TW201821654A - Acid copper electroplating process using insoluble anode and equipment therefor - Google Patents

Abstract

An acid copper electroplating process using an insoluble anode and equipment therefor. In the process and the equipment, a separator is used to separate electroplating solutions in a cathode region and an anode region, to avoid the phenomenon of reverse etching of a plated part at the cathode by the electroplating solution in the cathode region, bringing high current efficiency and preferable electroplating quality, and meeting quality requirements for acid copper plating. A regeneration tank is additionally provided for formulating a regenerative electroplating solution, in which copper metal, which is less expensive than copper oxide and phosphor copper can be used. The use of oxygen as an oxidizing agent to realize the energy-saving and environmentally-friendly process for formulating copper sulfate through regeneration by recycling the cathode electroplating solution achieves better economic effects than the prior art using copper oxide and phosphor copper, and can also prevent oxygen added during the regeneration from reverse etching a plating layer and impacting the quality of copper plating.

Description

Process and equipment for acid copper electroplating using insoluble anode

The invention relates to a process and equipment for acid copper electroplating, and in particular to a process and equipment for acid copper electroplating using an insoluble anode.

The existing acid copper plating process is divided into using a soluble anode and using an insoluble anode. The soluble anode used in the acid copper plating process is usually phosphor copper. Insoluble anodes refer to anodes that do not or rarely undergo anodic dissolution reactions during the electrochemical reaction process. Insoluble anodes are usually selected from titanium, graphite, platinum, and lead alloys coated with precious metal oxides during the acid copper plating process. Due to the high price of phosphorous copper used in soluble anodes, and the production and use of toxic phosphorus-containing wastewater, which is harmful to the liver and other organs when entering the human body, it is necessary to increase the cost of electroplating waste water in order to meet the wastewater discharge targets; and During the process, anodic polarization is prone to occur, and poor current distribution leads to unstable coating quality. Therefore, the use of insoluble anode process is becoming more and more common.

A common acid copper plating process using an insoluble anode uses an aqueous solution of copper sulfate and sulfuric acid as a plating solution. Water reacts on the anode to decompose to generate hydrogen ions and oxygen. The copper ions in the plating solution are reduced to metallic copper at the cathode. With the electroplating of copper, the sulfuric acid concentration in the plating solution is getting higher and higher, and copper oxide is added to react with it to replenish the lost copper ions in the plating solution and consume equivalent sulfuric acid accordingly. The shortcoming of this method is the quality problem caused by the adhesion of oxygen to the plating: due to the separation of water on the anode, oxygen is dissolved, and the oxygen dissolved in the plating solution is attached to the cathode plating, causing the coating to become black and loose, which affects the coating. Quality will also increase the consumption of organic brighteners and increase costs.

The specific reaction formula is as follows: Electrochemical reaction on the anode: Electrochemical reaction on the cathode: Reaction of copper sulfate plating bath regeneration: .

Another common acid copper plating process using an insoluble anode is to add iron ions on the basis of a plating solution containing copper sulfate and a sulfuric acid aqueous solution. The electrochemical reaction on the anode is the oxidation of divalent iron ions to trivalent iron ions. Copper The ions are reduced to metallic copper at the cathode. This process can reduce the amount of oxygen dissolved in the plating solution and avoid quality problems caused by oxygen, but the trivalent iron ions present in the plating solution may etch back the copper on the cathode and affect the plating rate.

The specific reaction formula is as follows: Electrochemical reaction on the anode: Electrochemical reaction on the cathode: Response of ferric ion to copper etch back: .

The first object of the present invention is to provide an acidic copper electroplating process using an insoluble anode, which can effectively solve the quality problem caused by oxygen in the acidic copper plating process of the existing insoluble anode, and does not attack the plating, and not only improves the electroplating. Quality, and it can also save the production cost of electroplating.

The first object of the present invention can be achieved by the following technical scheme: an acidic copper electroplating process using an insoluble anode, including the use of an insoluble anode, a cathode, an electroplating tank, and a copper sulfate plating solution, which is referred to as a plating solution hereinafter It is characterized in that it specifically includes the following steps: Step 1 Prepare process equipment: use a diaphragm to divide the electroplating tank into an anode area and a cathode area, the diaphragm allows electrons to pass freely, and simultaneously add a copper sulfate plating solution regeneration configuration tank, hereinafter referred to as The regeneration tank connects the overflow port of the cathode area with the regeneration tank by a pipeline, so that the cathode plating solution overflows into the regeneration tank when the cathode plating solution overflows; the regeneration tank is connected with a pump, and the pump passes the reflux The tube is connected to the cathode area to form a loop, so that the cathode electroplating solution circulates between the cathode area and the regeneration tank; the regeneration tank is also connected to an oxygen source feeding system, and the oxygen source feeding The feeding system is used to control the addition of oxygen; an automatic detection feeding control machine is added to detect the plating solution in the cathode area and / or the regeneration tank Acidity and / or colorimetric and / or redox potential parameters / or specific gravity parameters of the regenerated plating solution; Step 2 prepare the plating solution: prepare an anode plating solution and a cathode plating solution, and pour the anode plating solution into the anode In the zone, the cathode plating solution is poured into the cathode zone and the regeneration tank, and at the same time, copper metal is added to the regeneration tank; when the copper sulfate plating solution is recycled and prepared, the The solution is called regenerated copper sulfate plating solution, referred to as regenerated plating solution; Step 3 starts the plating operation: connect the insoluble anode to the positive electrode of the power supply, and immerse it in the anodic plating solution, connect the cathode plated part to the negative electrode of the power supply, and immerse the cathode In the plating solution, the pump in step 1 is turned on, and the electrode is powered on to perform the plating operation and the copper sulfate plating solution is regenerated and recycled. Step 4 Control the regeneration of the cathode plating solution: use an automatic detection and feeding controller to control the cathode area. The electroplating solution and / or the regeneration plating solution in the regeneration tank are used to detect the acidity and / or colorimetric and / or redox potential and / or specific gravity parameters and use them separately. Control the start-up and shutdown of the oxygen source dosing system: when the acidity of the cathode plating solution and / or the regeneration plating solution is higher than the set value, or the colorimetric or redox potential / or the specific gravity is lower than the set value, turn on The oxygen source adding system is used to supplement oxygen in the plating solution of the regeneration tank, accelerate the regeneration reaction of the copper sulfate plating solution in which sulfuric acid, metallic copper, and oxygen participate, so that sulfuric acid is regenerated into copper sulfate and becomes a regeneration plating solution; When it is detected that the acidity, colorimetric or redox potential, or specific gravity of the cathode plating solution and / or the regenerated plating solution reaches a set value, the oxygen source addition system is shut down to stop supplementing oxygen; step 5 cathode plating Liquid regeneration cycle: In step 4, the regeneration plating solution in the regeneration tank is infused into the cathode region through the pump, and the cathode plating solution flows into the cathode region overflow port through a pipe when the cathode region overflows. In the regeneration tank, a cyclic flow of a cathode plating solution is formed, so that the cathode plating solution is continuously replenished with copper ions and the sulfuric acid concentration is adjusted, so as to stabilize various parameters in the plating process.

Working principle of the present invention: Although the bipolar electrochemical reaction of the present invention is the same as that of the first common acidic copper plating process using an insoluble anode mentioned in the background, the latter uses copper oxide and Sulfuric acid reaction to replenish the lost copper ions in the plating solution and consume equivalent sulfuric acid accordingly. In the present invention, a separate regeneration tank is provided for the preparation of the regeneration plating solution. Metal copper and oxygen are used as the oxidant to react with sulfuric acid. The copper sulfate is regenerated at the same time as the sulfuric acid in the liquid is getting higher and higher. The regeneration chemical reaction equation of the present invention is as follows: .

Therefore, in the process of the present invention, metal copper, which is cheaper than copper oxide and phosphor copper, can be directly used to supplement copper ions in the plating solution, thereby achieving process stability. At the same time, since the regeneration reaction does not proceed in the cathode region, the added oxygen does not enter the cathode region and etch back the plating layer. In addition, the present invention uses a separator to separate the plating tank into the anode region and the cathode region. The design also prevents the oxygen generated in the anode region from approaching the cathode region, thereby preventing the metal of the cathode plating from being etched back and affecting the quality of the coating.

The metallic copper according to the present invention may be a copper powder, a copper block, or a copper rod.

The oxygen source adding and feeding system according to the present invention is mainly composed of an oxygen source and a adding and controlling device.

The oxygen source in the present invention may be one or more of the oxygen generated in the anode, the oxygen in the air, and the bottled compressed oxygen.

When the bottled compressed oxygen is used as the oxygen source, the charging and adding control device is a control valve or a jet vacuum aeration device; when the oxygen source uses the precipitated oxygen generated on the anode, the charging and adding control device is a suction hood fan. An extraction hood fan system is provided directly above the anode area, and the exhaust pipe outlet of the extraction hood fan is placed in the regeneration tank; when the oxygen source uses oxygen in the air, the additional investment control device may A jet vacuum aeration device is used. When the former is used, its suction area is connected to air, and its liquid inlet is connected to an aeration pump. The other end of the aeration pump is connected to the bottom of the regeneration tank through a pipe. The liquid outlet of the jet vacuum aeration device is placed in the regeneration tank; a compressed air machine or a zeolite molecular sieve oxygen generator can also be used to configure a control valve.

The invention can be optimized by the following technical measures.

In the present invention, the anode plating solution is a sulfuric acid aqueous solution having a concentration of 0.001 to 700 g / L; the cathode plating solution is a copper sulfate aqueous solution having a concentration of 35 to 240 g / L.

In the present invention, copper oxide may be additionally added in the regeneration tank, and the reaction between copper oxide and sulfuric acid can quickly obtain copper sulfate, which helps shorten the time required to increase the concentration of copper sulfate in the regeneration plating solution.

The present invention may further include copper sulfate in the anodizing solution, and the concentration is 0.001 to 240 g / L. By adding copper sulfate, the conductivity of the anode plating solution can be increased, the allowable current density can be increased, and the scorch phenomenon in the high current region can be effectively avoided.

Preferably, the cathode plating solution may further contain sulfuric acid, and the concentration is controlled within a range of 0.001 to 400 g / L, so as to effectively prevent the hydrolysis of copper sulfate to cuprous sulfate and then to cuprous oxide (Cu ₂ O), So as to avoid the occurrence of loosening in the coating due to the inclusion of cuprous oxide.

The present invention may further include 10 to 10,000 mg / L of chloride ions in the cathode plating solution, and the source of the chloride ions may be hydrochloric acid and / or sodium chloride. Because during the electroplating process, there may be a small amount of monovalent cuprous ions in the cathode plating solution, which will affect the flatness of copper on the cathode plating part, resulting in rough surface of the plating part. In order to avoid this problem, it is preferable to add an appropriate amount of chloride ions to the cathode plating solution, which can react with monovalent cuprous ions to form cuprous chloride which is slightly soluble in water, so as to reduce the influence of cuprous ions on the plated parts. .

The invention can further add a jet vacuum aeration device, whose suction area is connected to the air outlet of the dosing control device, and its liquid inlet is connected to an aeration pump, and the other end of the aeration pump passes A pipe is connected to the bottom of the regeneration tank, and a liquid outlet of the jet vacuum aeration device is placed in the regeneration tank. The jet vacuum aeration device is used to pass oxygen into the regeneration plating solution in the regeneration tank, and the oxygen and the regeneration plating solution can be compressed and mixed by the pressure formed in the jet vacuum aeration device, thereby accelerating the regeneration of the regeneration plating solution. chemical reaction.

More preferably, when detecting the acidity and / or colorimetric and / or redox potential and / or specific gravity parameters of the cathode plating solution and / or the regenerated plating solution using an automatic detection feeding control machine, the oxygen is controlled At the same time as the source plus investment system is turned on and off, the jet vacuum aeration device is also controlled separately: when the acidity of the cathode plating solution and / or the regeneration plating solution is higher than a set value, or a redox potential or ratio When the color / or specific gravity is lower than the set value, the jet vacuum aeration device is turned on to accelerate the regeneration reaction of oxygen in the copper sulfate plating solution in the regeneration tank, so as to keep the composition of the cathode plating solution stable.

The invention can further provide a screening program between the regeneration tank and the pump. The screening program can effectively prevent the copper sludge in the regeneration tank from entering the cathode area, thereby avoiding the cathode Copper mud appears near the plated parts and affects the quality of the coating.

Preferably, the separator used in step 1 uses an anion film. When the cathode plating solution is reduced to metallic copper with copper ions on the cathode plating, the remaining sulfate ions pass through the cathode region under the action of an electric field. The anion film enters the anode region and combines with hydrogen ions generated after water electrolysis on the anode to become sulfuric acid, so the sulfuric acid concentration in the anode plating solution is getting higher and higher. The overflow port of the anode zone is connected to the regeneration tank through a pipeline, and the anode is controlled by an automatic detection and feeding control machine containing one or more kinds of detectors such as a hydrometer, a level meter, an acidity meter, and an ORP meter. The specific gravity and / or liquid level and / or acidity and / or redox potential parameters of the plating solution are detected. On the one hand, when the specific gravity or liquid level or acidity or redox potential of the anode plating solution deviates from the set range, The automatic detection feeding control machine controls feeding of clean water into the anode area through a feeding pump, so that the component concentration of the anode plating solution is kept stable. On the other hand, after the anode plating solution overflows in the anode region and flows into the regeneration tank through the overflow port, the sulfuric acid added in the anode plating solution participates in the regeneration reaction of the copper sulfate plating solution in the regeneration tank, and further Stable electroplating process system to realize the regeneration cycle of electroplating solution.

Preferably, the diaphragm used in step 1 uses a cationic membrane. When hydrogen ions generated after water electrolysis occurs on the anode and enters the cathode region through the cationic membrane under the action of an electric field, the cathode plating solution and copper plating solution The cathode sulfate is reduced to metallic copper and the remaining sulfate ions are combined to become sulfuric acid. Therefore, the sulfuric acid concentration in the cathode plating solution is getting higher and higher, and a hydrometer, a liquid level meter, an acidity meter, an ORP may be further used. The automatic detection and feeding controller of one or more detectors in the meter detects the specific gravity and / or liquid level and / or acidity and / or redox potential parameters of the anode plating solution, and when the specific gravity or solution of the anode plating solution is When the level or acidity or redox potential deviates from the set range, the automatic detection feeding control machine controls the feeding of fresh water into the anode area through a feeding pump, so that part of the water lost in the anode plating solution due to water electrolysis and air extraction is obtained. supplement.

According to the present invention, a diaphragm may be provided in a pipe connected to the overflow port of the cathode region and the top of the regeneration tank, and the diaphragm can effectively prevent the passage of organic matter. The acidic copper sulfate electroplating solution usually contains an electroplating brightener whose main component is organic matter to obtain a brighter copper surface, and the electroplating brightener easily reacts with oxygen and / or an oxidant and is consumed, which increases the plating during the electroplating process. The amount of brightener used. Therefore, by providing the diaphragm, the pressure difference can be used to effectively pass the inorganic components with smaller molecules in the solution and reduce the plating brightener from entering the regeneration tank, so as to reduce the cost and improve the environmental protection.

A second object of the present invention is to provide an apparatus for the aforementioned acidic copper electroplating process using an insoluble anode.

The second object of the present invention can be achieved by the following technical solution: An acidic copper electroplating equipment using an insoluble anode, including the use of an insoluble anode, a cathode, a plating tank, and a copper sulfate plating solution, which is characterized in that: The tank is divided into an anode region and a cathode region. The diaphragm allows electrons to pass freely. At the same time, a regeneration tank is added so that the overflow port of the cathode region is connected to the regeneration tank by a pipeline so that when the cathode plating solution overflows, it overflows to In the regeneration tank, the regeneration tank is connected with a pump, and the pump is connected to the cathode region through a return pipe to form a loop, so that the cathode plating solution can circulate between the cathode region and the regeneration tank; The regeneration tank is also connected to an oxygen source dosing system, which is used to control the addition of oxygen; an automatic detection feeding controller is added to detect the plating solution and / or regeneration in the cathode area The acidity and / or colorimetric and / or redox potential parameters of the regeneration plating bath in the tank are used to control the startup and shutdown of the oxygen source dosing system, respectively; A green plating solution is infused into the cathode region through the pump, and when the cathode plating solution overflows, it flows into the regeneration tank through a pipe from the overflow port of the cathode region to form a circulating flow, thereby plating the cathode. The liquid continuously replenishes copper ions and adjusts the sulfuric acid concentration to achieve stability of various parameters in the electroplating process.

The oxygen source adding and feeding system according to the present invention is mainly composed of an oxygen source and a adding and controlling device. The adding and adding control device may be a control valve, a vacuum jet aeration device, a hood fan system, or a zeolite molecular sieve oxygen generator configuration.

The separator for separating the electroplating tank into the anode area and the cathode area according to the present invention may be an anion membrane or an anode separator.

The invention has the following beneficial effects: (1) The quality of copper plating is high and the efficiency is high: the invention uses a separator to separate the plating solution in the cathode and anode regions, which can avoid the phenomenon that the plating solution in the cathode region etches back the cathode plating part, making its current efficiency High, good electroplating quality, meeting the quality requirements of acid copper plating; (2) Low energy saving cost: The present invention separately sets a regeneration tank for the preparation of the regeneration electroplating solution, which can use copper metal which is cheaper than copper oxide and phosphor copper. The use of oxygen as an oxidant to realize the recycling and regeneration of cathode plating solution to prepare copper sulfate is an energy-saving and environmentally friendly process, which creates better economic effects than the existing technology using copper oxide and phosphorous copper. Corrosion affects the quality of copper plating; (3) Simple and environmentally friendly: The process of the present invention is simple and reliable, and can completely replace the acid copper plating process using soluble phosphor copper anodes, reducing environmental pollution.

Specific examples are given below to illustrate the present invention. It should be noted that the embodiments are only used to further explain the present invention, and do not represent the protection scope of the present invention. Non-essential modifications and adjustments made by others according to the present invention still belong to the protection scope of the present invention.

In the following examples, the copper sulfate used is preferably copper sulfate produced by Changzhou Hairun Chemical; the sulfuric acid used is preferably sulfuric acid produced by Guangzhou Chemical Reagent Factory; the metal copper used is preferably produced by Changsha Tianjiu Metal Materials Co., Ltd. Non-phosphorus copper powder or commercially available pure copper plate or pure copper rod; the anode used is preferably a titanium anode plate coated with precious metal oxide produced by Qixin Titanium Company; the zeolite molecular sieve oxygen generator used is preferably Qingdao Zeolite molecular sieve oxygen generator produced by Sankai Medical Technology Co., Ltd. The bottled compressed oxygen used is preferably compressed oxygen produced by Guangzhou Guangqi Gas Co., Ltd .; the diaphragm used is preferably a diaphragm produced by Membrane International of the United States; used The microscope is preferably a computer microscope produced by Guangzhou Optical Instrument Factory; the automatic detection feeding machine used is preferably an automatic detection feeding machine produced by Guangzhou Yegao Chemical Co., Ltd. In addition to the above list, those skilled in the art may also choose other products with similar properties to the above-listed products according to the conventional selection, and all of the objects of the present invention can be achieved.

The current efficiency calculation formula-1 is as follows: among them, Actual product quality; m theoretical product quality calculated according to Faraday's law; I current strength (A); t current time (h); k electrochemical equivalent (g / (A )).

Example 1

The regeneration system of the cathode plating solution shown in FIG. 1 is the equipment used in Examples 1 and 5-8 of the present invention, and includes an insoluble anode (not labeled), a cathode plating part (not labeled), a plating tank, and copper sulfate plating. Liquid, regeneration tank 4, metal copper (not shown in the figure), pump 6, oxygen source dosing system and automatic detection and feeding control machine (not shown in figure), the acid plating copper process using an insoluble anode specifically includes the following steps: 1 Preparation of process equipment: an anion membrane is used to separate the electroplating tank into an anode region 2 and a cathode region 1, and the overflow ports of the anode region and the cathode region are simultaneously connected to the top of the regeneration tank 4 by pipes; the regeneration tank is connected to a A pump 6, which is connected to the cathode region through a return pipe 13 to form a loop; the regeneration tank is also connected to an oxygen source addition and injection system, and the oxygen source in the oxygen source addition and injection system is generated on the anode The added oxygen control device is an extraction hood fan 3 disposed directly above the anode zone 2, and the air outlet of the exhaust pipe of the extraction hood fan 3 is placed in the plating solution in the regeneration tank; respectively Said Yang The electrode area 2 and the cathode area 1 are provided with automatic detection and feeding control machines for detecting the technical parameters of the plating solution in the two electrode areas respectively. Step 2 Prepare the plating solution: under normal temperature and pressure, according to Table-1 The anode plating solution and the cathode plating solution are prepared, wherein the anode plating solution: 300 g / L sulfuric acid aqueous solution; the cathode plating solution: 150 g / L copper sulfate aqueous solution; and pouring the anode plating solution into the anode region The cathode plating solution is poured into the cathode region and the regeneration tank filled with metallic copper, and the initial weight of the cathode plating is weighed; the amount of metallic copper is calculated according to the amount of copper that needs to be electroplated, That is, X grams of copper is plated on the cathode plating, and the total copper content of the metallic copper in the regeneration tank should be greater than or equal to X grams. Step 3 Start the electroplating operation: connect the insoluble anode with the positive electrode of the power supply and immerse it in the anode plating solution, connect the cathode plated part with the negative electrode of the power supply and immerse it in the cathode plating solution; Power on the electrode for electroplating operation and copper sulfate electroplating bath recycling regeneration preparation; Step 4 Control the cathode electroplating bath regeneration: use an automatic detection feeding control machine to detect the acidity of the cathode electroplating bath and the specific gravity parameters of the anode electroplating bath and separately Control the shutdown of the exhaust hood fan and the addition of fresh water in the anode zone 2, set the acidity setting value according to the acidity of the initial cathode plating solution, and set the specific gravity setting value according to the specific gravity of the initial anode plating solution; when the cathode plating When the acidity of the liquid is higher than the set value, the air extraction hood fan 3 is turned on, so as to supplement oxygen in the plating solution of the regeneration tank, accelerate the regeneration reaction of the copper sulfate plating solution involving sulfuric acid, metallic copper and oxygen, so that the sulfuric acid is regenerated into Copper sulfate becomes a regeneration plating solution; when the acidity of the cathode plating solution reaches a set value, the exhaust hood fan 3 is turned off, Stop adding oxygen; when the specific gravity of the anode plating solution is higher than the set value, the automatic inspection and feeding control machine controls the feeding of fresh water into the anode zone 2 through a feeding pump; Step 5: The regeneration process of the cathode plating solution: Step 4 After the electroplating solution is regenerated, it is infused into the cathode region 1 through the pump 6, and at the same time, the electroplating solution in the two electrode regions flows into the regeneration tank 4 from the overflow port through the pipeline to form a circulating flow, thereby The cathode plating solution is continuously supplemented with copper ions and adjusted with sulfuric acid concentration, so as to achieve stability of various parameters in the plating process.

Set the plating test time to 15 hours and the cathode current density to 3 A / dm ^2. When the set plating time is complete, take out the cathode plated parts; wash the cathode plated parts with clean water and dry them with hot air. Equation-1 calculates the current efficiency, and observes the plating surface using a computer microscope. The observation results are recorded in Table-1.

Example 2

The regeneration system of the cathode plating solution shown in FIG. 2 is the equipment used in Examples 2 and 10-12 of the present invention, and includes an insoluble anode (not labeled), a cathode plating part (not labeled), a plating tank, and copper sulfate plating. Liquid, regeneration tank 4, metallic copper (not shown), pump 6, screening program 5, oxygen source dosing system, automatic detection feeding control machine (not shown), and jet vacuum aeration device 11, which uses insolubility The process of the acidic copper electroplating of the anode specifically includes the following steps: Step 1 Prepare process equipment: use a cationic membrane to separate the electroplating tank into an anode region 2 and a cathode region 1, and the overflow port of the cathode region 1 and the top of the regeneration tank 4 are The pipeline is connected; the regeneration tank 4 is connected to the screening program 5 and the pump 6 in turn. The pump 6 is connected to the cathode region 1 through a return pipe 13 to form a loop; the regeneration tank 4 is also fed with an oxygen source. The system is connected. The oxygen source in the oxygen source adding and charging system is the oxygen generated on the anode, and the adding and controlling device is an extraction hood fan 3 disposed directly above the anode area. Outlet of exhaust pipe The suction area 9 of the jet vacuum aeration device 11 is connected, and the liquid inlet 7 of the jet vacuum aeration device is connected to the oxygen pump 12 and the bottom of the regeneration tank 4 through a pipe in order. The jet vacuum aeration device A liquid outlet 8 of 11 is placed in the regeneration tank 4; an automatic detection feeding control machine is respectively provided for the cathode region 1, the anode region 2 and the regeneration tank 4 to detect the plating solution in the two electrode regions respectively. Technical parameters; Step 2 Prepare the plating solution: Prepare the anodic plating solution and the cathodic plating solution as shown in Table-1 under normal temperature and pressure. Among them, the anodic plating solution: 200g / L copper sulfate, 100g / L sulfuric acid Aqueous solution; Cathodic plating solution: 200g / L copper sulfate, 100g / L sulfuric acid mixed solution; Pour the anode plating solution into the anode zone 2 and pour the cathode plating solution into the cathode zone 1 respectively. And a regeneration tank 4 containing a 1: 1 mixture of metal copper and copper oxide, and weighed the initial weight of the cathode plating part; the amount of the metal copper and copper oxide mixture was determined by plating X grams of copper on the cathode plating part , The total copper and copper oxide mixture in the regeneration tank Copper content greater than or equal X g. Step 3 starts the electroplating operation: connect the insoluble anode with the positive electrode of the power supply and immerse it in the anode plating solution, connect the cathode plated part with the negative electrode of the power supply and immerse the cathode plating solution; turn on the pump 6 in step 1, Turn on the electrode power to perform the electroplating operation and the copper sulfate electroplating liquid recycling regeneration preparation. Step 4 Control the cathode electroplating liquid regeneration: use an automatic detection and feeding control machine to compare the color of the cathode electroplating liquid and the regeneration electroplating liquid in the regeneration tank 4 and The liquid level parameters of the anode plating solution are detected, and the parameters are used to control the start and stop of the jet vacuum aeration device 11 and the exhaust hood fan 3, and the addition of fresh water in the anode area 2, according to The color depth of the initial cathode plating solution is set to the colorimetric setting value, and the liquid level setting value is set according to the liquid level of the initial anode plating solution; when the colorimetry of the cathode plating solution or the regeneration plating solution is lower than the set value, the jet is turned on The vacuum aeration device 11 and the exhaust hood fan 3 are used to supplement oxygen in the plating solution of the regeneration tank 4 to accelerate the sulfuric acid, copper metal and oxygen-containing copper sulfate. Liquid regeneration reaction, which regenerates sulfuric acid to copper sulfate, and becomes a regeneration plating solution; when the colorimetry of the cathode plating solution or the regeneration plating solution reaches a set value, the exhaust hood fan 3 is turned off to stop supplementing oxygen; when the When the liquid level of the anode plating solution is lower than the set value, the automatic inspection and feeding control machine controls the feeding of clean water into the anode zone 2 through a feeding pump; Step 5: The regeneration cycle of the cathode plating solution: in step 4 the regeneration tank 4 After the regeneration plating solution is configured, it is infused into the cathode region 1 through the pump 6, and at the same time, the cathode plating solution flows from the overflow port of the cathode region 1 into the regeneration tank 4 through a pipe to form a circulating flow, thereby The cathode plating solution is continuously supplemented with copper ions and adjusted with sulfuric acid concentration, so as to achieve stability of various parameters in the plating process. Set the plating test time to 15 hours and the cathode current density to 3 A / dm2. When the set plating time is complete, take out the cathode plated parts; wash the cathode plated parts with clean water and dry them with hot air and weigh them. -1 Calculate the current efficiency and observe the plating surface with a computer microscope. The results of the observation are recorded in Table-1.

Example 3

The regeneration system of the cathode plating solution shown in FIG. 3 is the equipment used in Embodiment 3 of the present invention, and includes an insoluble anode (not labeled), a cathode plating part (not labeled), a plating tank, a copper sulfate plating solution, a regeneration tank 4, Copper metal (not shown), pump 6, screening program 5, oxygen source dosing system, automatic detection feeding control machine (not shown), and jet vacuum aeration device 11, which uses an insoluble anode acid copper plating process Specifically, it includes the following steps: Step 1. Prepare the process equipment: use a cationic membrane to separate the plating tank into an anode region 2 and a cathode region 1. The overflow port of the cathode region 1 is connected to the top of the regeneration tank 4 by a pipeline. The pipeline The regeneration tank 4 is connected with the screening program 5 and the pump 6 in turn. The pump 6 is connected to the cathode region 1 through a return pipe 13 to form a loop. The regeneration tank 4 is also connected to an oxygen source. The dosing system is connected. The oxygen source in the oxygen source dosing system is bottled compressed oxygen. The dosing control device is a jet vacuum aeration device 11. The jet vacuum aeration device 11 is connected to the bottled compressed air. The liquid inlet 7 of the jet vacuum aeration device 11 is connected to the bottom of the regeneration tank 4 through a pipeline, and the liquid outlet 8 of the jet vacuum aeration device is placed in the regeneration tank 4; the cathode area 1 is respectively The anode area 2 and the regeneration tank 4 are provided with automatic detection and feeding control machines for detecting the technical parameters of the plating solution in the two electrode areas respectively. Step 2 Prepare the plating solution: under normal temperature and pressure, as shown in Table-1. An anode plating solution and a cathode plating solution were prepared. Among them, the anode plating solution: a mixed aqueous solution of 240 g / L copper sulfate and 50 g / L sulfuric acid; the cathode plating solution: 240 g / L copper sulfate, 50 g / L sulfuric acid, 10 mg / L mixed aqueous solution of hydrochloric acid; pour the anodic plating solution into the anode zone 2, pour the cathodic plating solution into the cathode zone 1 and a solution containing a 1: 1 mixture of metal copper and copper oxide In the regeneration tank 4, the initial weight of the cathode plating part is weighed; Step 3 starts the plating operation: connect the insoluble anode to the positive electrode of the power supply and immerse it in the anode plating solution, connect the cathode plating part to the negative electrode of the power supply and Dip into the cathode plating solution; turn on step 1 The pump 6 is connected to the electrode power supply for the electroplating operation and the copper sulfate electroplating bath recycling regeneration preparation. Step 4 Control the cathode electroplating bath regeneration: using an automatic detection and feeding control machine to the redox potential of the regeneration electroplating bath and the anode, respectively. The specific gravity of the plating solution and the redox potential parameters are detected, and the parameters are used to control the start-up and shutdown of the jet vacuum aeration device and the addition of fresh water in the anode zone 2. According to the redox of the initial cathode plating solution, The potential is set to the redox potential setting value of the cathode plating solution, and the specific gravity and the redox potential setting value of the anode plating solution are respectively set according to the specific gravity and the redox potential of the initial anode plating solution; when the redox potential of the regeneration plating solution is lower than the setting When the value is set, the jet vacuum aeration device 11 is turned on to supplement oxygen in the plating solution of the regeneration tank 4 to accelerate the regeneration reaction of the copper sulfate plating solution in which sulfuric acid, metallic copper and oxygen participate, so that the sulfuric acid is regenerated into copper sulfate and becomes Regeneration plating solution; when the oxidation-reduction potential of the regeneration plating solution reaches a set value, turn off The jet vacuum aeration device 11 stops supplying oxygen; when the specific gravity or ORP parameter of the anode plating solution is higher than a set value, the automatic inspection and feeding control machine controls the feeding of fresh water into the anode zone 2 through a feeding pump; Step 5 Cathodic plating solution regeneration cycle: After the regeneration plating solution in the regeneration tank 4 is configured in step 4, the pump 6 is infused into the cathode zone 1 while the cathode plating solution overflows from the cathode zone 1 The flow port flows into the regeneration tank 4 through a pipe to form a circulating flow, so that the cathode plating solution is continuously replenished with copper ions and adjusted the sulfuric acid concentration, thereby realizing the stability of various parameters in the plating process.

Set the plating test time to 15 hours and the cathode current density to 3 A / dm ^2. When the set plating time is complete, take out the cathode plated parts; wash the cathode plated parts with clean water and dry them with hot air. Equation-1 calculates the current efficiency, and observes the plating surface using a computer microscope. The observation results are recorded in Table-1.

Example 4

The regeneration system of the cathode plating solution shown in FIG. 4 is the equipment used in Embodiment 4 of the present invention, and includes an insoluble anode (not labeled), a cathode plating part (not labeled), a plating tank, a copper sulfate plating solution, a regeneration tank 4, Copper metal (not shown), pump 6, screening program 5, oxygen source dosing system, automatic detection feeding control machine (not shown), and jet vacuum aeration device 11, which uses an insoluble anode acid copper plating process Specifically, it includes the following steps: Step 1. Prepare a process equipment: use a cationic membrane to separate the electroplating tank into an anode region 2 and a cathode region 1. The overflow port of the cathode region 1 is connected to the top of the regeneration tank 4 by a pipeline. The pipeline is provided with a diaphragm; the regeneration tank 4 is connected to the screening program 5 and the pump 6 in turn, and the pump 6 is connected to the cathode region 1 through another pipeline 13 to form a loop; the regeneration tank 4 is also It is connected with an oxygen source adding and charging system. The oxygen source in the oxygen source adding and charging system is the generated oxygen on the anode and the oxygen in the air, and the adding and controlling device is an exhaust hood fan set directly above the anode area. 3 to Zeolite molecular sieve oxygen generator 14, the air outlet of the exhaust pipe of the exhaust hood fan 3 is connected to the suction area 9 of the jet vacuum aeration device 11, and the liquid inlet 7 of the jet vacuum aeration device is connected with the The oxygen pump 12 and the bottom of the regeneration tank 4 are connected by a pipe, and the liquid outlet 8 of the jet vacuum aeration device 11 is placed in the regeneration tank 4; the cathode region 1, the anode region 2 and the regeneration The tank 4 is provided with an automatic detection and feeding control machine for detecting the technical parameters of the plating solution in the two electrode areas respectively. Step 2 Prepare the plating solution: at normal temperature and pressure, prepare the anode plating solution and Cathodic plating solution, among which, anodic plating solution: 200 g / L copper sulfate, 90 g / L sulfuric acid mixed aqueous solution; cathode plating solution: 150 g / L copper sulfate, 150 g / L sulfuric acid, 205.6 mg / L hydrochloric acid An aqueous solution; said anode plating solution is poured into said anode region 2, said cathode plating solution is poured into said cathode region 1 and said regeneration tank 4 containing a 1: 1 mixture of metal copper and copper oxide, And weigh the initial weight of the cathode plating parts; Step 3 Start the plating operation: The source positive electrode is connected and immersed in the anode plating solution, and the cathode plating is connected to the power source negative electrode and immersed in the cathode plating solution; the pump 6 in step 1 is turned on, and the electrode power is turned on for electroplating operation and copper sulfate Electroplating bath recycling regeneration preparation; Step 4 Control of cathode plating bath regeneration: using an automatic detection feeding controller to detect the redox potential of the regeneration bath in the regeneration tank and the acidity parameter of the anode bath, and control them separately The start and stop of the jet vacuum aeration device 11 and the extraction hood fan 3 and the addition of fresh water in the anode zone 2 are set according to the specific gravity of the initial cathode plating solution and the acidity of the initial anode plating solution. Set value of acidity; when the redox potential of the regenerated plating solution is lower than the set value, turning on the jet vacuum aeration device 11 and the extraction hood fan 13 so as to supplement the plating solution in the regeneration tank 4 with oxygen, Accelerate the regeneration reaction of copper sulfate plating solution with the participation of sulfuric acid, metallic copper and oxygen to regenerate sulfuric acid into copper sulfate and become a regeneration plating solution; when said When the specific gravity of the plating solution is lower than the set value, the jet vacuum aeration device 11 and the exhaust hood fan 13 are closed to stop supplying oxygen; when the acidity of the anode plating solution is higher than the set value, the automatic inspection and feeding The controller controls the feeding of clean water into the anode area 2 through a feeding pump; Step 5: The cathode plating solution regeneration cycle: after the regeneration plating solution is configured in the regeneration tank 4 in step 4, it is infused into the cathode area through the pump 6. In 1, at the same time, the cathode plating solution flows from the overflow port of the cathode zone 1 into the regeneration tank 4 through a pipe to form a circulating flow, thereby continuously replenishing the cathode plating solution with copper ions and adjusting the sulfuric acid concentration to achieve electroplating Stability of various parameters in the manufacturing process.

Set the plating test time to 15 hours and the cathode current density to 3 A / dm ^2. When the set plating time is complete, take out the cathode plated parts; wash the cathode plated parts with clean water and dry them with hot air. Equation-1 calculates the current efficiency, and observes the plating surface using a computer microscope. The observation results are recorded in Table-1.

Example 5

The difference between Example 5 and Example 1 is that an anodic plating solution and a cathodic plating solution are prepared at normal temperature and pressure as shown in Table-1, wherein the anodic plating solution: 50 g / L copper sulfate, 150 g / L A mixed aqueous solution of sulfuric acid; a cathode plating solution: a mixed aqueous solution of 35 g / L copper sulfate, 220 g / L sulfuric acid, and 8239 mg / L hydrochloric acid.

Example 6

The difference between Example 6 and Example 1 is that at normal temperature and pressure, an anode plating solution and a cathode plating solution were prepared as shown in Table-1. Among them, the anode plating solution: 150 g / L copper sulfate, 90 g / L A mixed aqueous solution of sulfuric acid; a cathode plating solution: a mixed aqueous solution of 100 g / L copper sulfate, 190 g / L sulfuric acid, and 10282 mg / L hydrochloric acid.

Example 7

The difference between Example 7 and Example 1 is that at normal temperature and pressure, an anodic plating solution and a cathodic plating solution are prepared as shown in Table-1, wherein the anodic plating solution: 100 g / L copper sulfate, 60 g / L A mixed aqueous solution of sulfuric acid; a cathode plating solution: a mixed aqueous solution of 100 g / L copper sulfate, 220 g / L sulfuric acid, 4078 mg / L hydrochloric acid, and 5000 mg / L sodium chloride.

Example 8

The difference between Example 8 and Example 1 is that at normal temperature and pressure, an anodic plating solution and a cathodic plating solution were prepared as shown in Table-1, wherein the anodic plating solution: 35 g / L copper sulfate, 250 g / L A mixed aqueous solution of sulfuric acid; a cathode plating solution: a mixed aqueous solution of 50 g / L copper sulfate, 250 g / L sulfuric acid, and 10 mg / L hydrochloric acid.

Example 9

The regeneration system of the cathode plating solution shown in FIG. 1 is the equipment used in Examples 1 and 5-8 of the present invention, and includes an insoluble anode (not labeled), a cathode plating part (not labeled), a plating tank, and copper sulfate plating. Liquid, regeneration tank 4, metal copper (not shown in the figure), pump 6, oxygen source dosing system and automatic detection and feeding control machine (not shown in figure), the acid plating copper process using an insoluble anode specifically includes the following steps: 1 Preparation of process equipment: a common electroplating diaphragm is used to separate the electroplating tank into an anode region 2 and a cathode region 1. The overflow port of the cathode region 1 is connected to the top of the regeneration tank 4 by a pipeline; the regeneration tank is connected to a pump 6 The pump 6 is connected to the cathode region 1 through a return pipe 13 to form a loop; the regeneration tank 4 is also connected to an oxygen source addition and injection system, and the oxygen source in the oxygen source addition and injection system is generated on the anode. The added oxygen control device is an extraction hood fan 3 disposed directly above the anode area, and the air outlet of the exhaust pipe of the extraction hood fan 3 is connected to the bottom of the regeneration tank 4 through pipes; respectively For said yin Zone 1, anode zone 2 and regeneration tank are equipped with automatic detection and feeding controllers for detecting the technical parameters of the plating solution in the two electrode zones respectively. Step 2 Prepare the plating solution: under normal temperature and pressure, according to Table-1 The anode plating solution and the cathode plating solution are prepared. Among them, the anode plating solution: a mixed aqueous solution of 50 g / L copper sulfate and 0.001 g / L sulfuric acid; the cathode plating solution: 50 g / L copper sulfate and 0.001 g / L sulfuric acid. Mixed aqueous solution; the anode plating solution is poured into the anode zone 2, the cathode plating solution is poured into the cathode zone 1 and the regeneration tank 4 equipped with metal copper, and the Initial weight; Step 3 Start the plating operation: connect the insoluble anode to the positive electrode of the power supply and immerse it in the anode plating solution, connect the cathode plated part to the negative electrode of the power supply and immerse it in the cathode plating solution; turn on the pump in step 1 Pu 6, turn on the electrode power to perform the plating operation and the copper sulfate plating solution recycling regeneration preparation; Step 4 control the cathode plating solution regeneration: use an automatic detection feeding control machine to check the acidity of the cathode plating solution separately Measure and control the start and stop of the extraction hood fan 3, set the acidity set value according to the acidity of the initial cathode plating solution, and turn on the extraction hood fan 3 when the acidity of the cathode plating solution is higher than the set value In order to replenish oxygen in the plating solution of the regeneration tank 4 and accelerate the regeneration reaction of the copper sulfate plating solution in which sulfuric acid, metallic copper and oxygen participate, so that sulfuric acid is regenerated into copper sulfate and becomes a regeneration plating solution; when the acidity of the cathode plating solution is When the set value is reached, the exhaust hood fan 3 is turned off to stop supplying oxygen; Step 5 Cathodic plating solution regeneration cycle: After the regeneration plating solution is configured in the regeneration tank 4 in Step 4, it is infused into the pump 6 In the cathode region 1, at the same time, the cathode plating solution flows from the overflow port of the cathode region 1 into the regeneration tank 4 through a pipe to form a circulating flow, thereby continuously replenishing the cathode plating solution with copper ions and adjusting the sulfuric acid concentration. To achieve the stability of various parameters in the plating process.

Set the plating test time to 15 hours and the cathode current density to 3 A / dm ^2. When the set plating time is complete, take out the cathode plated parts; wash the cathode plated parts with clean water and dry them with hot air. Equation-1 calculates the current efficiency, and observes the plating surface using a computer microscope. The observation results are recorded in Table-1.

Example 10

The difference between Example 10 and Example 2 is that an anodic plating solution and a cathodic plating solution are prepared at normal temperature and pressure as shown in Table-1, wherein the anodic plating solution: 0.001 g / L copper sulfate, 400 g / L A mixed aqueous solution of sulfuric acid; a cathode plating solution: a mixed aqueous solution of 100 g / L copper sulfate and 300 g / L sulfuric acid.

Example 11

The difference between Example 11 and Example 2 is that an anode plating solution and a cathode plating solution are prepared at normal temperature and pressure as shown in Table-1, wherein the anode plating solution: 550 g / L sulfuric acid; the cathode plating solution: 200 g / L copper sulfate, 350 g / L sulfuric acid mixed solution.

Example 12

The difference between Example 12 and Example 2 is that an anode plating solution and a cathode plating solution are prepared at normal temperature and pressure as shown in Table-1, wherein the anode plating solution: 700 g / L sulfuric acid; the cathode plating solution: 240 g / L copper sulfate, 400 g / L sulfuric acid mixed solution.

Comparative Example 1

The components of the plating solution used in this comparative example are shown in Table-1. Among them, a mixed aqueous solution of 130 g / L copper sulfate, 70 g / L sulfuric acid, and 70 mg / L hydrochloric acid.

Step 1: Dissolve the components specified in Table 1 in water according to the mixing ratio to prepare a plating solution.

Step 2: Pour the plating solution obtained in step 1 into a plating tank, and weigh the initial weight of the cathode plating part.

Step 3: Use an insoluble anode, immerse the anode and cathode plating parts in the plating solution, and connect the anode and cathode of the power supply respectively.

Step 4: Apply electroplating, set the plating test time to 15 hours, and set the cathode current density to 3 A / dm ^{2. During the} plating process, add copper oxide to the electrolytic cell to supplement the copper ion content of the electrolyte. Remove the plated parts. After the plated parts are cleaned with fresh water and dried with hot air, the weight of the plated parts is weighed. The current efficiency was calculated according to Equation 1, and the surface of the plating layer was observed using a computer microscope. The observation results are recorded in Table 1.

Comparative Example 2

The difference between Comparative Example 2 and Comparative Example 1 is that the components of the plating solution used in this comparative example are shown in Table-1, of which 130 g / L copper sulfate, 70 g / L sulfuric acid, 60 g / L iron sulfate, 70 mg / L hydrochloric acid mixed aqueous solution.

Table 1

1‧‧‧ cathode area

2‧‧‧Anode area

3‧‧‧Exhaust Hood Fan

4‧‧‧ regeneration tank

5‧‧‧ Screening Program

6‧‧‧Pump

7‧‧‧ inlet

8‧‧‧ Outlet

9‧‧‧ Suction area

10‧‧‧ diaphragm

11‧‧‧jet vacuum aeration device

12‧‧‧ oxygen pump

13‧‧‧ return tube

14‧‧‧ cathode area overflow

15‧‧‧Anode area overflow

16‧‧‧ Zeolite molecular sieve oxygen generator

The invention is further described below with reference to the drawings and specific embodiments. FIG. 1 is a schematic diagram of an acid copper plating device according to Embodiments 1 and 5 to 8 of the present invention. FIG. 2 is a schematic diagram of an acid copper plating device according to Embodiments 2 and 10 to 12 of the present invention. FIG. 3 is a schematic diagram of an acid copper plating apparatus according to Embodiment 3 of the present invention. FIG. 4 is a schematic diagram of an acid copper plating apparatus according to Embodiment 4 of the present invention. FIG. 5 is a schematic diagram of an acid copper plating apparatus according to Embodiment 9 of the present invention. FIG. 6 is a schematic diagram of a jet vacuum aeration device according to Examples 2-4 and 10-12 of the present invention.

Claims (21)

An acidic copper electroplating process using an insoluble anode includes the use of an insoluble anode, a cathode, an electroplating tank, and a copper sulfate electroplating solution, and is characterized by including the following steps: Step 1. Prepare process equipment: use a diaphragm to divide the electroplating tank into an anode area And the cathode area, the diaphragm allows electrons to pass freely, and a regeneration tank is added at the same time, and the overflow port of the cathode area is connected to the regeneration tank by a pipeline; the regeneration tank is connected to a pump, and the pump passes a return pipe Connected to the cathode area to form a loop; the regeneration tank is also connected to an oxygen source dosing system, which is used to control the addition of oxygen; an automatic detection and feeding control machine is added to detect the Acidity and / or colorimetric and / or redox potential parameters / or specific gravity parameters of the plating solution in the cathode region and / or the regeneration plating solution in the regeneration tank; Step 2, preparing the plating solution: preparing an anode plating solution and a cathode plating solution And pouring the anode plating solution into the anode region, pouring the cathode plating solution into the cathode region and the regeneration tank, and simultaneously, in the regeneration tank Metal copper is added; the anode plating solution is a sulfuric acid aqueous solution, and the cathode plating solution is a copper sulfate aqueous solution; when the copper sulfate plating solution is recycled and prepared, the solution in the regeneration tank is a regeneration plating solution; step 3 Start the electroplating operation: connect the insoluble anode with the positive electrode of the power supply and immerse it in the anode plating solution, connect the cathode plated part with the negative electrode of the power supply and immerse it in the cathode plating solution, turn on the pump in step 1, and connect the The electrode's power source is used for electroplating operation and copper sulfate electroplating bath recycling regeneration preparation; Step 4, controlling the cathode electroplating bath regeneration: using an automatic detection and feeding control machine for the electroplating bath in the cathode zone and / or the regeneration electroplating bath in the regeneration tank Detecting acidity and / or colorimetric and / or redox potential parameters / or specific gravity parameters and respectively controlling the start-up and shutdown of the oxygen source dosing system: when the cathode plating solution and / or the regeneration plating solution When the acidity is higher than the set value, or the colorimetric or redox potential / or the specific gravity parameter is lower than the set value, the oxygen source addition and injection system is turned on; When the acidity, colorimetric or redox potential, or specific gravity parameter of the cathode electroplating solution and / or the regenerated electroplating solution reaches a set value, the oxygen source dosing system is shut down to stop supplementing oxygen; and step 5, the cathode Electroplating solution regeneration cycle: In step 4, the regeneration plating solution in the regeneration tank is infused into the cathode region through the pump, and the cathode plating solution flows from the cathode region overflow port into the regeneration tank through a pipe. Circulating flow. The acidic copper electroplating process using an insoluble anode according to item 1 of the patent application scope, wherein the anode plating solution in step 2 is a sulfuric acid aqueous solution having a concentration of 0.001 to 700 g / L; the cathode plating solution is a concentration of 35 to 240 g / L of copper sulfate aqueous solution. The acidic copper electroplating process using an insoluble anode according to item 2 of the scope of the patent application, wherein the oxygen source adding and adding system includes an oxygen source and an adding and controlling device, wherein the oxygen source is the precipitated oxygen generated on the anode One or more of the oxygen in the air and the bottled compressed oxygen; the adding and controlling device is one or more of a jet vacuum aeration device, a hood fan, a compressed air machine, and a zeolite molecular sieve oxygen generator . According to the acidic copper electroplating process using an insoluble anode as described in item 3 of the scope of the patent application, in step 1, when the oxygen source uses the oxygen generated from the anode to generate the precipitated oxygen, the additional investment control device is an extraction hood fan. An extraction hood fan system is provided directly above the anode area, and an exhaust pipe outlet of the extraction hood fan is placed in a plating solution in the regeneration tank. The acidic copper electroplating process using an insoluble anode as described in item 3 of the scope of patent application, wherein in step 2, copper oxide is additionally added to the regeneration tank, and the amount of metal copper and copper oxide mixture is based on the cathode plating. The amount of copper plating is determined, that is, the total copper content of the mixture of metallic copper and copper oxide in the regeneration tank should be greater than or equal to the amount of copper plating. According to the acidic copper electroplating process using an insoluble anode as described in any one of the scope of claims 1 to 4, when an anion membrane is used as the diaphragm in step 1, an overflow port in the anode region is added, And is connected to the regeneration tank through a pipeline; and in step 4, the specific gravity of the anode plating solution to the anode plating solution is controlled by using an automatic detection feeding control machine containing one or more kinds of detectors such as a hydrometer, a level meter, an acidity meter, and an ORP meter. And / or liquid level and / or acidity and / or redox potential parameters for detection, on the one hand, when the specific gravity or liquid level or acidity or redox potential of the anode plating solution deviates from a set range, the automatic detection feed The controller controls the feeding of clean water into the anode region through a feeding pump, so that the concentration of the composition of the anode plating solution remains stable; on the other hand, the anode plating solution overflows in the anode region and flows into the regeneration through the overflow port. After the tank, the sulfuric acid added in the anode plating solution participates in the regeneration reaction of the copper sulfate plating solution in the regeneration tank. According to the acidic copper electroplating process using an insoluble anode as described in any one of claims 1 to 4 of the scope of the patent application, wherein when the diaphragm used in step 1 is a cationic membrane, a specific gravity meter and a level gauge are used in step 4 , An acidity meter, an ORP meter of one or more detectors of the automatic detection feeding control machine to detect the specific gravity and / or liquid level and / or acidity and / or redox potential parameters of the anode plating solution; when the anode plating When the specific gravity or liquid level or acidity or redox potential of the liquid deviates from the set range, the automatic detection feeding control machine controls the feeding of fresh water into the anode area through a feeding pump to supplement the anode electroplating solution due to water electrolysis and pumping. Gas loss of water. The acidic copper electroplating process using an insoluble anode as described in item 7 of the scope of the patent application, wherein a jet vacuum aeration device is set in step 1 and its suction area is connected to the air outlet of the dosing control device. The liquid port is connected to an oxygen pump, the other end of the oxygen pump is connected to the bottom of the regeneration tank through a pipe, and the liquid outlet of the jet vacuum aeration device is placed in the regeneration tank. The acidic copper electroplating process using an insoluble anode according to item 8 of the scope of the patent application, wherein in step 4, an automatic detection feeding control machine is used to control the acidity and / or ratio of the cathode plating solution and / or the regenerated plating solution. When detecting the color and / or redox potential and / or specific gravity parameters, while controlling the opening and closing of the oxygen source dosing system, the opening and closing of the jet vacuum aeration device are also controlled separately: when the cathode plating solution and When the acidity of the regeneration plating solution is higher than the set value, or the redox potential, or the colorimetric or specific gravity parameter is lower than the set value, the jet vacuum aeration device is turned on to accelerate oxygen in the copper sulfate in the regeneration tank. Plating bath regeneration reaction. The acidic copper electroplating process using an insoluble anode according to item 9 of the scope of the patent application, wherein a screening program is set between the regeneration tank and the pump in step 1 to block the regeneration tank Copper sludge enters the cathode region. The acidic copper electroplating process using an insoluble anode according to item 10 of the scope of patent application, wherein in the step 1, the overflow of the cathode region is connected with a pipe connected to the top of the regeneration tank with a diaphragm to prevent the Traffic. The acidic copper electroplating process using an insoluble anode as described in item 5 of the scope of the patent application, wherein the anode plating solution in step 2 contains copper sulfate at a concentration of 0.001 to 240 g / L. The acidic copper electroplating process using an insoluble anode according to item 5 of the scope of the patent application, wherein the cathode plating solution in step 2 contains sulfuric acid at a concentration of 0.001 to 400 g / L. The acidic copper electroplating process using an insoluble anode according to item 13 of the scope of the patent application, wherein the cathode plating solution contains 10 to 10,000 mg / L of chloride ions, and the source of the chloride ions is hydrochloric acid and / or chloride sodium. A device using an acidic copper electroplating process using an insoluble anode as described in any one of the scope of claims 1 to 14 of the scope of patent application, including the use of an insoluble anode, a cathode, a plating bath, and a copper sulfate plating solution, characterized in that: The electroplating tank is divided into an anode area and a cathode area by a diaphragm, and the diaphragm allows electrons to pass freely. At the same time, a regeneration tank is added, so that the overflow port of the cathode area is connected to the regeneration tank by a pipeline so that the cathode plating solution When it overflows, it overflows into the regeneration tank; the regeneration tank is connected with a pump, and the pump is connected to the cathode region through a return pipe to form a loop, so that the cathode plating solution is in the cathode region and the regeneration tank. The regeneration tank is also connected with an oxygen source dosing system, which is used to control the addition of oxygen; an automatic detection feeding controller is added to detect the The acidity and / or colorimetric and / or redox potential parameters of the regeneration plating solution in the plating solution and / or the regeneration tank are used to control the startup and shutdown of the oxygen source dosing system respectively; in the regeneration tank Reproduced plating solution infused into the cathode region by said pump, said plating solution overflowing the cathode from the cathode region into said conduit through an overflow groove formed regeneration circulation. The equipment for the acid copper electroplating process using an insoluble anode according to item 15 of the scope of the patent application, wherein the oxygen source adding and charging system is mainly composed of an oxygen source and a adding and controlling device, and the adding and controlling device is a control valve Or one or more of a vacuum jet aeration device, or a hood fan system, or a zeolite molecular sieve oxygen generator. According to the equipment of the acidic copper electroplating process using an insoluble anode as described in item 16 of the scope of the patent application, when the oxygen source is the generated oxygen generated on the anode, the addition control device is a pumping device provided directly above the anode area. An air hood fan, the air outlet of the exhaust pipe of the air hood fan is placed in the regeneration tank. The equipment for the acidic copper electroplating process using an insoluble anode according to item 17 of the patent application scope, wherein the separator used to separate the electroplating tank as the anode area and the cathode area adopts an anion membrane or an anode membrane. When an anion membrane is used, the An overflow area is added in the anode area, and is connected to the regeneration tank through a pipeline. The equipment for the acidic copper electroplating process using an insoluble anode according to any one of claims 15 to 18, wherein a jet vacuum aeration device is added, and the suction area of the device is equal to that of the additional investment control device. The gas outlet is connected, and the liquid inlet is connected to an oxygen pump, the other end of the oxygen pump is connected to the bottom of the regeneration tank through a pipe, and the liquid outlet of the jet vacuum aeration device is placed in the regeneration In the slot. The equipment for the acid copper plating process using an insoluble anode according to item 19 of the scope of the patent application, wherein a screening program is provided between the regeneration tank and the pump. According to the equipment of the acidic copper electroplating process using an insoluble anode according to item 19 of the patent application scope, a diaphragm is provided in a pipe connected to the overflow port of the cathode region and the top of the regeneration tank.