeds and the copper ions that migrate to the cathode tank area accumulate, the copper ions in the solution in the cathode tank area of ​​the electrolytic copper dissolution tank will be electrolyzed into metallic copper by the cathode. Since the copper ion concentration of the electrolytic cathode solution is relatively low, the copper is electrolyzed into metallic copper in the form of fine particles, which is called sponge copper in the industry. These sponge coppers float in the solution and adhere to the anion exchange membrane. The adhered sponge copper particles act as secondary electrodes in the electric field, causing the particle shape to change and puncture the anion exchange membrane, thereby damaging the electrolysis equipment and increasing the replacement frequency of the anion exchange membrane, thereby increasing production costs. Similarly, in addition to the anion exchange membrane, the above-mentioned problems will also occur when other diaphragms are used. However, there is no solution for copper ion leakage in the prior art.

[0007] Summary of the Invention

[0008] The first object of the present invention is to provide a method for optimizing an insoluble anode copper plating process combined with electrolytic copper dissolution. When copper ions are replenished in the acidic plating solution in the acidic insoluble anode copper plating process by acidic electrolytic copper dissolution, a chemical method is used to improve equipment damage caused by copper ion leakage, and the sulfuric acid concentrations of the electrolyte and the electroplating solution in the system can be stabilized to enable the electrolytic copper dissolution operation and the copper electroplating operation to proceed smoothly.

[0009] A second object of the present invention is to provide an apparatus for optimizing the process of insoluble anode copper plating combined with electrolytic copper dissolution.

[0010] The technical solution adopted by the present invention to achieve the first purpose is:

[0011] A method for optimizing an insoluble anode copper plating process combined with electrolytic copper dissolution includes an electrolytic copper dissolution process and an insoluble anode copper plating process, and is characterized by comprising the following steps:

[0012] Step (1): using a copper dissolving electrolytic cell with an electrolytic cell separator and an insoluble anode electroplating cell to perform electrolysis and electroplating operations respectively;

[0013] The copper dissolving electrolytic cell is divided into an electrolytic anode cell area and an electrolytic cathode cell area by the electrolytic cell separator, and the electrolytic anode liquid and the electrolytic cathode liquid are respectively contained therein;

[0014] The insoluble anode electroplating tank is provided with an electroplating tank divider or is not provided with an electroplating tank divider. When the electroplating tank divider is provided, the tank is divided into an electroplating anode tank area and an electroplating cathode tank area, and the electroplating anode liquid and the electroplating cathode liquid are respectively contained therein. When the electroplating tank divider is not provided, the tank is filled with electroplating liquid.

[0015] During production operations, the electrolytic anode metal copper in the copper-dissolving electrolytic cell undergoes an electrochemical reaction in which it dissolves and turns into copper ions, while the cathode plating piece in the insoluble anode electroplating cell electroprecipitates copper, and the main components of the electrolytic anode solution, electroplating solution or electroplating cathode solution are a mixed solution of sulfuric acid and copper sulfate;

[0016] Step (2): adding the electrolytic anolyte as a copper sulfate copper source supplement solution into the electroplating tank to supplement the copper ion concentration of the plating solution; and,

[0017] When the electroplating tank is not provided with an electroplating tank divider, part or all of the electrolytic cathode liquid is taken out to react with a copper remover; when the electroplating tank is provided with an electroplating tank divider, part or all of the electrolytic cathode liquid and / or electroplating anode liquid is taken out to react with a copper remover, and then the reaction liquid is subjected to solid-liquid separation to obtain an insoluble solid copper salt and a filtrate containing sulfuric acid, and the filtrate containing sulfuric acid is added to the electrolytic anode liquid and / or electrolytic cathode liquid and / or electroplating anode liquid to allow the electrolysis and electroplating operations to continue.

[0018] The anodic copper dissolving electrolytic cell of the present invention is a device for preparing copper sulfate and / or adjusting the concentration of a copper sulfate solution; the insoluble anode electroplating cell is an electroplating cell used in an acidic copper sulfate electroplating process, wherein the plated workpiece is connected to the negative electrode of the electroplating cell power supply and immersed in the electroplating solution of the electroplating cell or the cathode cell plating solution. As the electrolytic copper dissolving reaction in the copper dissolving electrolytic cell proceeds, the copper ion concentration in the electrolytic anodic solution continuously increases. After reaching the copper ion concentration set by the process control, the copper ion concentration is added to the acidic copper sulfate electroplating solution as a copper sulfate source supplement.

[0019] The present invention combines the production processes of acid electrolytic copper dissolution and insoluble anode copper electroplating with acid copper sulfate, adopts a copper remover to obtain a solution with a higher sulfuric acid concentration from part of the electrolytic cathode liquid and / or the electroplating anode liquid, and uses the solution to adjust the sulfuric acid concentration of the electrolyte and / or the solution in the electroplating tank, thereby improving the problem of copper ion accumulation in the cathode tank area of ​​the copper dissolving electrolytic tank due to ion leakage during operation, resulting in sponge copper electrolysis on the cathode of the electrolytic tank and damage to the electrolytic separator.

[0020] In the scheme of the present invention, the purpose of the present invention can be achieved by using a mixed solution whose main components are sulfuric acid and copper sulfate, or a solution whose main component is sulfuric acid as the electrolytic anode solution initially added. The electroplating solution and the electroplating cathode solution are acidic copper sulfate electroplating solutions. The electrolytic cathode solution and the electroplating anode solution are aqueous solutions containing sulfuric acid. The sulfuric acid in the electrolytic cathode solution and the electroplating anode solution is mainly used to provide ions for the solution to establish an electric field so that the electrolytic copper dissolving reaction and the electroplating reaction proceed smoothly. The purpose of the present invention can be achieved when sulfuric acid is present. When the sulfuric acid concentration is not less than 0.1% by mass, the electrolysis and electroplating operations can be maintained more stably. Generally speaking, during the operation, the electrolytic cathode of the copper dissolving electrolytic cell will electrolyze hydrogen, while the insoluble anode of the electroplating cell will electrolyze oxygen.

[0021] The electrolytic cell separator of the present invention is selected from at least one of an anion exchange membrane, a bipolar membrane, and a reverse osmosis membrane, and the electroplating cell separator is selected from at least one of an anion exchange membrane, a bipolar membrane, and a reverse osmosis membrane.

[0022] As a preferred embodiment of the present invention: when the insoluble anode electroplating tank does not have a plating tank separator, the electrolytic tank separator is selected as a bipolar membrane and / or a reverse osmosis membrane; when the insoluble anode electroplating tank is provided with an anion exchange membrane as a plating tank separator, the electrolytic tank separator is selected as an anion exchange membrane; when the insoluble anode electroplating tank is provided with a bipolar membrane and / or a reverse osmosis membrane as a plating tank separator, the electrolytic tank separator is selected as a bipolar membrane and / or a reverse osmosis membrane.

[0023] When bipolar membranes and / or reverse osmosis membranes are used as electrolytic cell separators, copper ions and sulfate ions in the electrolytic anode area can be effectively prevented from entering the electrolytic cathode area, except for a small amount of leakage. However, the power consumption of the electrolytic operation is greater than when an anion exchange membrane is used as the electrolytic cell separator.

[0024] When adopting anion exchange membrane as electrolytic cell separator, the copper ions in the electrolytic anode area leak into the electrolytic cathode tank area on a small amount, and the sulfate ions in the electrolytic cathode tank area can be subjected to electric field attraction to pass through the anion exchange membrane and enter the electrolytic anode tank area. Now, anion exchange membrane is provided as electrolytic cell separator in described insoluble anode electroplating tank, so that some sulfate ions in the electroplating cathode liquid can be subjected to electric field attraction to pass through the anion exchange membrane and enter the electroplating anode tank area, thereby avoiding sulfate ions from constantly accumulating in the electroplating cathode liquid. When carrying out electrolytic operation for a long time, in order to maintain the electrolyte content in the electrolytic cathode liquid so that the electrolytic operation is carried out smoothly, it is necessary to supplement sulfate ions to the electrolytic cathode tank area. Supplementing the electrolytic cathode tank area with an aqueous solution containing sulfate radical can achieve the above purpose, preferably the electroplating anode liquid is added to the electrolytic cathode liquid, or the electroplating anode liquid and the electrolytic cathode liquid are mixed.

[0025] In step (1), when the insoluble anode electroplating tank is provided with an electroplating tank partition and is divided into an electroplating anode tank area and an electroplating cathode tank area, such structural improvement has three major advantages: first, the electroplating tank adopts a diaphragm partition structure, which can reduce the loss of electroplating brightener in the electroplating cathode liquid; second, the oxygen electrolyzed by the anode of the electroplating tank can be collected and reused; third, the corrosion of the cathode by the oxidizing gas of the anode is reduced.

[0026] Preferably, both the electrolytic cell separator and the electroplating cell separator are constructed from anion exchange membranes. The advantages of using anion exchange membranes are as follows: First, they are affordable and durable, and their electrolysis or electroplating cell pressure is lower than that of bipolar membranes or reverse osmosis membranes, saving energy. Second, when the chloride ion concentration in the electroplating cathode liquid is too high, the anodes of the insoluble anode electroplating cell can be used to divert excess chloride ions from the cathode liquid to the anode cell during the electroplating operation, where they are then electrolyzed and discharged out of the electroplating system, reducing excess chloride ions in the plating solution and preventing them from affecting production quality.

[0027] The copper remover described in step (2) is oxalic acid. According to the process requirements, part or all of the electrolytic cathode liquid is extracted and mixed with oxalic acid, so that the copper sulfate therein reacts with oxalic acid to obtain copper salt precipitate copper oxalate and generate sulfuric acid. Alternatively, when a plating tank partition is provided in the insoluble anode electroplating tank, and a scheme of adding the electroplating anode liquid to the electrolytic cathode liquid or a scheme of mixing the electroplating anode liquid and the electrolytic cathode liquid is adopted, according to the process requirements, part or all of the electrolytic cathode liquid and / or the electroplating anode liquid is extracted and mixed with oxalic acid to react. The chemical reaction principle of the copper remover oxalic acid and copper sulfate is as follows.

[0028] The reaction of oxalic acid and copper sulfate: CuSO4+H2C2O4→H2SO4+CuC2O4↓.

[0029] The copper ion accumulation rate of the cathode liquid in the copper-dissolving electrolytic cell is related to the performance of the copper-dissolving electrolytic cell separator, the installation process level of the cell, and the current used for copper dissolving. Generally, under normal production conditions, the number of copper ions leaked per unit time can be regarded as a constant, so the copper ion accumulation rate of the cathode liquid is mainly determined by the power of the copper dissolving. Therefore, the frequency and reaction volume of extracting the cathode liquid for copper removal can be set according to the specific process conditions and requirements. Preferably, according to the actual process conditions and requirements, the extraction of the cathode liquid for copper removal is controlled at a pre-set time.

[0030] The copper removal reaction liquid is subjected to solid-liquid separation to obtain insoluble solid copper salt and a filtrate containing sulfuric acid. The sulfuric acid concentration of the filtrate containing sulfuric acid is increased compared with that before the reaction with the copper removal agent, hereinafter referred to as a sulfuric acid-rich filtrate, and the filtrate may also contain unreacted copper sulfate and / or residual oxalic acid and / or other chemicals originally contained in the solution. The copper-dissolving electrolytic cell adopts different electrolytic cell separators and the insoluble anode electroplating cell adopts different electroplating cell separators to produce a variety of different chemical reaction conditions. Under the sulfuric acid concentration requirements set by the actual process, the sulfuric acid-rich filtrate is added to the electrolytic anode solution and / or electrolytic cathode solution and / or electroplating anode solution to stabilize the sulfuric acid concentration in each solution and ensure the smooth progress of the electrolytic reaction and the electroplating reaction.

[0031] When an excess of oxalic acid is added to the reaction solution, the resulting sulfuric acid-rich filtrate contains unreacted oxalic acid. When this filtrate is returned to the copper-dissolving electrolytic cell and / or electroplating tank, the oxalic acid reacts with the copper ions in the solution to produce solid copper oxalate, which can clog the separator membrane of the electrolytic cell or electroplating tank, affecting normal operation of the equipment. Therefore, the amount of oxalic acid added as a copper removal agent preferably does not exceed the molar amount of copper ions required to remove the reaction solution.

[0032] As a preferred embodiment of the present invention, an anode titanium basket and an anode bag are provided in the electrolytic anode tank area of ​​the copper dissolving electrolytic cell for containing metal copper blocks, the anode titanium basket is connected to the positive electrode of the copper dissolving electrolytic cell power supply, and the anode titanium basket is immersed in the electrolytic anode liquid.

[0033] The present invention can be improved as follows: a liquid circulation loop is added between the electrolytic anode tank area and an insoluble anode electroplating tank without an electroplating tank separator, or between the electrolytic anode tank area and an insoluble anode electroplating tank electroplating cathode tank area with an electroplating tank separator, so that the electrolytic anode liquid and the electroplating liquid (or the electroplating cathode liquid) are mixed by flow, so that the electroplating liquid (or the electroplating cathode liquid) with a reduced copper ion concentration and an increased sulfuric acid concentration after the electroplating operation participates in the electrolytic copper dissolution reaction to produce copper sulfate copper source replenishing solution.

[0034] The present invention can be further improved as follows: a solution mixing exchange tank for the electrolytic anode liquid and the electroplating liquid (or the electroplating cathode liquid) is added between the electrolytic anode tank area and the insoluble anode electroplating tank without an electroplating tank separator, or between the electrolytic anode tank area and the electroplating cathode tank area of ​​the insoluble anode electroplating tank with an electroplating tank separator, so that the electrolytic anode liquid and the electroplating liquid (or the electroplating cathode liquid) are mixed by flowing so that the copper ion concentration thereof is adjusted.

[0035] The present invention can be further improved as follows: an electrolytic anolyte circulation tank connected to the electrolytic anode tank area of ​​the copper-dissolving electrolytic cell is added, and the electroplating solution (or electroplating cathode solution) overflowing from the electroplating cell is drained into the electrolytic anolyte circulation tank to participate in the anodic copper-dissolving electrochemical reaction of the copper-dissolving electrolytic cell to produce copper sulfate copper source replenishing solution.

[0036] The present invention can be improved as follows: the electrolytic cathode liquid or the mixture of the electrolytic cathode liquid and the electroplating anode liquid is subjected to an oxidation treatment to oxidize the metallic copper particles floating in the electrolytic cathode liquid to convert them into copper oxide, which then reacts with sulfuric acid to form copper sulfate. This can also effectively reduce damage to the separators of the copper dissolving electrolytic cell.

[0037] Preferably, oxygen and / or ozone and / or hydrogen peroxide are used to oxidize the electrolytic cathode liquid or the mixed solution of the electrolytic cathode liquid and the electroplating anode liquid.

[0038] More preferably, the electrolytic cathode liquid is oxidized by oxygen electrolyzed from the anode of the electroplating tank.

[0039] More preferably, a gas-liquid mixing device is used to promote oxygen and / or ozone oxidation of the electrolytic cathode liquid or the mixture of the electrolytic cathode liquid and the electroplating anode liquid, thereby accelerating the conversion of metallic copper particles in the electrolytic cathode liquid into copper oxide, which then reacts with sulfuric acid to form copper sulfate, thereby more effectively reducing damage to the separators of the copper-dissolving electrolytic cell. The gas-liquid mixing device is preferably a vacuum ejector and / or a spray tower.

[0040] During research and development, the inventors discovered that when the electrolytic cathode liquid or the mixture of the electrolytic cathode liquid and the electroplating anode liquid is not subjected to an oxidation treatment, the electrolysis and electroplating operations can be continued preferably by keeping the copper ion concentration of the electrolytic cathode liquid at no more than 10 g / L. However, when the electrolytic cathode liquid or the mixture of the electrolytic cathode liquid and the electroplating anode liquid is subjected to an oxidation treatment, the electrolysis and electroplating operations can still be continued preferably even when the copper ion concentration of the electrolytic cathode liquid is higher. Therefore, as a preferred embodiment of the present invention, the copper ion concentration of the electrolytic cathode liquid is kept at no more than 10 g / L, and / or the electrolytic cathode liquid or the mixture of the electrolytic cathode liquid and the electroplating anode liquid is subjected to an oxidation treatment.

[0041] The present invention can be improved as follows: the insoluble anode electroplating tank is provided with an electroplating tank separator, and a liquid circulation loop is added between the electrolytic cathode tank area and the electroplating anode tank area, so that the two solutions are mixed by flow to adjust the sulfuric acid concentration, and the oxygen electrolyzed in the electroplating anode tank area is used to oxidize the electrolytic cathode liquid. This preferred solution also has the following advantages: (1) the oxygen electrolyzed in the electroplating anode tank area is brought into the electrolytic cathode liquid through solution mixing and exchange to oxidize the electrolytic cathode liquid; (2) the copper dissolving electrolytic tank realizes oxygen-containing electrolysis cathode liquid during operation, reducing the copper dissolving tank pressure and saving electricity; (3) the electroplating anode is used to oxidize and eliminate residual oxalic acid from the sulfuric acid-rich filtrate, further avoiding the chemical reaction between oxalic acid and copper ions in the tank solution to produce solid product copper oxalate and cause clogging of the separator membrane of the electrolytic tank or electroplating tank. When both the electrolytic cell separator and the electroplating cell separator are made of anion exchange membranes, the sulfate radicals in the electroplating cathode liquid can migrate to the electroplating anode tank area during the electroplating process and then enter the electrolytic cathode liquid of the copper-dissolving electrolytic cell through the solution mixing exchange tank, so that the copper-dissolving electrolytic cell can be directly replenished with sulfuric acid during operation.

[0042] The present invention can be further improved by providing a plating tank divider within the insoluble anode electroplating tank, and adding a solution mixing and exchange tank for the copper-dissolving electrolytic tank cathode solution and the plating tank anolyte solution between the electrolytic cathode tank area and the electroplating anode tank area, so that the two solutions are mixed within the solution mixing and exchange tank. This solution allows for better adjustment of the sulfuric acid concentration, while also allowing solution to be directly extracted from the solution mixing and exchange tank for copper removal. After copper removal, the sulfuric acid-rich filtrate can be returned to the solution exchange mixing tank for recycling.

[0043] The present invention can also be improved as follows: when a solution mixing exchange tank is provided between the electrolytic cathode tank area and the electroplating anode tank area, a solid-liquid separator is added to perform solid-liquid separation treatment on the solution flowing back from the solution exchange tank to the copper dissolving electrolytic tank and the electroplating tank, so as to reduce the entry of solid copper particles and copper oxalate into the copper dissolving electrolytic tank and the electroplating tank.

[0044] The present invention can also be improved as follows: before adding a copper sulfate copper source replenishing solution with a higher copper ion concentration into the electroplating cathode solution to replenish the copper ion concentration, the copper sulfate copper source replenishing solution is subjected to solid-liquid separation treatment to remove solid impurities to ensure the electroplating quality.

[0045] The present invention can also be improved as follows: when the copper ion concentration of the electrolytic anolyte is difficult to reach the set concentration by the electrolytic copper dissolving reaction alone, copper oxide is added to the electrolytic anolyte and / or electroplating solution (or electroplating cathode solution) as an auxiliary copper source to accelerate the increase of the copper ion concentration in the electrolytic anolyte and / or electroplating solution (or electroplating cathode solution) to reach the process set value. Preferably, copper oxide powder is added to at least one of the insoluble anode electroplating tank or its electroplating cathode area, the electrolytic anode tank area of ​​the copper dissolving electrolytic tank, the electrolytic anolyte circulation tank, and the solution mixing exchange tank of the electrolytic anolyte and electroplating solution (or electroplating cathode solution).

[0046] The present invention can also be improved as follows: When copper oxide containing a high amount of chloride ion impurities is used as a supplementary copper source or chloride ion impurities are introduced from other sources, the solution in the copper-dissolving electrolytic cell and / or the insoluble anode electroplating cell contains a high amount of chloride ions, resulting in the generation of chlorine gas at the electrolytic anode and / or the electroplating anode, and the chlorine gas is precipitated along with the generated oxygen. Therefore, the gas generated in the system of the present invention containing both chlorine and oxygen is scrubbed to remove the chlorine, and then discharged from the system or the remaining oxygen is reused.

[0047] The present invention can also be improved by heating the copper oxalate after the copper removal reaction to produce copper oxide, which is then recycled into the system as a supplementary copper source. Therefore, the present invention uses oxalic acid to react with a solution containing copper sulfate to produce sulfuric acid and copper oxalate. The resulting copper oxalate is then heated in an oxygen-containing environment to produce copper oxide. All of the reactants can be recycled into the production system, and no new pollution sources are generated in the process.

[0048] The second object of the present invention is achieved through the following technical solutions.

[0049] A device for optimizing an insoluble anode copper plating process combined with electrolytic copper dissolution comprises an insoluble anode electroplating tank, characterized in that a copper dissolving electrolytic tank, a chemical reaction tank, and a solid-liquid separator are additionally provided; wherein:

[0050] The copper dissolving electrolytic cell is divided into an electrolytic anode cell area and an electrolytic cathode cell area by an electrolytic cell separator, and is used to respectively contain an electrolytic anolyte and an electrolytic cathode liquid. The electrolytic anode of the copper dissolving electrolytic cell is copper metal, and the copper sulfate copper source replenishing solution required in the electroplating cell is produced by an electrolytic copper dissolving method using the electrolytic anolyte containing sulfuric acid.

[0051] The insoluble anode electroplating tank is used to hold electroplating solution, or is divided into an electroplating anode tank area and an electroplating cathode tank area by an electroplating tank divider, and is used to respectively hold electroplating anode solution and electroplating cathode solution, and uses the electroplating cathode tank area to electroplate the electrolytic cathode of the plated workpiece to produce acid copper sulfate; the insoluble anode electroplating tank without an electroplating tank divider, or the electroplating cathode tank area of ​​the insoluble anode electroplating tank with an electroplating tank divider, is connected to the electrolytic anode tank area of ​​the copper dissolving electrolytic tank via a pipeline, so that the copper sulfate copper source replenishing solution produced in the copper dissolving electrolytic tank can be added to the insoluble anode electroplating tank;

[0052] The chemical reaction tank is connected to the copper-dissolving electrolytic tank and / or the insoluble anode electroplating tank and the solid-liquid separator through pipelines, and the chemical reaction tank is used to react the electrolytic cathode liquid and / or the electroplating anode liquid with the copper removal agent oxalic acid to remove copper;

[0053] The solid-liquid separator is connected to the chemical reaction tank and the copper-dissolving electrolytic tank and / or the insoluble anode electroplating tank respectively through pipelines, and is used to perform solid-liquid separation on the solid-liquid mixture generated by the reaction in the chemical reaction tank to obtain copper salt filter residue and sulfuric acid-containing filtrate, and circulate the filtrate back to the copper-dissolving electrolytic tank and / or the insoluble anode electroplating tank through pipelines.

[0054] The solid-liquid separator can be a centrifuge, filter press, filter or other equipment capable of achieving solid-liquid separation.

[0055] The present invention can be improved as follows: at least two liquid flow communication channels are added between the electrolytic anode tank area of ​​the copper dissolving electrolytic cell and the insoluble anode electroplating cell without an electroplating cell separator, or between the electrolytic anode tank area of ​​the copper dissolving electrolytic cell and the electroplating cathode tank area of ​​the insoluble anode electroplating cell with an electroplating cell separator, to realize a liquid flow mixing circulation loop.

[0056] The present invention can be improved as follows: at least two liquid flow communication channels are added between the electrolytic cathode tank area of ​​the copper dissolving electrolytic tank and the electroplating anode tank area of ​​the insoluble anode electroplating tank provided with an electroplating tank separator to realize a liquid flow mixing circulation loop.

[0057] The present invention can be improved as follows: a temporary storage tank is added for use in chemical reactions, solution circulation and exchange, and temporary storage of materials; including but not limited to being used for mixing more than one solution, for dissolving copper oxide in the solution for subsequent addition to the electrolysis anode solution and / or the electroplating cathode solution, for temporarily storing sulfuric acid-rich filtrate or other solutions from the solid-liquid separator, etc.; the temporary storage tank is connected to the copper-dissolving electrolytic tank and / or the insoluble anode electroplating tank and / or the chemical reaction tank and / or the solid-liquid separator and / or other temporary storage tanks, or is arranged on a connecting pipe between at least two of the copper-dissolving electrolytic tank, the insoluble anode electroplating tank, and the chemical reaction tank.

[0058] The present invention can be further improved as follows: on the basis of the solid-liquid separator connected to the chemical reaction tank pipeline, an additional solid-liquid separator is provided and connected to the copper dissolving electrolytic tank and / or the insoluble anode electroplating tank and / or the temporary storage tank and / or other solid-liquid separators through the pipeline, so as to perform solid-liquid separation and impurity removal treatment on the solid matter in the solution.

[0059] The present invention can be further improved by adding a gas-liquid mixing device to the temporary storage tank to better oxidize the electrolytic cathode liquid or the mixture of the electrolytic cathode liquid and the electroplating anode liquid. The gas-liquid mixing device is preferably a vacuum ejector and / or a spray tower.

[0060] The present invention can also be improved as follows: an additional electroplating tank anode electrolysis gas washing tank is provided to wash and remove chlorine in the electrolyzed gas to reduce excess chloride ions in the electroplating cathode liquid and avoid affecting production.

[0061] The present invention can also be improved as follows: an overflow buffer tank is added to connect the above tanks to solve the process problem of solution flow between the tanks.

[0062] The present invention can also be improved as follows: a hydrogen safety treatment device is added to the copper dissolving electrolytic cell to safely treat the hydrogen generated by the copper dissolving electrolytic cell. The hydrogen safety treatment device can be a high-altitude discharge pipe and / or a hydrogen eliminator.

[0063] The present invention can also be improved as follows: an exhaust gas processor is added to connect the above-mentioned tanks to perform environmentally friendly treatment on the acidic exhaust gas produced by each tank.

[0064] The present invention can also be improved by adding sensors to the copper dissolving electrolytic cell and / or the insoluble anode electroplating cell and / or the chemical reaction cell and / or the temporary storage cell and / or the hydrogen safety handling equipment, as well as an automatic detection and feeding controller, to achieve automated safe production during the production process. The sensors can be one or more of a pH meter, an acidity meter, an electro-optical colorimeter, a redox potentiometer, a thermometer, a liquid level gauge, a hydrometer, a flow meter, and a hydrogen detector.

[0065] Compared with the prior art, the present invention has the following beneficial effects.

[0066] 1. The present invention uses oxalic acid to react with an acidic copper sulfate solution to produce a filtrate rich in sulfuric acid, which is then recycled. This solves the process problem caused by mutual leakage of the cathode and anode electrolytes between the copper-dissolving electrolytic cell and the electroplating cell. In addition, the amount of copper ions and sulfuric acid in the electrolytic system and the electroplating system is balanced during the production operation, allowing the production operation to continue for a long time.

[0067] 2. The present invention uses oxalic acid as a copper removal agent to react with an acidic copper sulfate solution to produce sulfuric acid for recycling. Therefore, compared with the technology of patent application number 201980055803.8, the present invention only needs to set up common chemical reaction tanks and pipelines, which can avoid the need to add an acid balance electrolysis system to separate the sulfuric acid component in the plating solution, thereby saving investment funds for some equipment in the project, reducing capital utilization, improving economic benefits, and avoiding the generation of additional hydrogen hazard sources.

[0068] 3. The present invention uses oxalic acid as a copper removal agent to react with copper sulfate solution to produce sulfuric acid for recycling, avoiding the high energy consumption process of adding an acid balance electrolysis system to separate the sulfuric acid component in the plating solution, thereby achieving the purpose of energy saving and emission reduction.

[0069] 4. The present invention adopts a copper dissolving method using metallic copper as an electrolytic anode, which is lower in cost than the traditional copper plating process using phosphorus copper and has no phosphorus pollution, thus reducing the cost of environmental protection treatment.

[0070] 5. The present invention can effectively avoid equipment damage caused by copper ion leakage by controlling the copper ion concentration of the electrolytic cathode liquid to not more than 10 g / L and / or combining the oxidation treatment of the mixed solution of the electrolytic cathode liquid and the electroplating anode liquid, and can stabilize the sulfuric acid concentration of the electrolyte and the electroplating solution in the system so that the electrolytic copper dissolution operation and the electroplating copper operation can proceed smoothly. BRIEF DESCRIPTION OF THE DRAWINGS

[0071] FIG1 is a schematic diagram of a device used in Example 1 of the present invention;

[0072] FIG2 is a schematic diagram of a device used in Example 2 of the present invention;

[0073] FIG3 is a schematic diagram of a device used in Example 3 of the present invention;

[0074] FIG4 is a schematic diagram of a device used in Example 4 of the present invention;

[0075] FIG5 is a schematic diagram of a device used in Example 5 of the present invention;

[0076] FIG6 is a schematic diagram of a device used in Example 6 of the present invention;

[0077] FIG7 is a schematic diagram of an apparatus used in a comparative example of the present invention.

[0078] Figure 1: 1-copper dissolving electrolytic cell, 2-anode titanium basket, 3-electrolytic cathode, 4-metal copper anode, 5-electrolytic cell separator, 6-insoluble anode electroplating cell, 7-insoluble anode, 8-cathode plating part, 9-electroplating cell separator, 10-electrolytic cell or electroplating cell sealing cover, 11-electrolytic cell power supply, 12-electroplating line power supply, 13-solution mixing exchange tank, 14-liquid flow buffer tank, 15-temporary storage tank, 16-solid-liquid separator, 17-impeller agitator, 18-liquid flow agitator, 19-vacuum ejector, 20-spray tower, 21-exhaust gas processor, 22-hydrogen removal Device, 23-Chemical reaction tank, 24-Solid feeder, 25-Hot and cold temperature exchanger, 26-Automatic detection and feeding controller, 27-Sensor, 28-Electro- or gas-controlled valve, 29-Valve, 30-Pump, 31-Sulfuric acid, 32-Copper sulfate, 33-Metal sponge copper, 34-Copper oxide, 35-Oxalic acid, 36-Oxygen, 37-Hydrogen, 38-Air, 39-Ozone, 40-Clean water, 41-Copper oxalate, 42-Electroplating tank cathode plating solution, 43-Overflow, 44-Hydrogen high-altitude discharge pipe, 45-Electroplating tank anode electrolysis gas washing tank, 46-Chlorine. DETAILED DESCRIPTION

[0079] The present invention is further illustrated below through specific examples. In the following examples, the electrolytic cell, electroplating cell, chemical reaction cell, temporary storage tank, hydrogen remover, and automatic detection and feeding controller used are manufactured by Yegao Environmental Protection Equipment Manufacturing Co., Ltd. in Foshan, Guangdong Province, China. The solid-liquid separator, sensor, electrolytic cell divider, chemical raw materials, pump, and valve used are all commercially available products. In addition to those listed above, those skilled in the art may also select other products with similar performance to those listed above, and any of these products can achieve the objectives of the present invention.

[0080] Example 1

[0081] As shown in FIG1 , a basic embodiment of an apparatus for optimizing an insoluble anode copper plating process in combination with electrolytic copper dissolution is shown. The apparatus includes a copper dissolving electrolytic cell 1, an anode titanium basket 2, an electrolytic cathode 3, a metal copper anode 4, an electrolytic cell separator 5, an insoluble anode electroplating cell 6, an insoluble anode 7, a cathode plating member 8, an electrolytic power supply 11, an electroplating power supply 12, a solid-liquid separator 16, a liquid flow buffer tank 14, a chemical reaction tank 23, sulfuric acid 31, oxalic acid 35, valves, and a pump.

[0082] The copper-dissolving electrolytic cell 1 is divided into an anode zone and a cathode zone by a cell divider 5. Each zone houses an anode titanium basket 2 (containing a metallic copper anode 4) and an electrolytic cathode 3, both connected to an electrolytic power source 11. The cell divider 5 is a bipolar membrane. The insoluble anode electroplating cell 6, lacking a cell divider, houses an insoluble anode 7 and a cathode plating element 8, connected to an electroplating power source 12.

[0083] This basic embodiment uses a metallic copper anode 4 to electrolyze copper in a sulfuric acid-containing electrolyte to produce copper sulfate, which serves as the copper source replenisher for the cathode plating solution in the insoluble anode electroplating tank. The initial electrolytic anolyte and catholyte are sulfuric acid solutions, and the initial electroplating solution is an acidic copper sulfate electroplating solution.

[0084] During operation, the electrolytic anode tank area of ​​the copper-dissolving electrolytic cell 1 is connected to the insoluble anode electroplating cell 6. Pump 30-1 injects a high-concentration copper sulfate solution into the electroplating cell. The overflow of the plating solution is returned to the electrolytic anode tank area through the liquid flow buffer tank 14 and pump 30-4.

[0085] During the operation, the electrolytic cathode tank area of ​​the copper dissolving electrolytic cell 1 is cyclically connected to the chemical reaction tank 23 and the solid-liquid separator 16. The pump 30-2 is intermittently used to pump all the copper-containing electrolytic cathode liquid to the chemical reaction tank 23, and oxalic acid is used to remove copper from the electrolyte by a chemical method. The solid-liquid mixture after the copper removal treatment is subjected to solid-liquid separation and the filtrate rich in sulfuric acid is all returned to the electrolytic cathode tank area. Then, the electrolytic power supply is turned on again to resume copper dissolving production.

[0086] In this embodiment, the molar amount of the copper removal agent oxalic acid added is the molar amount of copper ions in the solution in the reaction tank before the reaction.

[0087] During the operation of this embodiment, although solid sponge copper particles still adhered to the separator of the copper dissolving electrolytic cell, the electrolysis and electroplating operations were able to continue. The process data are listed in Table 1.

[0088] Example 2

[0089] As shown in FIG2 , the apparatus of the present invention for optimizing the insoluble anode copper plating process in combination with electrolytic copper dissolution includes a copper dissolving electrolytic cell 1, an anode titanium basket 2, an electrolytic cathode 3, a metal copper anode 4, an electrolytic cell separator 5, an insoluble anode electroplating cell 6, an insoluble anode 7, a cathode plating member 8, an electroplating cell separator 9, an electrolytic power supply 11, an electroplating power supply 12, a solid-liquid separator 16, a chemical reaction cell 23, a liquid flow buffer cell 14, sulfuric acid 31, oxalic acid 35, valves, and a pump.

[0090] The copper-dissolving electrolytic cell 1 is divided into an electrolytic anode cell area and an electrolytic cathode cell area by an electrolytic cell separator 5, each of which is provided with an anode titanium basket 2 (containing a metal copper anode 4) and an electrolytic cathode 3, and is connected to an electrolytic power supply 11. The insoluble anode electroplating cell 6 is divided into an electroplating anode cell area and an electroplating cathode cell area by an electroplating cell separator 9, each of which is provided with an insoluble anode 7 and a cathode plating member 8, and is connected to an electroplating power supply 12. The electrolytic cell separator 5 is a bipolar membrane, and the electroplating cell separator 9 is also a bipolar membrane.

[0091] In Example 2, a copper block 4 is electrolytically dissolved in a sulfuric acid-containing electrolyte to produce copper sulfate, which serves as a copper source replenisher for the cathode plating solution of an insoluble anode electroplating tank. The initial electrolytic anolyte is a mixed solution of sulfuric acid and copper sulfate, the initial electrolytic catholyte and electroplating anolyte are sulfuric acid solutions, and the initial electroplating catholyte is an acidic copper sulfate electroplating solution.

[0092] During operation, the electrolytic anode tank area of ​​the copper-dissolving electrolytic cell 1 is connected to the electroplating cathode tank area of ​​the insoluble anode electroplating cell 6. Pump 30-1 injects a high-concentration copper sulfate solution into the electroplating cathode tank area, and the overflow of the plating solution is returned to the electrolytic cell through the liquid flow buffer tank 14 and pump 30-5.

[0093] The electrolytic cathode tank area of ​​the copper-dissolving electrolytic tank 1 and the electroplating anode tank area of ​​the insoluble anode electroplating tank 6 are connected to the chemical reaction tank 23. Pumps 30-2 and 30-4 are used to pump the copper-containing electrolytic cathode liquid and the copper-containing electroplating anode liquid to the chemical reaction tank 23, respectively. Oxalic acid is used to remove copper from the electrolytic cathode liquid by a chemical method. The solid-liquid mixture after the copper removal treatment is subjected to solid-liquid separation, and the filtrate rich in sulfuric acid is returned to the electrolytic cathode tank area solution and the electroplating anode tank area solution, respectively.

[0094] In this embodiment, the molar amount of the copper removal agent oxalic acid added is the molar amount of copper ions in the solution in the reaction tank before the reaction.

[0095] Although a small amount of copper particles still remained in the cathode liquid of the copper-dissolving electrolytic cell and a small amount of solid copper particles adhered to the diaphragm in this embodiment, the electrolysis and electroplating operations were able to continue. The process data are listed in Table 1.

[0096] Example 3

[0097] As shown in FIG3 , the apparatus of the present invention for optimizing the insoluble anode copper plating process in combination with electrolytic copper dissolution includes a copper dissolving electrolytic cell 1, an anode titanium basket 2, an electrolytic cathode 3, a metal copper anode 4, an electrolytic cell separator 5, an insoluble anode electroplating cell 6, an insoluble anode 7, a cathode plating member 8, an electroplating cell separator 9, a solution mixing exchange cell 13, a solid-liquid separator 16, a chemical reaction cell 23, a liquid flow buffer cell 14, sulfuric acid 31, oxalic acid 35, copper oxalate 41, valves, and a pump.

[0098] The copper-dissolving electrolytic cell 1 is divided into an electrolytic anode zone and an electrolytic cathode zone by a cell divider 5. Each zone houses an anode titanium basket 2 (containing a metallic copper anode 4) and an electrolytic cathode 3, both connected to an electrolytic power supply 11. The cell divider 5 is an anion exchange membrane. The insoluble anode electroplating cell 6 is divided into an electroplating anode zone and an electroplating cathode zone by a cell divider 9. Each zone houses an insoluble anode 7 and a cathode plating element 8, both connected to an electroplating power supply 12. The cell divider 9 is an anion exchange membrane.

[0099] The solution mixing and exchange tank 13, which connects the electrolysis cathode tank area and the electroplating anode tank area, serves as a mixed circulation exchange tank for the electrolysis cathode solution and the electroplating anode solution. This system dissolves oxygen in the copper dissolving tank's cathode solution, creating an oxygen-containing cathode solution. This reduces the pressure within the copper dissolving tank and oxidizes the metallic copper powder electrolyzed at the cathode, causing some of the sponge copper powder to dissolve in sulfuric acid through an oxidation reaction. The solution mixing and exchange tank 13 is also connected to the chemical reaction tank 23 for circulation via a pump and a solid-liquid separator 16.

[0100] In Example 3, a soluble anode, a metallic copper block 4, is electrolytically dissolved in a sulfuric acid-containing electrolyte to produce copper sulfate, which serves as a copper source replenisher for the cathode plating solution of an insoluble anode electroplating tank. The initial electrolytic anolyte is a mixed solution of sulfuric acid and copper sulfate. The initial electrolytic catholyte and electroplating anolyte are mixed solutions of sulfuric acid and copper sulfate containing 1 g / L of copper ions. The initial electroplating catholyte is an acidic copper sulfate electroplating solution.

[0101] During operation, the electrolytic anode tank area of ​​the copper-dissolving electrolytic cell 1 is connected to the electroplating cathode tank area of ​​the insoluble anode electroplating cell 6. Pump 30-1 adds high-concentration copper sulfate solution to the electroplating cathode tank area as a copper source supplement according to process requirements. The overflow of the plating solution is returned to the electrolytic anode tank area through the liquid flow buffer tank 14 and pump 30-6.

[0102] The solution mixing and exchange tank 13 is used to mix and circulate the cathode solution from the copper electrolytic cell and the anodic plating solution from the electroplating cell, ensuring that the cathode solution in the copper electrolytic cell contains oxygen. As the copper electrolysis and electroplating process proceeds, the copper ion concentration in the solution mixing and exchange tank 13 continuously increases. According to process requirements, a portion of the solution is pumped via pump 30-4 to the chemical reaction tank 23 for copper removal. Specifically, oxalic acid 35 is added to the chemical reaction tank 23, and an impeller agitator 17 is activated to initiate the copper removal reaction. After the reaction is complete, the solution is transferred to the solid-liquid separator 16 for solid-liquid separation. The resulting sulfuric acid-rich filtrate is returned to the solution mixing and exchange tank 13 and then transported to the electrolytic cathode tank area and electroplating anode tank area for reuse.

[0103] In this embodiment, the molar amount of the copper removal agent oxalic acid added is 85% of the molar amount of copper ions in the solution in the reaction tank before the reaction.

[0104] In this example, trace copper particles were not removed from the cathode liquid in the copper electrolytic cell, resulting in sponge copper particles adhering to the diaphragm. However, by removing copper and recycling sulfuric acid, copper electrolysis and electroplating production continued. The process data are listed in Table 1.

[0105] Example 4

[0106] As shown in FIG4 , the apparatus of the present invention for optimizing the insoluble anode copper plating process in combination with electrolytic copper dissolution includes a copper dissolving electrolytic cell 1, an anode titanium basket 2, a metal copper anode 4, an electrolytic cathode 3, an electrolytic cell separator 5, an insoluble anode electroplating cell 6, an insoluble anode 7, a cathode plating member 8, an electroplating cell separator 9, an electrolytic power supply 11, an electroplating power supply 12, two solution mixing and exchange cells 13, multiple liquid flow buffer cells 14, two temporary storage cells 15, a solid-liquid separator 16, a chemical reaction cell 23, multiple sensors 27, sulfuric acid 31, copper sulfate 32, copper oxide 34, oxalic acid 35, copper oxalate 41, multiple valves, and a pump.

[0107] The copper dissolving electrolytic cell 1 is divided into an electrolytic anode cell area and an electrolytic cathode cell area by an electrolytic cell separator 5, and is respectively provided with an anode titanium basket 2 (containing a metal copper anode 4) and an electrolytic cathode 3, and is connected to an electrolytic power supply 11; the insoluble anode electroplating cell 6 is divided into an electroplating anode cell area and an electroplating cathode cell area by an electroplating cell separator 9, and is respectively provided with an insoluble anode 7 and a cathode plating piece 8, and is connected to an electroplating power supply 12; wherein, the electrolytic cell separator 5 and the electroplating cell separator 9 both use reverse osmosis membranes.

[0108] The solid-liquid separator 16 - 1 is a filter press, and the solid-liquid separators 16 - 2 , 16 - 3 , and 16 - 4 are filters.

[0109] The solution mixing and exchange tank 13-2 is used for the reaction between copper oxide powder and sulfuric acid solution. It is circulated through the liquid flow buffer tank 14-1 to the electrolytic anode tank area. The solution mixing and exchange tank 13-2 is also circulated through the electroplating cathode tank area. The solution mixing and exchange tank 13-1 is used for mixing and exchanging the cathode solution of the copper dissolving electrolytic cell with the anode solution of the electroplating cell. It connects the electrolytic cathode tank area and the electroplating anode tank area respectively. It is also circulated through the chemical reaction tank 23 through the solid-liquid separator and the temporary storage tank.

[0110] The copper oxide powder 34 is prepared from copper oxalate through a chemical reaction.

[0111] The sensor 27-1 in the device of this embodiment is a photoelectric colorimeter, 27-2 is a pH meter, 27-3 is a hydrometer, 27-4 is a photoelectric colorimeter, 27-5 and 27-6 are radar level gauges, 27-7 is a hydrometer, and 27-8 is a flow meter.

[0112] The characteristic of this embodiment 4 is that the solution mixing exchange tank 13-2 used is used for the circulation of the electrolytic anode solution of the copper dissolving electrolytic tank and the reflux collection of the overflow of the cathode plating solution of the electroplating tank.

[0113] The photoelectric colorimetric sensor 27-1 in the solution mixing exchange tank 13-2 is used to detect the copper ion concentration in the solution to control the working current of the electrolytic power supply 11 or shut it down; and the sensor 27-2 in the solution mixing exchange tank 13-2 is a pH meter to control the addition of copper oxide powder 34.

[0114] Solution mixing and exchange tank 13-1 is used for mixing and exchanging the electrolytic cathode liquid of the copper-dissolving electrolytic cell with the electroplating anode liquid of the electroplating cell. When the mixed liquid reaches the copper ion concentration value set by sensor 27-3, valve 29-2 is opened and pump 30-9 is started to drain part of the solution in solution mixing and exchange tank 13-1 into chemical reaction tank 23 for copper removal. After copper removal, the sulfuric acid-rich filtrate obtained by treatment in solid-liquid separators 16-1 and 16-2, i.e., a mixture of sulfuric acid and copper sulfate, is put into tank 15-2 for temporary storage, and then returned to solution mixing and exchange tank 13-1 according to process requirements, and then transported to the electrolytic cathode tank area and electroplating anode tank area for reuse.

[0115] In this embodiment, the molar amount of oxalic acid, a copper removal agent, added is 60% of the molar amount of copper ions in the solution in the reaction tank before the reaction. The initial electrolysis anolyte added is a mixed solution of sulfuric acid and copper sulfate. The initial electrolysis catholyte and electroplating anolyte added are mixed solutions of sulfuric acid and copper sulfate containing 5 g / L of copper ions. The initial electroplating catholyte added is an acidic copper sulfate electroplating solution.

[0116] In this embodiment, a small amount of sponge copper particles still adhere to the diaphragm of the copper dissolving electrolytic cell. However, the above operation ensures that the electrolytic copper dissolving and the insoluble anode plating cell can operate continuously and normally.

[0117] In addition, during the operation, the copper oxalate 41 separated by the filter press 16-1 is processed to produce copper oxide powder.

[0118] The process parameters are listed in Table 1.

[0119] Example 5

[0120] As shown in FIG5 , the device for optimizing the insoluble anode copper plating process in combination with electrolytic copper dissolution of the present invention comprises a copper dissolving electrolytic cell 1, an anode titanium basket 2, an electrolytic cathode 3, a metal copper anode 4, an insoluble anode electroplating cell 6, an insoluble anode 7, a cathode plating piece 8, an electrolytic cell separator 5, an electroplating cell separator 9, an electrolytic cell sealing cover 10-1, an electroplating cell sealing cover 10-2, an electrolytic power supply 11, an electroplating power supply 12, two solution mixing exchange cells 13, and a plurality of liquid flow Buffer tank 14, multiple temporary storage tanks 15, multiple solid-liquid separators 16, impeller agitator 17, two vacuum ejectors 19, spray tower 20, tail gas processor 21, hydrogen remover 22, two solid feeders 24, hot and cold temperature exchanger 25, automatic detection and feeding controller 26, multiple sensors 27, multiple valves and pumps, sulfuric acid 31, copper sulfate 32, copper oxide 34, oxalic acid 35, oxygen 36, hydrogen 37, chlorine 46, clean water 40, copper oxalate 41.

[0121] The copper dissolving electrolytic cell 1 is divided into an electrolytic anode cell area and an electrolytic cathode cell area by an electrolytic cell separator 5, and is respectively provided with an anode titanium basket 2 (containing a metal copper anode 4) and an electrolytic cathode 3, and is connected to an electrolytic power supply 11; the insoluble anode electroplating cell 6 is divided into an electroplating anode cell area and an electroplating cathode cell area by an electroplating cell separator 9, and is respectively provided with an insoluble anode 7 and a cathode plating piece 8, and is connected to an electroplating power supply 12; wherein, the electrolytic cell separator 5 is an anion exchange membrane, and the electroplating cell separator 9 adopts an anion exchange membrane.

[0122] The solid-liquid separator 16 - 2 is a centrifuge, and the solid-liquid separators 16 - 1 , 16 - 3 , 16 - 4 , and 16 - 5 are filters.

[0123] The sensor 27-1 in the device of this embodiment is a photoelectric colorimeter, the sensor 27-2 is a hydrometer, the sensor 27-3 is a thermometer, the sensor 27-4 is a liquid level gauge, the sensor 27-5 is a liquid level gauge, the sensor 27-6 is a pH meter, the sensor 27-9 is a thermometer, the sensor 27-10 is a photoelectric colorimeter, the sensor 27-11 is a liquid level gauge, the sensor 27-12 is an ORP meter, the sensors 27-7, 27-8, 27-13, and 27-14 are all flow sensors, the sensor 27-14 is a photoelectric colorimeter, the sensors 27-15 and 27-16 are liquid level gauges, the sensor 27-17 is a hydrometer, the sensor 27-18 is a photoelectric colorimeter, and the sensor 27-19 is a photoelectric colorimeter.

[0124] This embodiment utilizes electrolytic copper dissolution and the addition of external copper oxide powder as a copper source for the plating solution. A hydrogen remover 22 and an acidic tail gas processor 21 are also added to safely and environmentally treat the hydrogen and acidic tail gas, respectively. To address chloride ion contamination from the external copper oxide powder, a plating tank anode electrolysis gas scrubber 45 is added, connected to the plating tank sealing cover 10-2. Chloride ions that migrate from the plating solution into the electroplating anode tank area are electrolyzed as chlorine gas and then scrubbed and discharged to remove excess chloride ions from the plating solution. Furthermore, a dedicated temporary storage tank 15-1 is used to dissolve copper oxide. In addition, in order to overcome the process difficulty of the sponge copper 33 electrolyzed in the electrolytic cathode tank area damaging the electrolytic tank partition, a vacuum ejector 19-1 is installed on the solution mixing exchange tank 13-1, and all the oxygen obtained after washing and dechlorination of the gas escaping from the electroplating anode tank area is drained into the mixed exchange solution, and supplemented with ozone and hydrogen peroxide, the sponge metal copper powder from the electrolytic cathode liquid is oxidized to generate copper oxide, which reacts with sulfuric acid to generate copper sulfate. The filtered solution is then sent to the electrolytic cathode tank area and the electroplating anode tank area, thereby reducing the damage of the sponge metal copper to the equipment.

[0125] The device of this embodiment is equipped with an automatic detection and feeding controller 26 and a plurality of sensors, so that the entire device can realize automatic control of the entire copper dissolving and electroplating production process under a pre-programmed control system.

[0126] The operating steps of this embodiment 5 are as follows.

[0127] Step 1: Add an electroplating solution mainly composed of sulfuric acid and copper sulfate to the electrolytic anode tank area of ​​the copper dissolving electrolytic cell 1, add a metal copper block 4 to the anode titanium basket 2, and add a sulfuric acid solution to the electrolytic cathode tank area of ​​the copper dissolving electrolytic cell; the anode titanium basket 2 is immersed in the electrolyte in the electrolytic anode tank area and connected to the positive electrode of the electrolytic power supply, and a stainless steel cathode serving as the electrolytic cathode 3 is immersed in the electrolyte in the electrolytic cathode tank area and connected to the negative electrode of the electrolytic power supply; and the electrolytic anode solution of the copper dissolving electrolytic cell 1 is added to the solution mixing exchange tank 13-2 and the temporary storage tank 15-1.

[0128] Step 2: Add sulfuric acid to the electroplating anode tank area of ​​the insoluble anode electroplating tank 6, add an electroplating solution mainly composed of sulfuric acid and copper sulfate to its electroplating cathode tank area, immerse the titanium-based coated insoluble anode in the electroplating anode solution and connect it to the positive pole of the electroplating power supply, immerse the cathode plated part 8 in the electroplating solution in the electroplating cathode tank area and connect it to the negative pole of the electroplating power supply; and add the electroplating anode solution of the electroplating tank to the solution mixing exchange tank 13-1.

[0129] Step 3: Turn on pumps 30-1, 30-2, 30-5, 30-6, 30-7, 30-8, 30-10, and 30-11 to continuously circulate and mix the cathode and anode solutions of the copper-dissolving electrolytic cell and the cathode and anode solutions of the insoluble anode electroplating cell, and filter the solutions flowing into the electrolytic cathode tank area and the electroplating anode tank area to reduce the entry of solid matter into the electrolytic cell and the electroplating cell;

[0130] The electrolytic power supply is turned on to perform the electrolytic copper dissolution operation. The working status of the electrolytic power supply is detected by the sensor 27-1 in the solution mixing exchange tank 13-2, and the data is transmitted to the automatic detection and feeding controller 26 for processing and controlling the working status of the electrolytic power supply 11. During the operation, the copper blocks in the anode titanium basket are continuously dissolved, and hydrogen is electrolyzed at the electrolytic cathode.

[0131] The electroplating power supply is connected to perform the electroplating operation. The insoluble anode of the electroplating tank electrolyzes oxygen, and the cathode electrolyzes copper on the surface of the plated workpiece 8. The electroplating power supply is turned off and the plated workpiece is taken out according to the time requirement of the electroplating process.

[0132] Step 4: As the electrolytic copper dissolution and electroplating proceed, sensor 27-9 in the solution mixing exchange tank 13-1 detects that the solution temperature is too high and controls the hot and cold temperature exchanger 25-2 to cool it down. Sensor 27-12 is an ORP meter that detects the oxidizing properties of the solution, indirectly monitoring the treatment of fine copper particles. Sensor 27-10 detects the concentration of copper sulfate in the solution. When sensor 27-10 reaches the set concentration, pump 30-13 is activated to pump a portion of the solution in the mixing exchange tank 13-1 into the chemical reaction tank 23 for copper removal reaction with oxalic acid.

[0133] Step 5: The reaction product in the chemical reaction tank 23 is separated into solid and liquid by a centrifuge 16-2 to obtain a mixed filtrate of sulfuric acid and copper sulfate, which is then filtered by a filter 16-3 and pumped to a temporary storage tank 15-3 for temporary storage. During this process, a small amount of water and sulfuric acid is lost in the temporary storage tank 15-3 and is replenished by external addition, while the filter residue copper oxalate is stored in the temporary storage tank 15-2.

[0134] Step 6: The solution in the temporary storage tank 15-3 is added to the solution mixing exchange tank 13-1 according to process control for recycling; the filter residue copper oxalate is heated to generate copper oxide and mixed with the external copper oxide powder for recycling.

[0135] Step 7: During the electroplating process, the sensor 27-19 in the electroplating cathode tank area controls the pump 30-1 to add the replenishing liquid;

[0136] When sensor 27-1 in solution mixing and exchange tank 13-2 reaches the set value, that is, the copper sulfate concentration of the solution meets the process requirements, but the hydrometer of sensor 27-2 exceeds the set value, it indicates that the sulfuric acid content of the solution in solution mixing and exchange tank 13-2 is too high. At this time, the automatic detection and feeding controller 26 controls the start of pump 30-3 and solid feeder 24-1 to add part of the solution in solution mixing and exchange tank 13-2 and copper oxide 204 to the temporary storage tank 15-1, and starts the agitator to dissolve the copper oxide. When the measured value of the solution in temporary storage tank 15-1 drops below the set value of sensor 27-6, the feeding operation of solid feeder 24-1 is stopped, indicating that the excessive sulfuric acid concentration in the solution has been consumed.

[0137] Step 8: The electrolyzed hydrogen is introduced into the inlet of the hydrogen remover to react with air, oxygen and ozone to achieve the purpose of hydrogen removal; the exhaust gas escaping from each tank is introduced into the exhaust gas processor 21 for environmental protection treatment.

[0138] In this embodiment, the molar amount of oxalic acid, a copper removal agent, added is 57% of the molar amount of copper ions in the solution in the reaction tank before the reaction.

[0139] Through the above multiple steps and the use of an automated control system, and by making full use of the oxygen electrolyzed in the electroplating tank, supplemented by ozone and hydrogen peroxide, the copper particles produced on the cathode of the copper dissolving tank are completely oxidized and dissolved in the electrolyte, thereby realizing a process method for optimizing the insoluble anode copper plating process combined with electrolytic copper dissolving, ensuring that the electroplating operation and the electrolysis operation are continuously carried out according to the process, and no sponge metal copper adheres to the diaphragms of the copper dissolving electrolytic tank and the electroplating tank during the process.

[0140] The process data are listed in Table 1.

[0141] Example 6

[0142] As shown in Figure 6, the device of the present invention is used for the optimization method of the insoluble anode copper plating process combined with electrolytic copper dissolution, which includes a copper dissolving electrolytic cell 1, an anode titanium basket 2, an electrolytic cathode 3, a metal copper anode 4, two insoluble anode electroplating cells 6, a cathode plating part 8, an electrolytic cell sealing cover 10-1, electroplating cell sealing covers 10-2 and 10-3, an electrolytic power supply 11, two electroplating power supplies 12, two solution mixing and exchange tanks 13, multiple liquid flow buffer tanks 14, multiple temporary storage tanks 15, multiple solid-liquid separators 16, two impeller agitators 17, a vacuum ejector 19, a spray tower 20, a solid feeder 24, an automatic detection feeder 26, multiple sensors 27, sulfuric acid 31, copper sulfate 32, copper oxide 34, oxalic acid 35, oxygen 36, hydrogen 37, copper oxalate 41, a hydrogen high-altitude discharge pipe 44, multiple valves and pumps.

[0143] The copper dissolving electrolytic cell 1 is divided into an electrolytic anode cell area and an electrolytic cathode cell area by an electrolytic cell separator 5, and is respectively provided with an anode titanium basket 2 (which contains a metal copper anode 4) and an electrolytic cathode 3, which are connected to an electrolytic power supply 11; the insoluble anode electroplating cells are divided into an electroplating anode cell area and an electroplating cathode cell area by an electroplating cell separator, and are respectively provided with insoluble anode and cathode plating parts, and are connected to an electroplating power supply; wherein, the electrolytic cell separator 5 and the electroplating cell separators 9-1 and 9-2 are all anion exchange membranes.

[0144] The solid-liquid separators are all filters.

[0145] Sensors 27-1 and 27-2 in the device of this embodiment are photoelectric colorimeters, sensor 27-3 is a hydrometer, sensors 27-4, 27-5, and 27-6 are liquid level gauges, sensor 27-7 is a photoelectric colorimeter, sensor 27-8 is a liquid level gauge, sensor 27-9 is an ORP meter, sensors 27-10 and 27-11 are liquid level gauges, sensor 27-12 is a photoelectric colorimeter, sensor 27-13 is a liquid level gauge, sensor 27-14 is a photoelectric colorimeter, sensor 27-15 is a liquid level gauge, sensor 27-16 is a photoelectric colorimeter, sensors 27-17 and 27-18 are liquid level gauges, sensor 27-19 is a hydrometer, and sensors 27-20 and 27-21 are liquid level gauges.

[0146] This embodiment utilizes a copper-dissolving electrolytic cell and two insoluble anode electroplating cells. A hydrogen overhead discharge pipe 44 serves as a safe hydrogen handling device, and a temporary storage tank 15-2 is added for replenishing the sulfuric acid solution. Furthermore, to improve electroplating quality, temporary storage tank 15-1 is used specifically for dissolving copper oxide. To address the process challenge of sponge copper particles electrolyzed in the cathode zone of the copper-dissolving electrolytic cell damaging the cell dividers, a vacuum ejector 19 and a spray tower 20 are installed in the solution mixing exchange tank 13-1. This directs all oxygen escaping from the two electroplating anode zones into the solution in the solution mixing exchange tank 13-1 to oxidize the sponge copper. The copper particles are oxidized to copper oxide, which then reacts with sulfuric acid to form copper sulfate. The filtered solution is then fed to the electrolytic cathode zone and electroplating anode zone, minimizing damage to the equipment caused by fine copper particles. Furthermore, the copper oxalate produced in the chemical reaction tank 23 is heat-treated to produce copper oxide powder.

[0147] The equipment of this embodiment is equipped with an automatic detection and feeding controller 26 and multiple sensors, and two solid feeders 24-1 and 24-2. After inputting a pre-programmed program into the automatic detection and feeding controller 26, the entire set of copper dissolving and electroplating equipment can be automatically controlled.

[0148] The operating steps of this embodiment 6 are as follows.

[0149] Step 1: A mixed solution mainly composed of sulfuric acid and copper sulfate is added to the electrolytic anode tank area of ​​the copper dissolving electrolytic cell 1, a metal copper block 4 is added to the anode titanium basket 2, and a sulfuric acid solution is added to the electrolytic cathode tank area of ​​the copper dissolving electrolytic cell 1. The anode titanium basket 2 is placed in the electrolyte in the electrolytic anode tank area and connected to the positive electrode of the electrolytic power supply. A stainless steel cathode serving as the electrolytic cathode 3 is placed in the electrolyte in the electrolytic cathode tank area and connected to the negative electrode of the electrolytic power supply. The electrolytic anode solution of the copper dissolving electrolytic cell 1 is also added to the solution mixing exchange tank 13-2 and the temporary storage tank 15-1.

[0150] Step 2: Add sulfuric acid to the electroplating anode tank area of ​​the insoluble anode electroplating tank, add a plating solution mainly composed of a mixture of sulfuric acid and copper sulfate to its electroplating cathode tank area, immerse the titanium-based coating insoluble anode in the electroplating anode plating solution and connect it to the positive pole of the electroplating power supply, immerse the cathode plated part in the plating solution in the electroplating cathode tank area and connect it to the negative pole of the electroplating power supply; and add the electroplating anode solution of the electroplating tank to the solution mixing exchange tank 13-1.

[0151] Step 3: Turn on pumps 30-3, 30-7, 30-8, 30-9, and 30-10 to circulate the electrolytic anolyte of the copper-dissolving electrolytic cell 1, and circulate the electroplating anolyte of the insoluble anode electroplating cells 6-1 and 6-2 and the electrolytic cathode of the copper-dissolving electrolytic cell 1 back into the anolyte.

[0152] The electrolytic power supply 11 is connected to perform the electrolytic copper dissolution operation. The working status of the electrolytic power supply is detected by the sensor 27-1 in the solution mixing exchange tank 13-2. The data is transmitted to the automatic detection and feeding controller 26 for processing and control of the electrolytic power supply. During the operation, the copper block 4 in the anode titanium basket is continuously dissolved, the copper ion concentration of the electrolytic anolyte is continuously increased, and hydrogen is electrolyzed at the electrolytic cathode.

[0153] Two electroplating power supplies 12-1 and 12-2 are connected to perform electroplating operations. The insoluble anodes of the two electroplating tanks electrolyze oxygen, and copper is electroplated on the surfaces of the two plated parts 8-1 and 8-2. During the operation, the sensor 27-14 of the electroplating tank 6-1 controls the pump 30-2, and the sensor 27-16 of the electroplating tank 6-2 controls the pump 30-1 to add copper source replenishing liquid to each electroplating cathode liquid. After completion, the respective electroplating power supplies are turned off according to the time requirements of the electroplating process, and the two plated parts are taken out respectively.

[0154] Step 4: As the electrolytic copper dissolution and electroplating proceed, when the solution mixing exchange tank 13-2 is full of liquid, the sensor 27-4 controls the pump 30-17 to pump part of the solution in the tank to the temporary storage tank 15-3 for temporary storage, and then pumps it to the chemical reaction tank 23 through the pump 30-18 for copper removal according to the process; the sensor 27-11 in the solution mixing exchange tank 13-1 is a liquid level meter to control the normal operation of the spray tower 20 and vacuum ejector 19 matched with it; the sensor 27-12 is a photoelectric colorimeter for detecting the copper sulfate concentration of the solution in the solution mixing exchange tank 13-1. When the photoelectric colorimeter 27-12 reaches the set value, the pump 30-23 is turned on to pump part of the solution in the solution mixing exchange tank 13-1 to the chemical reaction tank 23 and react with the accurately measured amount of oxalic acid to perform a copper removal reaction.

[0155] Step 5: The reaction product of the chemical reaction tank 23 is selectively separated into solid and liquid by filters 16-2, 16-3, 16-4, and 16-5. The filtrate is pumped through the liquid flow buffer tank 14-8 to the temporary storage tank 15-4 for temporary storage and preparation for recycling, while the filter residue copper oxalate is retained in each filter.

[0156] Step 6: The solution in the temporary storage tank 15-4 is added to the solution mixing exchange tanks 13-1 and 13-2 according to process control for recycling; the filter residue copper oxalate is heated to generate copper oxide for reuse.

[0157] Step 7: During the electroplating process, when the sensor 27-1 in the solution mixing exchange tank 13-2 reaches the set value, that is, the copper sulfate concentration of the solution meets the process requirements, the electrolytic power supply 11 is shut down, and the sensor 27-2 serves as a safety interlock for the electrolytic power supply to be turned on; when the hydrometer of the sensor 27-3 exceeds the set value, it means that the sulfuric acid content of the solution in the solution mixing exchange tank 13-2 is too high, and the on-site detection data of the sensor 27-4 is sent to the automatic detection and feeding controller 26 for processing, and the pump 30-4 is controlled to pump part of the solution in the solution mixing exchange tank 13-2 to the temporary storage tank 15-1 for processing. The photoelectric colorimeter detection data of the sensor 27-7 in the temporary storage tank 15-1 is used to control the solid feeder 24-1 to add copper oxide 34 to the temporary storage tank 15-1 through the controller 26, and the agitator is started to dissolve the copper oxide; when the detection value of the solution in the temporary storage tank 15-1 rises to the set value of the sensor 27-7, the solid feeder 24-1 is stopped and the pump 30-5 is started to pump the treated solution in the temporary storage tank 15-1 back to the tank 15-1 to adjust the sulfuric acid concentration of the solution in the tank 15-1. In this way, copper oxide is added to adjust the composition of the electroplating cathode liquid in the electroplating tank.

[0158] Step 8: Lead the electrolyzed hydrogen into the hydrogen high-altitude discharge pipe for high-altitude safe discharge treatment.

[0159] Step 9: The sulfuric acid lost in the process is added to the electrolytic cathode tank area of ​​the copper dissolving electrolytic cell for replenishment.

[0160] In this embodiment, the molar amount of the copper removal agent oxalic acid added is 70% of the molar amount of copper ions in the solution in the reaction tank before the reaction.

[0161] Through these multiple steps and the use of an automated control system, the process optimizes the insoluble anode copper plating process combined with electrolytic copper dissolution by fully utilizing the oxygen generated by the electroplating tank's anode to oxidize the copper particles produced by the copper dissolution tank's cathode and dissolve them in the electrolyte. This ensures that the electroplating and electrolysis operations proceed continuously according to the process. No copper particles were found adhering to the diaphragms of the copper dissolution tank or the electroplating tank during the process.

[0162] The process data are listed in Table 1.

[0163] Comparative Example

[0164] As shown in FIG7 , an apparatus for optimizing an insoluble anode copper plating process combined with electrolytic copper dissolution is provided, which includes a copper dissolving electrolytic cell 1, an anode titanium basket 2, an electrolytic cathode 3, a metal copper anode 4, an insoluble anode electroplating cell 6, an insoluble anode 7, a cathode plating member 8, an electrolytic power supply 11, an electroplating power supply 12, copper sulfate plating solutions 31+32, valves, and a pump.

[0165] The copper-dissolving electrolytic cell 1 is divided into an anode zone and a cathode zone by a cell divider 5. Each zone houses an anode titanium basket 2 (containing a metallic copper anode 4) and an electrolytic cathode 3, both connected to an electrolytic power source 11. The cell divider 5 is a reverse osmosis membrane. The insoluble anode electroplating cell 6, lacking a cell divider, houses an insoluble anode 7 and a cathode plating element 8, connected to an electroplating power source 12.

[0166] The electrolysis power supply 11 and the electroplating power supply 12 are turned on to start the operation. The metallic copper anode 4 in the copper dissolving electrolytic cell continues to dissolve, and the electrolytic cathode electrolyzes hydrogen and sponge copper. The insoluble anode in the electroplating cell electrolyzes oxygen, and the cathode electrolyzes metallic copper on the plated parts.

[0167] During operation, the cathode in the copper dissolving tank continuously produces sponge copper, which floats in the cathode liquid. At the same time, a large amount of sponge copper adheres to the separator membrane of the copper dissolving tank, affecting production. Therefore, this copper dissolving and electroplating process structure system cannot maintain continuous production.

[0168] The process data are listed in Table 1.

[0169] Copper removal process data table 1

Claims

1. A method for optimizing an insoluble anode copper plating process combined with electrolytic copper dissolution, comprising an electrolytic copper dissolution process and an insoluble anode copper plating process, characterized in that: The following steps are involved: Step (1): using a copper dissolving electrolytic cell with an electrolytic cell separator and an insoluble anode electroplating cell to perform electrolysis and electroplating operations respectively; The copper dissolving electrolytic cell is divided into an electrolytic anode cell area and an electrolytic cathode cell area by the electrolytic cell separator, and the electrolytic anode liquid and the electrolytic cathode liquid are respectively contained therein; The insoluble anode electroplating tank is provided with an electroplating tank divider or is not provided with an electroplating tank divider. When the electroplating tank divider is provided, the tank is divided into an electroplating anode tank area and an electroplating cathode tank area, and the electroplating anode liquid and the electroplating cathode liquid are respectively contained therein. When the electroplating tank divider is not provided, the tank is filled with electroplating liquid. During production operations, the electrolytic anode metal copper in the copper-dissolving electrolytic cell undergoes an electrochemical reaction in which it dissolves and turns into copper ions, while the cathode plating piece in the insoluble anode electroplating cell electroprecipitates copper, and the main components of the electrolytic anode solution, electroplating solution or electroplating cathode solution are a mixed solution of sulfuric acid and copper sulfate; Step (2): adding the electrolytic anolyte as a copper sulfate copper source supplement solution into the electroplating tank to supplement the copper ion concentration of the plating solution; and, When the electroplating tank is not provided with an electroplating tank divider, part or all of the electrolytic cathode liquid is taken out to react with a copper remover; when the electroplating tank is provided with an electroplating tank divider, part or all of the electrolytic cathode liquid and / or electroplating anode liquid is taken out to react with a copper remover, and then the reaction liquid is subjected to solid-liquid separation to obtain an insoluble solid copper salt and a filtrate containing sulfuric acid, and the filtrate containing sulfuric acid is added to the electrolytic anode liquid and / or electrolytic cathode liquid and / or electroplating anode liquid to allow the electrolysis and electroplating operations to continue.

2. The method according to claim 1, characterized in that The electrolytic cell separator is selected from at least one of an anion exchange membrane, a bipolar membrane, and a reverse osmosis membrane; the electroplating cell separator is selected from at least one of an anion exchange membrane, a bipolar membrane, and a reverse osmosis membrane; and the copper remover is oxalic acid.

3. The method according to claim 2, characterized in that When the insoluble anode electroplating tank does not have an electroplating tank separator, the electrolytic tank separator is selected as a bipolar membrane and / or a reverse osmosis membrane; when the insoluble anode electroplating tank is provided with an anion exchange membrane as an electroplating tank separator, the electrolytic tank separator is selected as an anion exchange membrane; when the insoluble anode electroplating tank is provided with a bipolar membrane and / or a reverse osmosis membrane as an electroplating tank separator, the electrolytic tank separator is selected as a bipolar membrane and / or a reverse osmosis membrane.

4. The method according to claim 3, characterized in that A liquid circulation loop is added between the electrolytic anode tank area and an insoluble anode electroplating tank without an electroplating tank divider, or between the electrolytic anode tank area and an electroplating cathode tank area of ​​an insoluble anode electroplating tank with an electroplating tank divider, so that the electrolytic anode liquid and the electroplating liquid or the electroplating cathode liquid are mixed through flow, so that the electroplating liquid or the electroplating cathode liquid with reduced copper ion concentration and increased sulfuric acid concentration after the electroplating operation participates in the electrolytic copper dissolving reaction to produce copper sulfate copper source replenishing solution.

5. The method according to claim 4, characterized in that An electrolytic anode liquid circulation tank connected to the electrolytic anode tank area of ​​the copper dissolving electrolytic cell is added, and the electroplating liquid or electroplating cathode liquid overflowing from the electroplating tank is drained into the electrolytic anode liquid circulation tank to participate in the anode copper dissolving electrochemical reaction of the copper dissolving electrolytic cell to produce copper sulfate copper source replenishing solution.

6. The method according to claim 5, characterized in that The copper ion concentration of the electrolytic cathode liquid is maintained at no more than 10 g / L, and / or the electrolytic cathode liquid or the mixed solution of the electrolytic cathode liquid and the electroplating anode liquid is subjected to oxidation treatment.

7. The method according to claim 6, characterized in that A gas-liquid mixing device is used to promote oxygen and / or ozone to oxidize the electrolytic cathode liquid or the mixed liquid of the electrolytic cathode liquid and the electroplating anode liquid.

8. The method according to claim 7, characterized in that The insoluble anode electroplating tank is provided with an electroplating tank partition, and a liquid circulation loop is added between the electrolytic cathode tank area and the electroplating anode tank area, so that the two solutions are mixed by flow to adjust their sulfuric acid concentrations, and the oxygen electrolyzed in the electroplating anode tank area can oxidize the electrolytic cathode liquid.

9. The method according to claim 8, characterized in that The copper oxalate after the copper removal reaction is heated to produce copper oxide, which is then recycled into the system as an auxiliary copper source.

10. A device for optimizing an insoluble anode copper plating process in combination with electrolytic copper dissolution, comprising an insoluble anode electroplating tank, characterized in that: Add copper dissolving electrolytic cells, chemical reaction tanks and solid-liquid separators; among which: The copper dissolving electrolytic cell is divided into an electrolytic anode cell area and an electrolytic cathode cell area by an electrolytic cell separator, and is used to respectively contain an electrolytic anolyte and an electrolytic cathode liquid. The electrolytic anode of the copper dissolving electrolytic cell is copper metal, and the copper sulfate copper source replenishing solution required in the electroplating cell is produced by an electrolytic copper dissolving method using the electrolytic anolyte containing sulfuric acid. The insoluble anode electroplating tank is used to hold electroplating solution, or is divided into an electroplating anode tank area and an electroplating cathode tank area by an electroplating tank divider, and is used to respectively hold electroplating anode solution and electroplating cathode solution, and uses the electroplating cathode tank area to electroplate the electrolytic cathode of the plated workpiece to produce acid copper sulfate; the insoluble anode electroplating tank without an electroplating tank divider, or the electroplating cathode tank area of ​​the insoluble anode electroplating tank with an electroplating tank divider, is connected to the electrolytic anode tank area of ​​the copper dissolving electrolytic tank via a pipeline, so that the copper sulfate copper source replenishing solution produced in the copper dissolving electrolytic tank can be added to the insoluble anode electroplating tank; The chemical reaction tank is connected to the copper-dissolving electrolytic tank and / or the insoluble anode electroplating tank and the solid-liquid separator through pipelines, and the chemical reaction tank is used to react the electrolytic cathode liquid and / or the electroplating anode liquid with the copper removal agent oxalic acid to remove copper; The solid-liquid separator is connected to the chemical reaction tank and the copper-dissolving electrolytic tank and / or the insoluble anode electroplating tank respectively through pipelines, and is used to perform solid-liquid separation on the solid-liquid mixture generated by the reaction in the chemical reaction tank to obtain copper salt filter residue and sulfuric acid-containing filtrate, and circulate the filtrate back to the copper-dissolving electrolytic tank and / or the insoluble anode electroplating tank through pipelines.

11. The device according to claim 10, characterized in that At least two liquid flow communication channels are added between the electrolytic anode tank area of ​​the copper dissolving electrolytic cell and the insoluble anode electroplating cell without an electroplating cell separator, or between the electrolytic anode tank area of ​​the copper dissolving electrolytic cell and the electroplating cathode tank area of ​​the insoluble anode electroplating cell with an electroplating cell separator, to realize a liquid flow mixing circulation loop.

12. The device according to claim 11, characterized in that At least two liquid flow communication channels are added between the electrolytic cathode tank area of ​​the copper dissolving electrolytic tank and the electroplating anode tank area of ​​the insoluble anode electroplating tank provided with an electroplating tank partition to realize a liquid flow mixing circulation loop.

13. The device according to claim 12, characterized in that A temporary storage tank is added for use in chemical reactions, solution circulation and exchange, and temporary storage of materials; the temporary storage tank is connected to the copper-dissolving electrolytic tank and / or the insoluble anode plating tank and / or the chemical reaction tank and / or the solid-liquid separator and / or other temporary storage tanks, or is arranged on a connecting pipe between at least two of the copper-dissolving electrolytic tank, the insoluble anode plating tank, and the chemical reaction tank.

14. The device according to claim 13, characterized in that A gas-liquid mixing device is added to the temporary storage tank, and the gas-liquid mixing device is a vacuum ejector and / or a spray tower.

15. The device according to claim 14, characterized in that Add hydrogen safety treatment equipment to the copper dissolving electrolytic cell.

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