A persulfate micro-etching solution circulation and regeneration device system

Abstract

This invention provides a persulfate micro-etching solution recycling and regeneration device system, including an electrodialysis unit, an electrolysis unit, and a regeneration electrolysis unit. The electrodialysis unit includes an electrodialysis tank with a cathode and an anode arranged opposite each other on both sides. An anion exchange membrane and a cation exchange membrane divide the part of the electrodialysis tank between the cathode and anode chambers into several desalination chambers and several concentrate chambers. The inlets of the desalination chambers and the concentrate chambers are used to introduce persulfate micro-etching solution. The outlet of the desalination chamber is connected to the anode inlet of the regeneration electrolysis unit, and the outlet of the concentrate chamber is connected to the inlet of the electrolysis unit. By combining the electrodialysis unit, the electrolysis unit, and the regeneration electrolysis unit, this invention can not only recover residual sodium persulfate in the waste liquid, but also recover high-quality metallic copper from the cathode. The regenerated micro-etching solution can be 100% reused in the production line, with no wastewater discharge. The equipment investment is small and the energy consumption is low.

Description

Technical Field

[0001] This utility model belongs to the field of persulfate micro-etching solution recycling and regeneration technology, and relates to a persulfate micro-etching solution recycling and regeneration device system. Background Technology

[0002] Persulfate micro-etching solutions are commonly used for etching copper. However, as etching progresses, the accumulation of sulfate in the persulfate micro-etching solution limits the amount of copper that can be dissolved. In this case, the persulfate micro-etching solution needs to be regenerated after etching.

[0003] Traditional persulfate micro-etching solution regeneration devices for copper electrolysis only achieve a copper recovery rate of 70-80%. Furthermore, the residual liquid after electrolysis requires secondary treatment before discharge, wasting chemical raw materials and increasing labor costs as micro-etching line workers need to prepare persulfate micro-etching solution daily. Additionally, the equipment requires manual operation and has low automation. While BBD offline electrolysis can recover copper from the waste liquid and regenerate sodium persulfate, the uneven current distribution during electrolysis due to the material and size of the BBD electrode results in poor quality copper recovered from the cathode.

[0004] In other words, currently available persulfate etching solutions rarely allow for recycling, and not all copper in the persulfate etching solution can be recovered. Either the equipment investment is large, resulting in high-quality recovered copper, or the equipment investment is small, resulting in poor-quality recovered copper. Therefore, there is an urgent need to design a persulfate micro-etching solution recycling and regeneration device system to overcome the shortcomings of existing technologies and meet practical application needs. Utility Model Content

[0005] To address the shortcomings of existing technologies, the purpose of this invention is to provide a persulfate micro-etching solution recycling and regeneration device system. This system, through the combined use of an electrodialysis unit, an electrolysis unit, and a regeneration electrolysis unit, not only recovers residual sodium persulfate from the waste liquid, but also yields high-quality copper from the cathode. The regenerated micro-etching solution can be 100% reused in the production line, with no wastewater discharge. The entire recycling and regeneration system for copper recovery features low equipment investment, low energy consumption, simple structure, and high reliability.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] This utility model provides a persulfate micro-etching solution circulation and regeneration device system, including an electrodialysis unit, an electrolysis unit, and a regeneration electrolysis unit;

[0008] The electrodialysis unit includes an electrodialysis tank, in which a cathode and an anode are arranged opposite each other on both sides. An anion exchange membrane and a cation exchange membrane are alternately arranged between the cathode and the anode. The anion exchange membrane and the cathode form a cathode chamber, and the cation exchange membrane and the anode form an anode chamber. The anion exchange membrane and the cation exchange membrane divide the part of the electrodialysis tank between the cathode chamber and the anode chamber into several desalination chambers and several concentrate chambers.

[0009] The inlet of the freshwater chamber and the inlet of the concentrated water chamber are both used to connect to the persulfate micro-etching solution.

[0010] The outlet of the freshwater chamber is connected to the anode inlet of the regeneration electrolysis unit, and the anode outlet of the regeneration electrolysis unit is used to recycle the product liquid into the micro-etching line.

[0011] The outlet of the concentrate chamber is connected to the inlet of the electrolysis unit, and the outlet of the electrolysis unit is used to recycle the product liquid into the micro-etching line.

[0012] The persulfate micro-etching solution recycling and regeneration device system provided by this utility model uses a combination of an electrodialysis unit, an electrolysis unit, and a regeneration electrolysis unit. It can not only recover residual sodium persulfate in the waste liquid, but also recover high-quality metallic copper from the cathode. The regenerated micro-etching solution can be 100% reused in the production line without any wastewater discharge. The entire recycling and regeneration device system has low equipment investment, low energy consumption, simple structure, and high reliability in the process of copper recovery.

[0013] As a preferred technical solution of this utility model, the anode is an iridium-tantalum-titanium-based anode or a lead dioxide-titanium-based anode.

[0014] In a preferred embodiment of this invention, the cathode is a platinum electrode, a stainless steel electrode, or a pure titanium electrode.

[0015] As a preferred technical solution of this utility model, the electrodialysis cell is a polypropylene cell or a polyvinyl chloride cell.

[0016] As a preferred technical solution of this utility model, the regeneration electrolysis unit includes a regeneration electrolysis cell, in which a first cathode assembly and a first anode assembly are arranged opposite to each other on both sides, and a cation membrane is arranged between the first cathode assembly and the first anode assembly.

[0017] As a preferred technical solution of this utility model, the first cathode component is a stainless steel electrode or a pure titanium electrode.

[0018] As a preferred technical solution of this utility model, the first anode component is a high oxygen evolution potential insoluble anode.

[0019] As a preferred technical solution of this utility model, the electrolysis unit includes an electrolysis cell, and a second cathode assembly and a second anode assembly are arranged opposite to each other on both sides of the electrolysis cell.

[0020] As a preferred technical solution of this utility model, the second cathode component is a copper foil electrode, a stainless steel electrode, or a pure titanium electrode.

[0021] As a preferred technical solution of this utility model, the second anode component is a lead dioxide titanium-based anode or an iridium-tantalum titanium-based anode.

[0022] The system refers to an equipment system, device system, or production device.

[0023] Compared with the prior art, the beneficial effects of this utility model are as follows:

[0024] The persulfate micro-etching solution recycling and regeneration device system provided by this utility model uses a combination of an electrodialysis unit, an electrolysis unit, and a regeneration electrolysis unit. It can not only recover residual sodium persulfate in the waste liquid, but also recover high-quality metallic copper from the cathode. The regenerated micro-etching solution can be 100% reused in the production line without any wastewater discharge. The entire recycling and regeneration device system has low equipment investment, low energy consumption, simple structure, and high reliability in the process of copper recovery. Attached Figure Description

[0025] Figure 1 A schematic diagram of the persulfate micro-etching solution circulation and regeneration device system provided in a specific embodiment of this utility model;

[0026] Wherein, 1-anode; 2-cathode; 3-second anode assembly; 4-second cathode assembly; 5-first cathode assembly; 6-first anode assembly. Detailed Implementation

[0027] It should be understood that in the description of this utility model, the terms "center," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used solely for the convenience of describing this utility model and for simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this utility model. Furthermore, the terms "first," "second," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, features defined with "first," "second," etc., may explicitly or implicitly include one or more of that feature. In the description of this utility model, unless otherwise stated, "a plurality of" means two or more.

[0028] It should be noted that, in the description of this utility model, unless otherwise explicitly specified and limited, the terms "set," "connected," and "linked" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this utility model based on the specific circumstances.

[0029] The technical solution of this utility model will be further described below with reference to the accompanying drawings and specific embodiments.

[0030] In one specific embodiment, this utility model provides a persulfate micro-etching solution circulation and regeneration device system, such as... Figure 1 As shown, the system includes an electrodialysis unit, an electrolysis unit, and a regeneration electrolysis unit. The electrodialysis unit includes an electrodialysis tank, with a cathode 2 and an anode 1 arranged opposite each other on both sides. An anion exchange membrane and a cation exchange membrane are alternately arranged between the cathode 2 and the anode 1. The anion exchange membrane and the cathode 2 form a cathode chamber, and the cation exchange membrane and the anode 1 form an anode chamber. The anion exchange membrane and the cation exchange membrane divide the part of the electrodialysis tank between the cathode chamber and the anode chamber into several desalination chambers and several concentrate chambers. The inlets of the desalination chambers and the concentrate chambers are used to introduce persulfate micro-etching solution. The outlet of the desalination chamber is connected to the anode inlet of the regeneration electrolysis unit, and the anode outlet of the regeneration electrolysis unit is used to recycle the product solution into the micro-etching line. The outlet of the concentrate chamber is connected to the inlet of the electrolysis unit, and the outlet of the electrolysis unit is used to recycle the product solution into the micro-etching line.

[0031] In this invention, the micro-etching solution before entering the electrodialysis unit can be collected by a waste liquid collection tank. The waste liquid collection tank collects waste liquid from the copper wire etching tank and the pre-electroplating treatment micro-etching tank. The collected waste liquid mainly contains sulfuric acid, sodium persulfate, sodium sulfate, and copper sulfate. The micro-etching waste liquid is first treated by the electrodialysis unit to separate the sodium persulfate and copper sulfate. The concentrated water chamber yields a solution of copper sulfate, sulfuric acid, and sodium sulfate, while the desalinated water chamber yields a solution of sulfuric acid, sodium persulfate, and sodium sulfate. The copper sulfate solution in the concentrated water chamber can be used to recover copper through the electrolysis unit. The residual liquid after the electrolysis unit mainly contains sulfuric acid and sodium sulfate. The solution in the desalinated water chamber is then treated by the regeneration electrolysis unit. The anolyte in the regeneration electrolysis unit is electrodialyzed to obtain the desalinated water, and the catholyte is the residual electrolytic liquid after copper recovery. When the regeneration electrolysis unit is running, the anode 1BBD electrolysis oxidizes sulfate ions into persulfate ions. When the persulfate concentration reaches a certain value, it can be recycled back to the micro-etching line. The cathode 2 generates hydrogen gas, which is drawn to the exhaust tower for treatment and discharge through the exhaust pipe.

[0032] This device employs an offline regeneration process for persulfate micro-etching solutions. It not only recovers copper from the waste solution but also allows for 100% recycling of the regenerated solution. The entire system is highly automated and requires no manual intervention. Compared to direct regeneration of sodium persulfate via a BBD electrode (which is a semiconductor with a small size, resulting in uneven current density during electrolysis and poor copper quality from the cathode), this system separates copper sulfate and sodium persulfate through electrodialysis. This not only yields high-quality recovered copper but also requires less investment and is easier to maintain. Furthermore, compared to a process that first recovers copper and then regenerates sodium persulfate (where lead dioxide is first used to recover metallic copper at the anode, and the cathode decomposes residual sodium persulfate in the waste solution during electrolysis, with the remaining liquid then used for sodium persulfate regeneration), this system fully utilizes the sodium persulfate in the waste solution, resulting in low power consumption during the regeneration process.

[0033] In some embodiments, anode 1 is an iridium-tantalum-titanium-based anode or a lead dioxide-titanium-based anode.

[0034] In some embodiments, the cathode 2 is a platinum electrode, a stainless steel electrode, or a pure titanium electrode.

[0035] In some implementations, the electrodialysis cell is a polypropylene cell or a polyvinyl chloride cell.

[0036] The electrodialysis tank in this invention is mainly a polypropylene tank or a polyvinyl chloride tank. A cathode 2 and an anode 1 are installed within the electrodialysis tank. Anode 1 is an iridium-tantalum titanium-based anode or a lead dioxide-coated titanium-based anode. Cathode 2 is made of stainless steel. A cation exchange membrane and an anion exchange membrane are alternately arranged between the anode and cathode. Starting from anode 1, the sequence is: cation exchange membrane, anion exchange membrane, cation exchange membrane, anion exchange membrane, and cathode 2 (cation exchange membrane and anode 1 form the anode chamber, anion exchange membrane and cathode 2 form the cathode chamber, and anion exchange membrane and cation exchange membrane form the concentrate chamber and desalination chamber, respectively). During electrodialysis, the cathode chamber can use a 0.1 mol / L sodium sulfate solution, and the anode chamber can use a 3-4% sodium sulfate solution. Waste liquid enters from the feed inlet of the electrodialysis unit, with a current density of 300-400 A / m³. 2 The concentrate chamber recovers copper sulfate, sulfuric acid, and sodium sulfate solution, while the desalination chamber yields sodium persulfate, sodium sulfate, and sulfuric acid solution.

[0037] In some embodiments, the regeneration electrolysis unit includes a regeneration electrolysis cell, in which a first cathode assembly 5 and a first anode assembly 6 are arranged opposite each other on both sides, and a cation membrane is disposed between the first cathode assembly 5 and the first anode assembly 6.

[0038] In some embodiments, the first cathode component 5 is a stainless steel electrode or a pure titanium electrode.

[0039] In some embodiments, the first anode component 6 is a high oxygen evolution potential insoluble anode.

[0040] In this invention, the desalination solution treated by the electrodialysis unit enters the regeneration electrolysis unit. The regeneration electrolysis unit mainly includes a regeneration electrolysis cell, an anode, a cathode, and a cation exchange membrane. The anode is primarily a high oxygen evolution potential insoluble anode, such as a BBD electrode. The cathode can be made of pure titanium, stainless steel, etc. A cation exchange membrane is also installed in the middle of the regeneration electrolysis cell to divide it into an anode chamber and a cathode chamber. The desalination solution from the electrodialysis unit enters the anode chamber of the regeneration electrolysis unit, while the cathode chamber uses the residual liquid after electrolysis. The current density during electrolysis is 400–600 A / m³. 2 Once the sodium persulfate concentration in the anolyte reaches the preset value, it enters the sub-liquid storage tank for storage and is then returned to the micro-etching production line for recycling.

[0041] In some embodiments, the electrolysis unit includes an electrolytic cell, with a second cathode assembly 3 and a second anode assembly 4 disposed opposite each other on both sides of the electrolytic cell.

[0042] In some embodiments, the second cathode assembly 4 is a copper foil electrode, a stainless steel electrode, or a pure titanium electrode.

[0043] In some embodiments, the second anode component 3 is a lead dioxide titanium-based anode or an iridium-tantalum titanium-based anode.

[0044] In this invention, the solution obtained from the concentrate chamber enters the electrolysis unit to recover copper. The electrolysis unit mainly includes an electrolytic cell, an anode, and a cathode. The anode can be a lead dioxide-coated titanium-based anode, an iridium-tantalum titanium-based anode, etc., and the cathode can be copper foil, stainless steel, or pure titanium, etc. The current density during electrolysis is 150–300 A / m³. 2 Electrolysis is stopped when the concentration of copper ions in the waste liquid is less than 5 g / L.

[0045] Example 1

[0046] This embodiment provides a persulfate micro-etching solution circulation and regeneration device system, wherein:

[0047] The system includes an electrodialysis unit, an electrolysis unit, and a regeneration electrolysis unit. The electrodialysis unit includes an electrodialysis tank with a cathode 2 and an anode 1 arranged opposite each other on opposite sides. Anion exchange membranes and cation exchange membranes are alternately arranged between the cathode 2 and anode 1. The anion exchange membrane and cathode 2 form a cathode chamber, and the cation exchange membrane and anode 1 form an anode chamber. The anion exchange membranes and cation exchange membranes divide the portion of the electrodialysis tank between the cathode and anode chambers into several desalination chambers and several concentrate chambers. The inlets of both the desalination chambers and concentrate chambers are used to introduce persulfate micro-etching solution. The outlet of the desalination chamber is connected to the anode inlet of the regeneration electrolysis unit, and the anode outlet of the regeneration electrolysis unit is used to recycle the product solution into the micro-etching line. The outlet of the concentrate chamber is connected to the inlet of the electrolysis unit, and the outlet of the electrolysis unit is used to recycle the product solution into the micro-etching line.

[0048] Anode 1 is an iridium-tantalum-titanium-based anode, cathode 2 is a stainless steel electrode, and the electrodialysis cell is a polypropylene cell.

[0049] The regeneration electrolysis unit includes a regeneration electrolysis cell, in which a first cathode assembly 5 and a first anode assembly 6 are arranged opposite each other on both sides. A cation membrane is arranged between the first cathode assembly 5 and the first anode assembly 6. The first cathode assembly 5 is a stainless steel electrode, and the first anode assembly 6 is a high oxygen evolution potential insoluble anode.

[0050] The electrolysis unit includes an electrolytic cell, and a second cathode assembly 3 and a second anode assembly 4 are arranged opposite each other on both sides of the electrolytic cell. The second cathode assembly 3 is a copper foil electrode, and the second anode assembly 4 is a lead dioxide titanium-based anode.

[0051] In summary, the persulfate micro-etching solution recycling and regeneration device system provided by this utility model, through the combined use of an electrodialysis unit, an electrolysis unit, and a regeneration electrolysis unit, can not only recover residual sodium persulfate in the waste liquid, but also recover high-quality metallic copper from the cathode. The regenerated micro-etching solution can be 100% reused in the production line without any wastewater discharge. The entire recycling and regeneration device system has low equipment investment, low energy consumption, simple structure, and high reliability in the process of copper recovery.

[0052] The above description is only a specific embodiment of the present utility model, but the protection scope of the present utility model is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present utility model fall within the protection and disclosure scope of the present utility model.

Claims

1. A device system for the cyclic regeneration of a persulfate microetching solution, characterized in that, It includes an electrodialysis unit, an electrolysis unit, and a regenerative electrolysis unit; The electrodialysis unit includes an electrodialysis tank, in which a cathode and an anode are arranged opposite each other on both sides. An anion exchange membrane and a cation exchange membrane are alternately arranged between the cathode and the anode. The anion exchange membrane and the cathode form a cathode chamber, and the cation exchange membrane and the anode form an anode chamber. The anion exchange membrane and the cation exchange membrane divide the part of the electrodialysis tank between the cathode chamber and the anode chamber into several desalination chambers and several concentrate chambers. The inlet of the freshwater chamber and the inlet of the concentrated water chamber are both used to connect to the persulfate micro-etching solution. The outlet of the freshwater chamber is connected to the anode inlet of the regeneration electrolysis unit, and the anode outlet of the regeneration electrolysis unit is used to recycle the product liquid into the micro-etching line. The outlet of the concentrate chamber is connected to the inlet of the electrolysis unit, and the outlet of the electrolysis unit is used to recycle the product liquid into the micro-etching line.

2. The system for circulating and regenerating a persulfate microetchant according to claim 1, wherein The anode is either an iridium-tantalum-titanium-based anode or a lead dioxide-titanium-based anode.

3. The system for circulating and regenerating a persulfate micro-etchant according to claim 1, wherein The cathode is a platinum electrode, a stainless steel electrode, or a pure titanium electrode.

4. The system for circulating and regenerating a persulfate micro-etchant according to claim 1, wherein The electrodialysis cell is a polypropylene cell or a polyvinyl chloride cell.

5. The system for circulating and regenerating a persulfate micro-etchant according to claim 1, wherein The regeneration electrolysis unit includes a regeneration electrolysis cell, in which a first cathode assembly and a first anode assembly are arranged opposite each other on both sides, and a cation membrane is arranged between the first cathode assembly and the first anode assembly.

6. The system for circulating and regenerating a persulfate micro-etchant according to claim 5, wherein The first cathode component is a stainless steel electrode or a pure titanium electrode.

7. The system for circulating and regenerating a persulfate micro-etchant according to claim 5, wherein The first anode assembly is a high oxygen evolution potential insoluble anode.

8. The persulfate microetchant recycling device system of claim 1, wherein, The electrolysis unit includes an electrolytic cell, and a second cathode assembly and a second anode assembly are arranged opposite each other on both sides of the electrolytic cell.

9. The system for circulating and regenerating a persulfate micro-etchant according to claim 8, wherein The second cathode assembly is a copper foil electrode, a stainless steel electrode, or a pure titanium electrode.

10. The persulfate microetchant recycling device system of claim 8, wherein, The second anode assembly is a lead dioxide titanium-based anode or an iridium-tantalum titanium-based anode.

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