TWI648435B - Acidic copper plating process using infused anode and its equipment - Google Patents

Abstract

The invention discloses an acid electroplating copper process and an equipment thereof using an insoluble anode, and the separator is used to separate the electroplating liquid in the anode and the anode regions, thereby avoiding the phenomenon that the electroplating solution in the cathode region is back-etched and the electroplating quality is high. Good, meet the quality requirements of acid copper plating; separately set up a regeneration tank for the preparation of regenerated plating solution, can use copper metal which is cheaper than copper oxide and phosphorous copper, and use oxygen as oxidant to realize the recycling of cathode electroplating solution to prepare sulfuric acid The energy-saving and environmentally friendly process of copper creates better economic effects than the existing technology of using copper oxide and phosphor bronze. It also prevents the added oxygen from regenerating without causing corrosion of the coating and affecting the quality of copper plating.

Description

Acidic copper plating process using insoluble anode and its equipment

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

Existing acid copper plating processes are divided into the use of soluble anodes and the use of insoluble anodes. The soluble anode used in the acid copper plating process is typically phosphor bronze. An insoluble anode refers to an anode that does not occur or rarely undergoes an anodic dissolution reaction during an electrochemical reaction. In an acidic copper plating process, an insoluble anode is usually selected from titanium, graphite, platinum, and a lead alloy coated with a noble metal oxide. Since the phosphorus and copper used in the soluble anode are expensive, and the toxic phosphorus-containing wastewater is generated during the production and use thereof, and the human body is extremely harmful to the liver and the like, the treatment cost of the electroplating waste liquid needs to be increased in order to achieve the wastewater discharge index; In the process of process, anodic polarization and poor current distribution lead to unstable coating quality, so it is more and more common to use insoluble anode process.

A common acid copper plating process using an insoluble anode uses an aqueous solution of copper sulfate and sulfuric acid as a plating solution, and water is decomposed on the anode to form hydrogen ions and oxygen, and copper ions in the plating solution are reduced to metallic copper at the cathode. With the electroplating of copper, the concentration of sulfuric acid in the plating solution is getting higher and higher, and copper oxide is added to react with it. The copper ions lost in the plating solution are replenished and the equivalent amount of sulfuric acid is consumed accordingly. The shortcoming of this method is the quality problem caused by the adhesion of oxygen to the plating plate: due to the water on the anode, the oxygen is dissolved in the plating solution, and the oxygen dissolved in the plating solution is attached to the cathode plating member, causing the coating to be black and loose, thereby affecting the plating. Quality also increases the consumption of organic brighteners and increases costs.

The specific reaction formula is as follows:

Electrochemical reaction on the anode: 2 H ₂ O -4 e ^- → O ₂ ↑ + 4 H ⁺

Electrochemical reaction on the cathode: Cu ²⁺ +2 e ^- → Cu ↓

2 H ⁺ +2 e ^- → H ₂ ↑

Reaction for regeneration of copper sulfate plating solution: CuO + H ₂ SO ₄ → CuSO ₄ + H ₂ O .

Another common acid copper plating process using an insoluble anode is to add iron ions to a plating solution having a main component of copper sulfate and an aqueous sulfuric acid solution, and the electrochemical reaction on the anode is oxidation of divalent iron ions to ferric 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 the quality problems caused by oxygen. However, the presence of ferric ions in the plating solution may cause back-etching of the metallic copper on the cathode, which affects the plating rate.

The specific reaction formula is as follows:

Electrochemical reaction on the anode: Fe ²⁺ - e ^- → Fe ³⁺

Electrochemical reaction on the cathode: Cu ²⁺ +2 e ^- → Cu ↓

Reaction of trivalent iron ions to metallic copper back-etching: Cu +2 Fe ³⁺ → Cu ²⁺ +2 Fe ²⁺ .

A first object of the present invention is to provide an acid electroplating copper process using an insoluble anode, which can effectively solve the quality problem caused by oxygen in the acid copper plating process of the existing insoluble anode, without attacking and corrosion on the plating layer, and not only improving plating Quality, but also save on plating production costs.

The first object of the present invention can be achieved by the following technical solution: an acid electroplating copper process using an insoluble anode, including using an insoluble anode, a cathode, a plating bath, and a copper sulfate plating solution, which is hereinafter referred to as a plating solution. Specifically, the method comprises the following steps: Step 1: preparing a process device: separating the plating tank into an anode region and a cathode region by using a separator, the separator allowing ions to pass through, and adding a copper sulfate plating solution regeneration configuration tank, hereinafter referred to as regeneration a tank, wherein the overflow port of the cathode region is connected to the regeneration tank by a pipe so that the cathode plating solution overflows into the regeneration tank when overflowing; the regeneration tank is connected to a pump, and the pump passes through the return pipe Connected to the cathode region to form a loop, so that the cathode plating solution flows cyclically between the cathode region and the regeneration tank; the regeneration tank is also connected to an oxygen source addition system, and the oxygen source is added The system is used for controlling the addition of oxygen; an automatic detection and feeding control machine is added for detecting the regeneration in the plating solution and/or the regeneration tank in the cathode region Acidity and/or colorimetric and/or redox potential parameter/or specific gravity parameter of the plating solution; Step 2 Preparing a plating solution: preparing an anodizing solution and a cathode plating solution, and pouring the anodizing solution into the anode region Pour the cathode plating solution into the cathode region and the regeneration tank, and at the same time, add metal copper in the regeneration tank; after the copper sulfate plating solution circulation regeneration preparation work starts, the solution in the regeneration tank is called For regeneration Copper sulfate plating solution, referred to as regenerated plating solution; Step 3: Initiating electroplating operation: connecting the insoluble anode to the positive electrode of the power source, immersing in the anodizing solution, connecting the cathode plating member to the negative electrode of the power source, and immersing in the cathode plating solution. Turning on the pumping in step 1, turning on the power of the electrode to perform electroplating operation and circulating regeneration of copper sulfate plating solution; and step 4 controlling the regeneration of the cathode electroplating solution: using the automatic detection feeding controller to the plating solution in the cathode region And/or the regenerated plating solution in the regeneration tank for detection of acidity and/or colorimetric and/or redox potential/or specific gravity parameters and for controlling the start and stop of the oxygen source addition system, respectively: when the cathode plating When the acidity of the liquid and/or the regenerated plating solution is higher than a set value, or the colorimetric or redox potential/or specific gravity is lower than a set value, the oxygen source addition system is turned on to prepare a plating solution in the regeneration tank. Replenishing oxygen, accelerating the regeneration reaction of copper sulfate electroplating solution involving sulfuric acid, metallic copper and oxygen, regenerating sulfuric acid into copper sulfate, and regenerating the plating solution; detecting the cathode When the acidity of the plating solution and/or the regenerated plating solution or the colorimetric or redox potential/or specific gravity reaches a set value, the oxygen source addition and investment system is turned off to stop the supplementation of oxygen; and the cathode electroplating solution regeneration cycle is performed in step 5: Step 4: the regenerated plating solution in the regeneration tank is infused into the cathode region by the pump, and the cathode plating solution flows into the regeneration tank through the pipeline from the cathode region overflow port when the cathode region overflows. Forming a circulating flow of the cathode plating solution, thereby continuously supplementing the cathode plating solution with copper ions and adjusting the sulfuric acid concentration to achieve stabilization of various parameters in the electroplating process.

The working principle of the present invention: although the bipolar electrochemical reaction of the present invention is the same as the electrochemical reaction of the first common acid copper plating process using an insoluble anode mentioned in the background art, the latter uses copper oxide and The sulfuric acid reaction supplements the copper ions lost in the plating solution and consumes the equivalent amount of sulfuric acid accordingly. In the present invention, a regeneration tank is separately provided for the preparation of the regeneration plating solution, and the metal copper and oxygen are used as the oxidant to react with the sulfuric acid, and the cathode plating is consumed. The regenerated chemical reaction equation of the present invention is as follows when the sulfuric acid is regenerated at the same time as the sulfuric acid having a higher concentration in the liquid: O ₂ + H ₂ SO ₄ + Cu → CuSO ₄ + H ₂ O .

Therefore, the process of the present invention can directly use copper metal which is cheaper than copper oxide and phosphorous copper to supplement copper ions in the plating solution, thereby achieving process stability. At the same time, since the regeneration reaction is not carried out in the cathode region, the added oxygen does not enter the cathode region, causing back erosion to the plating layer; in addition, the present invention uses a separator to separate the plating tank into the anode region and the cathode region, so that The design also blocks the oxygen generated by the anode region from approaching the cathode region, thereby preventing the cathode plated metal from being etched back and affecting the quality of the coating.

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

The oxygen source addition and investment system of the present invention is mainly composed of an oxygen source and a feeding control device.

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

When the oxygen source uses bottled compressed oxygen, the feeding control device is a control valve or a jet vacuum aerator; when the oxygen source uses the generated oxygen on the anode, the feeding control device is an exhaust fan, Set directly above the anode region An exhaust fan system, the exhaust pipe outlet of the exhaust fan fan is placed in the regeneration tank; when the oxygen source uses oxygen in the air, the feeding control device may adopt a jet vacuum aeration device. When the former is used, the suction zone is connected to the air, and the liquid inlet is connected to an aeration pump, and the other end of the aeration pump is connected to the bottom of the regeneration tank through a pipe. The jet vacuum aerator The liquid outlet is placed in the regeneration tank; a control valve can also be configured using a compressed air machine or a zeolite molecular sieve oxygen generator.

The present invention can be optimized by the following technical measures.

The anodizing solution of the present invention is an aqueous solution of sulfuric acid having a concentration of 0.001 to 700 g/L; and the cathode plating solution is an aqueous solution of copper sulfate having a concentration of 35 to 240 g/L.

In the present invention, it is also possible to additionally add copper oxide to the regeneration tank, and the copper oxide reacts with the sulfuric acid to rapidly obtain copper sulfate, which contributes to shortening the time required to increase the concentration of copper sulfate in the regenerated plating solution.

The present invention may further comprise copper sulfate in the anodizing solution at a concentration of 0.001 to 240 g/L. By adding copper sulfate, the electrical conductivity of the anodizing 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 hydrolysis of copper sulfate into cuprous sulfate and further into cuprous oxide (Cu ₂ O), thereby Avoid loosening in the coating due to the inclusion of cuprous oxide.

The present invention may further comprise 10 to 10000 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 a small amount of monovalent copper may exist in the cathode plating solution during the electroplating process. The ions affect the flatness of the copper on the cathode plated part, resulting in a rough surface of the plated part. In order to avoid this problem, it is preferred to add an appropriate amount of chloride ions to the cathode plating solution, which can react with monovalent cuprous ions to form copper 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, wherein the suction region is connected to the air outlet of the feeding control device, and the liquid inlet is connected to an oxygen pump, and the other end of the oxygen pump is passed. A pipe is connected to the bottom of the regeneration tank, and a liquid outlet of the jet vacuum aerator is placed in the regeneration tank. The jet vacuum aeration device is used to pass oxygen into the regenerated plating solution in the regeneration tank, and the oxygen can be compressed and mixed with the regenerated plating solution by the pressure formed in the jet vacuum aeration device, thereby accelerating the regeneration of the regenerated plating solution. chemical reaction.

More preferably, the oxygen is controlled when the acidity and/or colorimetric and/or redox potential/or specific gravity parameters of the cathodic plating solution and/or the regenerated plating solution are detected using an automatic detection dosing control machine. While the source feeding system is opened and closed, the opening and closing of the jet vacuum aerator is separately controlled: when the acidity of the cathode plating solution and/or the regenerated plating solution is higher than a set value, or an oxidation-reduction 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 the copper sulfate plating solution in the regeneration tank to stabilize the composition of the cathode plating solution.

The present invention may further provide a screening program between the regeneration tank and the pump, the screening program being capable of effectively blocking copper mud in the regeneration tank from entering the cathode region, thereby avoiding the cathode Copper mud appears near the plated parts and affects the coated products quality.

Preferably, the membrane used in step 1 employs an anion membrane, and when the cathode plating solution is reduced to metallic copper on the cathode plating member with copper ions, the remaining sulfate ions pass through the cathode region under the action of an electric field. The anion membrane enters the anode region and combines with hydrogen ions generated after electrolysis of the anode water to form sulfuric acid, so that the concentration of sulfuric acid in the anode plating solution is higher and higher. An overflow port of the anode region is connected to the regeneration tank through a pipe, and the anode is automatically detected by a charge control machine including one or more detectors including a hydrometer, a liquid level meter, a pH meter, and an ORP meter. The specific gravity and/or the liquid level and/or the acidity and/or the redox potential parameter of the plating solution are detected. On the one hand, when the specific gravity or the liquid level or the acidity or the redox potential of the anodizing solution deviates from the set range, The automatic detection feeding control machine controls the feeding of clean water into the anode region by the feeding pump to keep the concentration of the anode plating solution constant. 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 increased sulfuric acid in the anode plating solution participates in the regeneration reaction of the copper sulfate plating solution in the regeneration tank, and further A stable electroplating process system that achieves a plating fluid regeneration cycle.

Preferably, the membrane used in the step 1 uses a cation membrane, and when hydrogen ions generated after water electrolysis on the anode enter the cathode region through the cation membrane under the action of an electric field, the cathode plating solution is accompanied by copper ions. The cathode plating member is reduced to metal copper and the remaining sulfate ions are combined into sulfuric acid, so that the concentration of sulfuric acid in the cathode plating solution is higher and higher, and the hydrometer, the liquid level meter, the acidity meter, the ORP can be further used. Automatic detection of one or more detectors The specific gravity and/or liquid level and/or acidity and/or redox potential parameters of the anodizing solution are detected by the automatic when the specific gravity or liquid level or acidity or redox potential of the anodizing solution deviates from the set range The detecting and feeding control machine controls the feeding of the clean water into the anode region by the feeding pump, so that part of the water lost by the water electrolysis and the pumping in the anodizing solution is replenished.

The present invention can also provide a diaphragm in the pipe connecting 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. Since the acidic copper sulfate plating solution is usually added with an electroplating brightener whose main component is organic to obtain a brighter copper surface, the electroplating brightener is easily consumed by reacting with oxygen and/or an oxidizing agent, thereby increasing plating during the electroplating process. The amount of brightener used. Therefore, the separator is provided, and the inorganic component having a small molecule in the solution can be effectively passed through the pressure difference to reduce the plating brightener from entering the regeneration tank, thereby achieving the purpose of reducing cost and improving environmental protection.

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

The second object of the present invention can be achieved by the following technical solutions: an acid electroplating copper apparatus using an insoluble anode, including using an insoluble anode, a cathode, a plating bath, and a copper sulfate plating solution, characterized in that the plating is performed using a separator. The trough is divided into an anode region and a cathode region, and the separator allows ions to pass therethrough, and a regeneration tank is additionally provided, so that the overflow port of the cathode region is connected to the regeneration tank by a pipeline, so that the cathode plating solution overflows to the regeneration when it overflows. In the tank; the regeneration tank is connected to a pump, and the pump is connected to the cathode region through a return pipe to form a circuit, so that the cathode plating solution is Circulating flow between the cathode zone and the regeneration tank; the regeneration tank is further connected to an oxygen source addition and investment system, the oxygen source addition and investment system is used for controlling the addition of oxygen; and an automatic detection and feeding control machine is added. For detecting the acidity and/or colorimetric and/or redox potential parameters of the plating solution in the cathode zone and/or the regeneration bath in the regeneration tank, and respectively for controlling the startup and shutdown of the oxygen source addition and investment system Stopping; the regenerated plating solution in the regeneration tank is infused into the cathode region by the pump, and when the cathode plating solution overflows, flowing from the cathode region overflow port into the regeneration tank through a pipeline to form a circulating flow, Thereby, the cathode plating solution is continuously supplemented with copper ions and the sulfuric acid concentration is adjusted to achieve stability of various parameters in the electroplating process.

The oxygen source addition and investment system of the present invention is mainly composed of an oxygen source and a feeding control device. The additional control device may be a control valve, or a vacuum jet aeration device, or an exhaust fan system, or a zeolite molecular sieve oxygen generator configuration.

The separator for separating the plating bath into the anode region and the cathode region according to the present invention may be an anion membrane or an anode separator.

The invention has the following beneficial effects: (1) high quality and high efficiency of copper plating: the present invention utilizes a separator to separate the plating liquid in the anode and cathode regions, thereby avoiding the phenomenon that the cathode plating material in the cathode region is back-etched and the current efficiency is improved. High, good plating quality, meet the quality requirements of acid copper plating; (2) Low energy saving cost: The invention separately provides a regeneration tank for the preparation of the regenerated plating solution, and can use copper metal which is cheaper than copper oxide and phosphor bronze. The use of oxygen as an oxidant to achieve the energy-saving and environmentally friendly process for the preparation of copper sulphate in the recycling of cathode plating solution, which creates better economic effects than the existing technology of using copper oxide and phosphor bronze, and can also avoid The oxygen added by the regeneration does not cause back erosion on the plating layer, which affects the quality of copper plating. (3) Simple and environmentally friendly: The process of the invention is simple and reliable, and can completely replace the acid copper plating process using the soluble phosphorous copper anode to reduce environmental pollution.

1‧‧‧ cathode area

2‧‧‧Anode area

3‧‧‧Exhaust hood fan

4‧‧‧Regeneration tank

5‧‧‧ screening program

6‧‧‧ pump

7‧‧‧Inlet

8‧‧‧liquid outlet

9‧‧‧Inhalation zone

10‧‧‧Separator

11‧‧‧Jet vacuum aeration device

12‧‧‧Oxygen pump

13‧‧‧Return pipe

14‧‧‧ Cathode area overflow

15‧‧‧Anode area overflow

16‧‧‧Zeolite molecular sieve oxygen generator

The invention will now be further described with reference to the drawings and specific embodiments.

1 is a schematic view of an acid copper plating apparatus according to Embodiment 1 and Embodiments 5 to 8 of the present invention.

2 is a schematic view of an acid copper plating apparatus according to Embodiment 2 and Embodiments 10 to 12 of the present invention.

3 is a schematic view of an acid copper plating apparatus according to Embodiment 3 of the present invention.

4 is a schematic view of an acid copper plating apparatus according to Embodiment 4 of the present invention.

Figure 5 is a schematic view of an acid copper plating apparatus according to Embodiment 9 of the present invention.

Figure 6 is a schematic view of the apparatus of the jet vacuum aerator according to Embodiment 2-4 of the present invention and Embodiments 10-12.

The invention is illustrated by the following specific examples. It should be noted that the embodiments are only used to further illustrate the present invention, and do not represent the scope of the present invention. The non-essential modifications and adjustments made by others according to the present invention are still within the scope of the present invention.

In the following examples, the copper sulfate used is preferably Changzhou Hairun Chemical The produced copper sulfate; the sulfuric acid used is preferably sulfuric acid produced by Guangzhou Chemical Reagent Factory; the metal copper used is preferably non-phosphorus copper powder produced by Changsha Tianjiu Metal Materials Co., Ltd. or commercially available pure copper plate or pure copper rod; The anode is preferably a titanium anode plate coated with noble metal oxide produced by Yanxin Titanium Co., Ltd.; the zeolite molecular sieve oxygen generator used is preferably a zeolite molecular sieve oxygen generator produced by Qingdao Sankai Medical Technology Co., Ltd.; The bottled compressed oxygen is preferably compressed oxygen produced by Guangzhou Guangqi Gas Co., Ltd.; the diaphragm used is preferably a diaphragm produced by Membrane International, USA; the microscope used is preferably a computer microscope produced by Guangzhou Optical Instrument Factory; The inspection feeder is preferably an automatic inspection feeder produced by Guangzhou Shigao Chemical Co., Ltd. In addition to the above enumerated, those skilled in the art can achieve the object of the present invention by selecting other products having similar properties to those of the above-listed products according to the conventional selection.

The current efficiency calculation formula-1 is as follows: current efficiency η = m ' ÷ m × 100% = m ' ÷ (I.t.k) × 100% where m ' actual product quality; m theoretical product obtained by Faraday's law Quality; I current intensity (A); t power-on time (h); k electrification equivalent (g / (A. ^h )).

Example 1

The cathode plating solution regeneration cycle system shown in FIG. 1 is an embodiment of the present invention. 1 and the equipment used in Examples 5-8, including insoluble anode (not labeled), cathode plating (not labeled), plating bath, copper sulfate plating solution, regeneration tank 4, metallic copper (not shown), pump 6 The oxygen source feeding system and the automatic detecting feeding control machine (not shown), the acid electroplating copper process using the insoluble anode specifically includes the following steps: Step 1 Prepare the process equipment: use an anion membrane to separate the plating tank into the anode region 2 and In the cathode region 1, the overflow ports of the anode region and the cathode region are simultaneously connected to the top of the regeneration tank 4 by a pipe; the regeneration tank is connected to a pump 6, and the pump passes through the return pipe 13 and the cathode region. Turning on to form a loop; the regeneration tank is further connected to an oxygen source addition and investment system, wherein the oxygen source in the oxygen source addition and investment system is a precipitated oxygen on the anode, and the addition control device is disposed in the anode region 2 The upper air hood fan 3, the air outlet of the exhaust pipe of the air hood fan 3 is placed in the plating solution in the regeneration tank; the anode area 2 and the cathode area 1 are respectively provided with automatic detection and feeding control Machine for detecting the two Technical parameters of the plating solution in the polar region; Step 2 Preparation of the plating solution: Under normal temperature and normal 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; Cathodic plating solution: 150 g/L copper sulfate aqueous solution; and pouring the anodizing solution into the anode region, and pouring the cathode plating solution into the cathode region and the regeneration tank containing metal copper And weigh the initial weight of the cathode plated part; the amount of metal copper is calculated according to the amount of copper to be electroplated, that is, the cathode plating part is plated with X grams of copper, and the total copper content of the metal copper in the regeneration tank should be greater than Or equal to X grams.

Step 3: initiate an electroplating operation: connecting an insoluble anode to a positive electrode of the power source and immersing in the anodizing solution, connecting the cathode plating member to a negative electrode of the power source, and immersing the same In the cathode plating solution; the pumping in step 1 is turned on, the electrode power source is turned on for electroplating operation and the copper sulfate plating solution is recycled and regenerated; and the step 4 controls the cathode plating solution regeneration: using the automatic detection feeding controller to the cathode plating solution The acidity and the specific gravity parameter of the anodizing solution are detected and respectively controlled to shut down the suction blower fan and the clean water addition of the anode region 2, and the acidity setting value is set according to the acidity of the initial cathode plating solution, according to the initial anode The specific gravity of the plating solution is set to a specific gravity setting value; when the acidity of the cathode plating solution is higher than a set value, the air blower fan 3 is turned on to supplement oxygen in the plating solution of the regeneration tank to accelerate sulfuric acid, metal copper and Oxygen-assisted copper sulfate electroplating solution regeneration reaction, regenerating sulfuric acid into copper sulfate to become a regenerated plating solution; when the acidity of the cathode electroplating solution reaches a set value, the exhaust fan 3 is turned off to stop replenishing oxygen; When the specific gravity of the anodizing solution is higher than the set value, the automatic inspection and feeding control machine controls the feeding of the clean water into the anode region 2 by the feeding pump; 5 Cathodic plating solution regeneration cycle: after the plating solution is regenerated in step 4, the pump 6 is infused into the cathode region 1 while the plating solution in the two electrode regions flows through the pipe from the overflow port thereof respectively. A circulating flow is formed in the regeneration tank 4, thereby continuously supplementing the cathode plating solution with copper ions and adjusting the sulfuric acid concentration to achieve stabilization of various parameters in the plating process.

The plating test time is set to 15 hours, the cathode current density is 3 A/dm ² , and the cathode plating member is taken out after the plating time is set; the cathode plating member is cleaned with water and dried by hot air, and then weighed. -1 The current efficiency was calculated, and the surface of the plating was observed using a computer microscope, and the results of the observation were recorded in Table-1.

Example 2

The cathodic plating solution regeneration cycle system shown in Fig. 2 is the apparatus used in the embodiment 2 and the embodiment 10-12 of the present invention, including an insoluble anode (not labeled), a cathode plated member (not labeled), a plating bath, and a copper sulfate plating. Liquid, regeneration tank 4, metal copper (not shown), pump 6, screening program 5, oxygen source addition and investment system, automatic detection and feeding control machine (not shown) and jet vacuum aerator 11 are insoluble. The acid electroplating copper process of the anode specifically includes the following steps: Step 1 Prepare a process device: use a cation film to separate the electroplating bath into an anode region 2 and a cathode region 1, the overflow port of the cathode region 1 and the top of the regeneration tank 4 The regeneration tank 4 is connected to the screening program 5 and the pump 6 in sequence, and the pump 6 is connected to the cathode region 1 through a return pipe 13 to form a circuit; the regeneration tank 4 is also added to the oxygen source. The system is connected, the oxygen source in the oxygen source feeding system is the oxygen generated on the anode, and the feeding control device is an air extracting fan 3 disposed directly above the anode region, and the exhaust fan 3 Exhaust pipe outlet and jet vacuum aeration The suction zone 9 of the jet 11 is connected, and the liquid inlet 7 of the jet vacuum aerator is sequentially connected to the bottom of the oxygen pump 12 and the regeneration tank 4 through a pipe, and the liquid of the jet vacuum aerator 11 is discharged. The port 8 is placed in the regeneration tank 4; an automatic detection and feeding control machine is arranged for the cathode region 1, the anode region 2 and the regeneration tank 4, respectively, for respectively detecting technical parameters of the plating solution in the two electrode regions; Step 2: Preparing a plating solution: at normal temperature and pressure, according to Table-1, preparing an anodizing solution and a cathode plating solution, wherein the anodizing solution: a mixed aqueous solution of 200 g/L copper sulfate and 100 g/L sulfuric acid; Liquid: 200g / L copper sulfate, 100g / L sulfur a mixed aqueous solution of acid; pouring the anodizing solution into the anode region 2, and pouring the cathode plating solution into the cathode region 1 and a regeneration tank containing a mixture of 1:1 metal copper and copper oxide 4, and weigh the initial weight of the cathode plated part; the amount of metal copper and copper oxide mixture is determined by plating X grams of copper on the cathode plated part, and the total copper content of the mixture of metal copper and copper oxide in the regeneration tank Should be greater than or equal to X grams.

Step 3: Initiating a plating operation: connecting an insoluble anode to a positive electrode of the power source and immersing it in the anodizing solution, connecting the cathode plating member to a negative electrode of the power source, and immersing in the cathode plating solution; and turning on the pump 6 in step 1, Turning on the electrode power source to perform the plating operation and the copper sulfate plating solution circulation regeneration preparation; Step 4 controlling the cathode plating solution regeneration: using the automatic detection and feeding control machine to respectively compare the colorimetric color of the cathode plating solution and the regeneration plating solution in the regeneration tank 4 and The liquid level parameter of the anodizing solution is detected, and the starting and stopping of the jet vacuum aerator 11 and the extraction hood fan 3 and the clean water addition of the anode zone 2 are respectively controlled by the parameters, according to The color depth of the initial cathodic plating solution is set to a color setting value, and the liquid level setting value is set according to the liquid level of the initial anodizing solution; when the color ratio of the cathode plating solution or the regenerated plating solution is lower than a set value, the jet is turned on The vacuum aerator 11 and the air hood fan 3 are used to supplement oxygen in the plating solution of the regeneration tank 4 to accelerate the copper sulfate plating solution in which sulfuric acid, metallic copper and oxygen participate. Regenerating the reaction, regenerating the sulfuric acid into copper sulfate to become a regenerated plating solution; when the color ratio of the cathode plating solution or the regenerated plating solution reaches a set value, turning off the extraction hood fan 3, stopping the supplemental oxygen; When the liquid level of the plating solution is lower than the set value, it is controlled by the automatic inspection material The machine controls the feeding of the clean water into the anode region 2 by the feeding pump; the step 5: the cathode plating solution regeneration cycle: after the reconstituted plating solution in the regeneration tank 4 is configured in step 4, the pump 6 is infused into the cathode region 1 At the same time, the cathode plating solution flows into the regeneration tank 4 through the pipeline from the overflow port of the cathode region 1 to form a circulating flow, thereby continuously supplementing the cathode plating solution with copper ions and adjusting the sulfuric acid concentration to realize the electroplating process. The stability of each parameter.

The plating test time is set to 15 hours, the cathode current density is 3 A/dm ² , and the cathode plating member is taken out after the plating time is set; the cathode plating member is cleaned with water and dried by hot air, and then weighed. -1 The current efficiency was calculated, and the surface of the plating was observed using a computer microscope, and the results of the observation were recorded in Table-1.

Example 3

The cathode plating solution regeneration cycle system shown in FIG. 3 is the apparatus used in the third embodiment of the present invention, and includes an insoluble anode (not labeled), a cathode plating member (not labeled), a plating tank, a copper sulfate plating solution, and a regeneration tank 4. Metal copper (not shown), pump 6, screening program 5, oxygen source addition system, automatic detection feeding controller (not shown) and jet vacuum aeration device 11, which uses an acid-plated copper process with an insoluble anode Specifically, the method includes the following steps: Step 1: preparing a process device: separating a plating tank into an anode region 2 and a cathode region 1 by using a cationic membrane, and an overflow port of the cathode region 1 is connected to a top of the regeneration tank 4 by a pipeline, the pipeline a diaphragm is disposed thereon; the regeneration tank 4 is sequentially connected to the screening program 5 and the pump 6, and the pump 6 is connected to the cathode region 1 through a return pipe 13 to form a circuit; the regeneration tank 4 is also connected to an oxygen source. The feeding system is connected, and the oxygen source is added to the investment system. The oxygen source is bottled compressed oxygen, and the addition control device is a jet vacuum aeration device 11 connected to the bottled compressed air, and the liquid inlet 7 of the jet vacuum aerator 11 is The bottom of the regeneration tank 4 is connected by a pipe, and the liquid outlet 8 of the jet vacuum aerator is placed in the regeneration tank 4; the cathode zone 1, the anode zone 2 and the regeneration tank 4 are respectively provided with automatic detection and feeding. a control machine for respectively detecting technical parameters of the plating solution in the two electrode regions; and step 2 preparing a plating solution: at normal temperature and pressure, according to Table-1, preparing an anodizing solution and a cathode plating solution, wherein Anodizing solution: a mixed aqueous solution of 240 g/L copper sulfate and 50 g/L sulfuric acid; a cathode plating solution: a mixed aqueous solution of 240 g/L copper sulfate, 50 g/L sulfuric acid, and 10 mg/L hydrochloric acid; and the anode plating solution is poured In the anode region 2, the cathode plating solution is poured into the cathode region 1 and the regeneration tank 4 containing a mixture of 1:1 metal copper and copper oxide, and the initial weight of the cathode plating member is weighed; Step 3 Start the plating operation: the insoluble anode and The source positive electrode is connected and immersed in the anodizing solution, the cathode plating member is connected to the negative electrode of the power source and immersed in the cathode plating solution; the pump 6 is turned on in step 1, the electrode power source is turned on for electroplating operation and copper sulfate The electroplating solution is recycled and regenerated; the step 4 controls the cathode electroplating solution regeneration: the auto-detection feeding control machine is used to respectively detect the oxidation-reduction potential of the regenerated electroplating solution, the specific gravity of the anodizing solution, and the oxidation-reduction potential parameter, and utilize the The parameters respectively control the start and stop of the jet vacuum aeration device and the clean water addition of the anode region 2, and set the redox potential setting value of the cathode plating solution according to the oxidation reduction potential of the initial cathode plating solution, according to the initial anode The specific gravity of the plating solution and the oxidation-reduction potential are respectively set to the anode a specific gravity of the plating solution and a redox potential setting value; when the redox potential of the regenerated plating solution is lower than a set value, the jet vacuum aerator 11 is turned on to supplement oxygen in the plating solution of the regeneration tank 4, Accelerating the regeneration reaction of the copper sulfate plating solution in which sulfuric acid, metallic copper and oxygen participate, and regenerating the sulfuric acid into copper sulfate to become a regenerated plating solution; when the redox potential of the regenerated plating solution reaches a set value, the jet vacuum aeration device 11 is turned off. Stopping the supplemental oxygen; when the specific gravity or ORP parameter of the anodizing solution is higher than the set value, the automatic inspection and feeding control machine controls the feeding of the clean water into the anode region 2 through the feeding pump; Circulation: after the reconstituted plating solution in the regeneration tank 4 is configured in step 4, it is infused into the cathode region 1 through the pump 6, while the cathode plating solution flows from the overflow port of the cathode region 1 through the pipeline. A circulating flow is formed in the regeneration tank 4, thereby continuously supplementing the cathode plating solution with copper ions and adjusting the sulfuric acid concentration to achieve stabilization of various parameters in the plating process.

The plating test time is set to 15 hours, the cathode current density is 3 A/dm ² , and the cathode plating member is taken out after the plating time is set; the cathode plating member is cleaned with water and dried by hot air, and then weighed. -1 The current efficiency was calculated, and the surface of the plating was observed using a computer microscope, and the results of the observation were recorded in Table-1.

Example 4

The cathode electroplating solution regeneration cycle system shown in FIG. 4 is the apparatus used in the fourth embodiment of the present invention, and includes an insoluble anode (not labeled), a cathode plating member (not labeled), a plating tank, a copper sulfate plating solution, a regeneration tank 4, Metal copper (not shown), pump 6, screening program 5, oxygen source addition and investment system, automatic detection and feeding control machine (not shown) And the jet vacuum aeration device 11, the acid electroplating copper process using the insoluble anode specifically includes the following steps: Step 1 Prepare the process equipment: use a cationic membrane to separate the electroplating bath into an anode region 2 and a cathode region 1, the cathode region 1 The overflow port is connected to the top of the regeneration tank 4 by a pipe, and the pipe is provided with a diaphragm; the regeneration tank 4 is sequentially connected to the screening program 5, and the pump 6 is passed, and the pump 6 passes through another pipe 13 Connected to the cathode region 1 to form a loop; the regeneration tank 4 is also connected to an oxygen source addition system, wherein the oxygen source in the oxygen source addition system is a precipitated oxygen on the anode and oxygen in the air, plus The injection control device is an air hood fan 3 and a zeolite molecular sieve oxygen generator 14 disposed directly above the anode region, and an air outlet of the exhaust pipe of the air hood fan 3 and an air suction of the jet vacuum aerator 11 The area 9 is connected, and the liquid inlet 7 of the jet vacuum aerator is sequentially connected to the bottom of the oxygen pump 12 and the regeneration tank 4 through a pipe, and the liquid outlet 8 of the jet vacuum aerator 11 is placed In the regeneration tank 4; respectively, the cathode 1. The anode zone 2 and the regeneration tank 4 are provided with an automatic detection feeding control machine for respectively detecting the technical parameters of the plating solution in the two electrode zones; and step 2 preparing the plating solution: under normal temperature and pressure, according to Table-1 An anode plating solution and a cathode plating solution are prepared, wherein the anode 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 a mixed aqueous solution of hydrochloric acid; the anode plating solution is poured into the anode region 2, and the cathode plating solution is poured into the cathode region 1 and the regeneration tank containing a mixture of 1:1 metal copper and copper oxide. 4, and weigh the initial weight of the cathode plated part; step 3 initiates the plating operation: connect the anode to the positive electrode of the power source and immerse the anode In the electroplating solution, the cathode plating member is connected to the negative electrode of the power source and immersed in the cathode plating solution; the pump 6 is turned on in step 1, the electrode power source is turned on for electroplating operation, and the copper sulfate plating solution is recycled and reconstituted; 4 controlling the cathode plating solution regeneration: detecting the oxidation-reduction potential of the regenerated plating solution in the regeneration tank and the acidity parameter of the anode plating solution by using an automatic detection feeding controller, and respectively controlling the jet vacuum aeration device 11 and the start and stop of the hood fan 3 and the clean water addition of the anode zone 2, setting the specific gravity setting value according to the specific gravity of the initial cathode plating solution, and setting the acidity setting value according to the acidity of the initial anodizing solution; When the oxidation-reduction potential of the regenerated plating solution is lower than a set value, the jet vacuum aeration device 11 and the extraction hood fan 13 are turned on to supplement oxygen in the plating solution of the regeneration tank 4 to accelerate sulfuric acid, metallic copper and oxygen. Reactive reaction of the participating copper sulfate plating solution to regenerate sulfuric acid into copper sulfate to become a regenerated plating solution; when the specific gravity of the plating solution is lower than a set value, Closing the jet vacuum aeration device 11 and the air hood fan 13 to stop replenishing oxygen; when the acidity of the anodizing solution is higher than a set value, the automatic inspection material control machine controls the anode through the feeding pump The clean water is discharged in the zone 2; the cathode electroplating solution regeneration cycle in step 5: after the reconstituted 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 is The overflow region of the cathode region 1 flows into the regeneration tank 4 through a pipeline to form a circulating flow, thereby continuously supplementing the cathode plating solution with copper ions and adjusting the sulfuric acid concentration to achieve stabilization of various parameters in the electroplating process.

The plating test time is set to 15 hours, and the cathode current density is 3 A/dm ² . After the plating time is set, the cathode plating member is taken out; the cathode plating member is cleaned with water and dried by hot air, and then weighed. -1 The current efficiency was calculated, and the surface of the plating was observed using a computer microscope, and the results of the observation were recorded in Table-1.

Example 5

The difference between the embodiment 5 and the embodiment 1 is that the anode plating solution and the cathode plating solution are prepared according to Table-1 under normal temperature and normal pressure, wherein the anode plating solution: 50 g/L copper sulfate, 150 g/L sulfuric acid. Mixed aqueous solution; cathode plating solution: a mixed aqueous solution of 35 g/L of copper sulfate, 220 g/L of sulfuric acid, and 8239 mg/L of hydrochloric acid.

Example 6

The difference between the embodiment 6 and the embodiment 1 is that the anode plating solution and the cathode plating solution are prepared according to Table-1 under normal temperature and normal pressure, wherein the anode plating solution: 150 g/L copper sulfate, 90 g/L sulfuric acid. Mixed aqueous solution; cathodic plating solution: a mixed aqueous solution of 100 g/L of copper sulfate, 190 g/L of sulfuric acid, and 10282 mg/L of hydrochloric acid.

Example 7

The difference between the embodiment 7 and the embodiment 1 is that the anode plating solution and the cathode plating solution are prepared according to Table-1 under normal temperature and normal pressure, wherein the anode plating solution: 100 g/L copper sulfate, 60 g/L sulfuric acid. Mixed aqueous solution; cathodic plating solution: a mixed aqueous solution of 100 g/L of copper sulfate, 220 g/L of sulfuric acid, 4078 mg/L of hydrochloric acid, and 5000 mg/L of sodium chloride.

Example 8

The difference between the embodiment 8 and the embodiment 1 is that, under normal temperature and normal pressure, an anodizing solution and a cathodic plating solution are prepared according to Table-1, wherein the anodizing solution: A mixed aqueous solution of 35 g/L of copper sulfate and 250 g/L of sulfuric acid; a cathode plating solution: a mixed aqueous solution of 50 g/L of copper sulfate, 250 g/L of sulfuric acid, and 10 mg/L of hydrochloric acid.

Example 9

The cathodic plating solution regeneration cycle system shown in Fig. 1 is the apparatus used in the first embodiment and the examples 5-8 of the present invention, including an insoluble anode (not labeled), a cathode plated member (not labeled), a plating bath, and a copper sulfate plating. Liquid, regeneration tank 4, metal copper (not shown), pump 6, oxygen source feeding system and automatic detection feeding control machine (not shown), the acid electroplating copper process using insoluble anode specifically includes the following steps: 1 preparation process equipment: using a common electroplating diaphragm to separate the electroplating tank into an anode zone 2 and a cathode zone 1, the overflow port of the cathode zone 1 is connected to the top of the regeneration tank 4 by a pipe; the regeneration tank is connected to the 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 system, and the oxygen source in the oxygen source addition system is generated on the anode. The evolved oxygen, the addition control device is an air hood fan 3 disposed directly above the anode region, and the air outlet of the exhaust pipe of the air hood fan 3 is connected to the bottom of the regeneration tank 4 through a pipeline; For the cathode region 1, the anode region 2 and The regeneration tank is provided with an automatic detection feeding control machine for respectively detecting the technical parameters of the plating solution in the two electrode regions; Step 2 preparing the plating solution: at normal temperature and pressure, according to Table-1, preparing the anode plating solution and Cathodic plating solution, wherein: anodizing solution: 50 g / L copper sulfate, 0.001 g / L sulfuric acid mixed aqueous solution; cathode plating solution: 50 g / L copper sulfate, 0.001 g / L sulfuric acid mixed aqueous solution; the anodizing solution Pour into the anode region 2, and pour the cathode plating solution into the cathode region 1 and the metal copper-containing regeneration tank 4, And weighing the initial weight of the cathode plating member; step 3 starts the plating operation: connecting the insoluble anode to the positive electrode of the power source and immersing in the anodizing solution, connecting the cathode plating member to the negative electrode of the power source and immersing in the cathode plating solution The pump 6 is turned on in step 1, the electrode power is turned on for electroplating operation and the copper sulfate plating solution is recycled and regenerated; and the step 4 controls the cathode electroplating solution regeneration: the acidity of the cathode electroplating solution is separately performed by using an automatic detecting and feeding control machine. Detecting and controlling the start and stop of the air hood fan 3, setting an acidity setting value according to the acidity of the initial cathode plating solution, and opening the air hood fan 3 when the acidity of the cathode plating solution is higher than a set value. In order to supplement oxygen in the plating solution of the regeneration tank 4, accelerate the regeneration reaction of the copper sulfate plating solution in which sulfuric acid, metallic copper and oxygen participate, and regenerate the sulfuric acid into copper sulfate to become a regenerated plating solution; when the cathode plating solution is acidity When the set value is reached, the air blower fan 3 is turned off, and the supplemental oxygen is stopped; Step 5: Cathodic plating liquid regeneration cycle: in the regeneration tank 4 in step 4 After the plating solution is configured, it is infused into the cathode region 1 through the pump 6, and the cathode plating solution flows into the regeneration tank 4 through the pipeline from the overflow port of the cathode region 1 to form a circulating flow, thereby The cathode plating solution continuously replenishes copper ions and adjusts the concentration of sulfuric acid to achieve stability of various parameters in the electroplating process.

The plating test time is set to 15 hours, the cathode current density is 3 A/dm ² , and the cathode plating member is taken out after the plating time is set; the cathode plating member is cleaned with water and dried by hot air, and then weighed. -1 The current efficiency was calculated, and the surface of the plating was observed using a computer microscope, and the results of the observation were recorded in Table-1.

Example 10

The difference between the embodiment 10 and the embodiment 2 is that the anode plating solution and the cathode plating solution are prepared according to Table-1 under normal temperature and normal pressure, wherein the anode plating solution: 0.001 g/L copper sulfate, 400 g/L sulfuric acid. Mixed aqueous solution; cathode plating solution: a mixed aqueous solution of 100 g/L copper sulfate and 300 g/L sulfuric acid.

Example 11

The difference between the embodiment 11 and the embodiment 2 is that the anode plating solution and the cathode plating solution are prepared according to Table-1 under normal temperature and normal pressure, wherein the anode plating solution: 550 g/L sulfuric acid; the cathode plating solution: 200 g/ A mixed aqueous solution of L copper sulfate and 350 g/L sulfuric acid.

Example 12

The difference between the embodiment 12 and the embodiment 2 is that the anode plating solution and the cathode plating solution are prepared according to Table-1 under normal temperature and normal pressure, wherein the anode plating solution: 700 g/L sulfuric acid; the cathode plating solution: 240 g/ A mixed aqueous solution of L copper sulfate and 400 g/L sulfuric acid.

Comparative example 1

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

Step 1: The components specified in Table 1 were dissolved in water according to the ratio to prepare a plating solution.

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

Step 3: Using an insoluble anode, the anode and cathode plating members are immersed in the plating solution and respectively connected to the positive and negative electrodes of the power source.

Step 4: Conducting electroplating operation, setting the electroplating test time to 15 hours, and the cathode current density to 3 A/dm ² . During the electroplating process, copper oxide is added to the electrolytic cell to supplement the copper ion content of the electrolyte, and the cathode is plated after the electroplating is completed. Remove the pieces. After the plated parts were cleaned with clean water and dried with hot air, the weight of the plated parts was weighed. The current efficiency was calculated according to Equation 1, and the surface of the plating was observed using a computer microscope, and the results of the observation were recorded in Table 1.

Comparative example 2

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

Claims (21)

An acid electroplating copper process using an insoluble anode, comprising using an insoluble anode, a cathode, a plating bath, and a copper sulfate plating solution, comprising the steps of: Step 1, preparing a process equipment: dividing the electroplating tank into an anode region using a separator And a cathode region, the separator allows passage of ions while adding a regeneration tank, the overflow port of the cathode region is connected to the regeneration tank by a pipeline; the regeneration tank is connected to a pump, and the pump is passed through a return pipe The cathode region is turned on to form a loop; the regeneration tank is further connected to an oxygen source feeding system for controlling the addition of oxygen; and an automatic detecting feeding controller is provided for detecting the cathode Acidity and / or colorimetric and / or redox potential parameters / or specific gravity parameters of the plating solution in the plating solution and / or regeneration tank in the zone; Step 2, preparing the plating solution: preparing the anode plating solution and the cathode plating solution, And pouring the anodizing solution into the anode region, pouring the cathode plating solution into the cathode region and the regeneration tank, and simultaneously adding metal to the regeneration tank The anode plating solution is an aqueous solution of sulfuric acid, and the cathode plating solution is an aqueous solution of copper sulfate; after the start of the circulation regeneration preparation of the copper sulfate plating solution, the solution in the regeneration tank is a regenerated plating solution; and step 3, the plating operation is started. : connecting the insoluble anode to the positive electrode of the power source, immersing in the anode plating solution, connecting the cathode plating member to the negative electrode of the power source, immersing in the cathode plating solution, turning on the pumping in step 1, and turning on the power of the electrode Performing electroplating operations and recycling of copper sulfate plating solution; Step 4, controlling the cathode plating solution regeneration: using an automatic detection feeding controller to perform acidity and/or colorimetric and/or redox potential parameters on the plating solution in the cathode region and/or the regeneration plating solution in the regeneration tank. The detection of the specific gravity parameter is respectively used to control the starting and shutting down of the oxygen source feeding system: when the acidity of the cathode plating solution and/or the regenerated plating solution is higher than a set value, or a colorimetric or redox potential/ When the specific gravity parameter is lower than the set value, the oxygen source feeding system is turned on; when the cathode plating solution and/or the regenerated plating solution is detected, the acidity, or the colorimetric or redox potential/or specific gravity parameter reaches the set value. Turning off the oxygen source addition system to stop replenishing oxygen; and step 5, a cathode electroplating solution regeneration cycle: the regenerated plating solution in the regeneration tank in step 4 is infused into the cathode region by the pump, Cathodic plating solution flows into the regeneration tank from the overflow region of the cathode region through a pipe to form a circulating flow. An acid electroplating copper process using an insoluble anode according to claim 1, wherein the anodizing solution in step 2 is a sulfuric acid aqueous solution having a concentration of 0.001 to 700 g/L; and the cathode plating solution is at a concentration of 35 to 240 g/L. An aqueous solution of copper sulfate. An acid electroplating copper process using an insoluble anode according to claim 2, wherein the oxygen source addition system comprises an oxygen source and a charging control device, wherein the oxygen source is a precipitated oxygen on the anode. One or more of oxygen in the air and oxygen emitted from the bottled compressed oxygen; the feeding and controlling device is one or more of a jet vacuum aerator, an air hood fan, a compressed air machine, and a zeolite molecular sieve oxygen generator. . Acidic electricity using insoluble anodes as described in claim 3 a copper plating process, wherein in step 1, when the oxygen source is used to generate precipitated oxygen on the anode, the additional control device is an air hood fan, and an air hood fan system is disposed directly above the anode region, The exhaust pipe outlet of the exhaust fan fan is placed in the plating solution in the regeneration tank. An acid electroplating copper process using an insoluble anode according to claim 3, wherein in the step 2, copper oxide is additionally added to the regeneration tank, and the amount of the metal copper and the copper oxide mixture is on the cathode plating member. The amount of copper plating is determined such that 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. An acid electroplating copper process using an insoluble anode according to any one of claims 1 to 4, wherein when the anion membrane is selected as the membrane in the step 1, the overflow port of the anode region is added. And connected to the regeneration tank through a pipeline; and in step 4, the proportion of the anodizing solution is automatically determined by using an automatic inspection and feeding control machine including one or more detectors of a hydrometer, a liquid level meter, a pH meter, and an ORP meter. And/or the liquid level and/or the acidity and/or the redox potential parameter are detected. On the one hand, when the specific gravity or the liquid level or the acidity or the redox potential of the anodizing solution deviates from the set range, the automatic detection is performed by the automatic detection. The control machine controls the feeding of clean water into the anode region by the feed pump to keep the concentration of the anode plating solution constant; on the other hand, the anode plating solution overflows in the anode region and flows into the regeneration through the overflow port. After the bath, the increased sulfuric acid in the anodizing bath participates in the copper sulfate plating solution regeneration reaction in the regeneration tank. Insoluble use as described in any one of claims 1 to 4 An acidic electroplating copper process for an anode, wherein when the membrane used in step 1 uses a cationic membrane, in step 4, an automatic detection dosing control pair comprising one or more detectors including a hydrometer, a liquid level gauge, a pH meter, and an ORP meter is used. The specific gravity and/or the liquid level and/or the acidity and/or the redox potential parameter of the anodizing solution are detected; when the specific gravity or the liquid level or the acidity or the redox potential of the anodizing solution deviates from the set range, The automatic detection feeding control machine controls the feeding of clean water into the anode region by the feeding pump to supplement the water lost in the anodizing solution due to water electrolysis and pumping. An acid electroplating copper process using an insoluble anode according to claim 7, wherein in the step 1, a jet vacuum aeration device is provided, the suction region of which is connected to the gas outlet of the additional control device, The liquid port is connected to an oxygen pump, and 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 aerator is placed in the regeneration tank. An acid electroplating copper process using an insoluble anode according to claim 8, wherein the acidity and/or ratio of the cathode plating solution and/or the regenerated plating solution is automatically used in step 4 using an automatic detection dosing controller. When the color and/or redox potential/or specific gravity parameter is detected, the opening and closing of the jet vacuum aerator is separately controlled while controlling the opening and closing of the oxygen source feeding system: when the cathode plating solution and / or the acidity of the regenerated plating solution is higher than a set value, or the oxidation-reduction potential or the colorimetric or specific gravity parameter is lower than a set value, the jet vacuum aeration device is turned on to accelerate the copper sulfate in the regeneration tank The plating solution is regenerated. An acid electroplating copper process using an insoluble anode according to claim 9, wherein a screening is performed between the regeneration tank and the pump in step 1. a program for blocking copper mud in the regeneration tank from entering the cathode region. An acid electroplating copper process using an insoluble anode according to claim 10, wherein in the step 1, the overflow port of the cathode region and the pipe connected to the top of the regeneration tank are provided with a separator to block organic matter. Pass. An acid electroplating copper process using an insoluble anode according to claim 5, wherein in the step 2, the anodizing solution contains copper sulfate at a concentration of 0.001 to 240 g/L. An acid electroplating copper process using an insoluble anode according to claim 5, wherein in the step 2, the cathodic plating solution contains sulfuric acid having a concentration of 0.001 to 400 g/L. An acid electroplating copper process using an insoluble anode according to claim 13, wherein the cathodic plating solution contains 10 to 10000 mg/L of chloride ions, and the source of the chloride ions is hydrochloric acid and/or sodium chloride. . An apparatus for using an acid electroplating copper process using an insoluble anode according to any one of claims 1 to 14, comprising using an insoluble anode, a cathode, a plating bath, and a copper sulfate plating solution, characterized in that: The electroplating bath is divided into an anode region and a cathode region by using a diaphragm, the diaphragm allows ions to pass through, and 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 the cathode plating solution is full. Overflowing into the regeneration tank; the regeneration tank is connected to a pump, and the pump is connected to the cathode region through a return pipe to form a circuit, so that the cathode plating solution is in the cathode region and the regeneration tank Inter-circulation flow; the regeneration tank is also connected to an oxygen source addition system for controlling the addition of oxygen Adding an automatic detection and feeding control machine for detecting the acidity and/or colorimetric and/or redox potential parameters of the plating solution in the cathode region and/or the regeneration plating solution in the regeneration tank, and respectively for controlling Starting and shutting down the oxygen source addition system; the regenerated plating solution in the regeneration tank is instilled into the cathode zone by the pump, and the cathode plating solution overflows from the cathode area overflow port through the pipeline when the cathode plating solution overflows A circulating flow is formed in the regeneration tank. The apparatus of the acidic electroplating copper process using an insoluble anode according to claim 15, wherein the oxygen source addition and investment system is mainly composed of an oxygen source and a feeding control device, and the feeding control device is a control valve. Or one or more of a vacuum jet aeration device, or an extraction hood fan system, or a zeolite molecular sieve oxygen generator. The apparatus of the acid electroplating copper process using an insoluble anode according to claim 16, wherein when the oxygen source is used to generate precipitated oxygen on the anode, the additional control device is pumped directly above the anode region. A hood fan, the exhaust pipe of the hood fan is placed in the regeneration tank. An apparatus for an acid electroplating copper process using an insoluble anode according to claim 17, wherein the separator for separating the plating bath into the anode region and the cathode region is an anion membrane or an anode separator, and when an anion membrane is used, An overflow port is added to the anode region, and is connected to the regeneration tank through a pipe. An apparatus for an acid electroplating copper process using an insoluble anode according to any one of claims 15 to 18, wherein a jet vacuum aeration device is added, an intake region thereof and the additional control device The air outlet is connected, and its inlet port Then, an oxygen-enriched pump is connected, and the other end of the oxygen-enriched pump is connected to the bottom of the regeneration tank through a pipeline, and a liquid outlet of the jet vacuum aerator is placed in the regeneration tank. An apparatus for an acid electroplating copper process using an insoluble anode according to claim 19, wherein a screening program is provided between the regeneration tank and the pump. An apparatus for an acid electroplating copper process using an insoluble anode according to claim 19, wherein the overflow port of the cathode region is provided with a separator in a pipe connected to the top of the regeneration tank.