CN213142198U - Preplating tank for acidic etching waste liquid electrolysis regeneration process - Google Patents

Preplating tank for acidic etching waste liquid electrolysis regeneration process Download PDF

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Publication number
CN213142198U
CN213142198U CN202021483538.XU CN202021483538U CN213142198U CN 213142198 U CN213142198 U CN 213142198U CN 202021483538 U CN202021483538 U CN 202021483538U CN 213142198 U CN213142198 U CN 213142198U
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plating
cathode
waste liquid
liquid
etching waste
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叶涛
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/46—Regeneration of etching compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The utility model discloses a preplating groove for acid etching waste liquid electrolysis regeneration technology, including power, preplating positive pole, preplating negative pole and preplating cell body, wherein, the edge of preplating negative pole on enclose and set firmly the insulating material frame. The preplating tank is used for matching with the electrolytic regeneration process of the acidic etching waste liquid after the copper layer is preplated on the current electrolytic cathode, and can achieve good effect of copper recovery.

Description

Preplating tank for acidic etching waste liquid electrolysis regeneration process
Technical Field
The utility model belongs to etching waste liquid recovery field, concretely relates to a pre-plating bath for acid etching waste liquid electrolysis regeneration technology.
Background
Printed Circuit Board (PCB) production factories generate a large amount of copper-containing waste liquid every day, etching liquid used in an etching process comprises acidic etching liquid and alkaline etching liquid, and the generated etching waste liquid is the acidic etching waste liquid and the alkaline etching waste liquid respectively.
The main components of the common acidic etching solution are copper chloride, hydrochloric acid, optional chloride salt and optional additives, and part of the acidic etching solution simultaneously contains the combination of copper and iron, copper and nickel, copper and iron and nickel and other metal ions. In the actual etching production process, in order to keep the components of the acidic etching solution stable, a supplementary solution needs to be added continuously, and inevitably, the etching solution in the etching tank is increased and overflows out of the etching tank, thereby generating a large amount of acidic etching waste liquid.
The components and the concentration of the acidic etching waste liquid are very similar to those of the acidic etching waste liquid, and the acidic etching waste liquid contains a large amount of copper ions, so that heavy metal pollution can be caused if the acidic etching waste liquid is directly discharged into the environment; if the recovery is carried out, higher economic value can be brought. At present, the acid etching solution is generally sold to environment-friendly and dangerous waste companies for treatment, and part of conditional enterprises can directly carry out electrolysis on the acid etching solution in a factory by using electrolysis equipment to recover copper and regenerate the acid etching solution for recycling.
In the prior art, the electrolytic treatment of the acidic etching waste liquid adopts the acidic etching waste liquid or the acidic etching waste liquid added with additives and/or water and/or existing component raw materials for adjustment as an electrolyte, copper ions in the electrolytic waste liquid are reduced into metallic copper by performing an electrochemical reduction reaction on an electrolytic cathode, and an oxidation reaction of the metallic ions and/or a generation reaction of chlorine gas occur on an electrolytic anode. The main electrochemical reaction formula of the electrolytic process is as follows:
anode: cl- – e- → 1/2Cl2↑；
Cu+ – e- → Cu2+；
Cathode: cu2+ + e- → Cu+；
Cu+ + e- → Cu。
In addition to the above electrochemical reaction, the following reaction occurs with respect to an acidic etching waste liquid containing iron and/or nickel:
anode: fe2+ – e- → Fe3+；
Cathode: fe3+ + e- → Fe2+。
If the copper sheet with compact structure and capable of being stripped and separated by electrolysis in a whole block can be formed on the electrolytic cathode, or the thin copper plate is directly used as cathode electroanalysis copper and then is used as a whole copper plate for collection, the metal copper obtained by electrolysis can be collected and stored more conveniently.
In general, as the electrolysis proceeds, the electrolytic current tip effect is more effective, so that the copper surface precipitated by electrolysis becomes rough, and particularly, the copper layer precipitated on the electrolytic cathode becomes loose and uneven due to the corrosion of the acidic electrolyte solution because of containing a large amount of chloride ions in the acidic etching waste liquid. After the concave-convex difference of the copper surface is increased, the current point discharge effect is further aggravated, so that the copper surface becomes rougher, even needling is grown on coarse grain points of the copper surface, and a vicious circle is formed.
On the other hand, the electrolysis current is concentrated on the copper asperity sites on the surface of the electrolysis cathode, causing the asperity to grow rapidly. The copper surface of the other part is difficult to continue depositing copper due to the over-small current, and under the corrosion action of copper etching agents such as copper chloride and/or ferric chloride contained in the acidic etching waste liquid, the part of the copper surface becomes thin continuously, so that a relatively flat and compact copper layer obtained in the initial stage of electrolysis becomes loose and fragile, a complete copper precipitation plate is difficult to form, and a part of the copper layer falls off in the electrolytic cell in the electrolytic process, so that the collection of metal copper is inconvenient.
One solution in the prior art is to add an organic brightening and flattening agent into the etching waste liquid and then carry out electrolysis so as to solve the difficult problems of looseness and more burrs of an electrolytically precipitated copper layer. However, the addition of the polishing agent can cause the waste etching solution to be subjected to electrolytic treatment, and if the electrolyte is used as a regenerated etching solution to be recycled to an etching production line, the etching production quality is affected, and environment-friendly recycling can not be well realized.
In addition, in order to make the copper scale separated by electrolysis easier to peel and collect, the prior art uses a method of coating a titanium cathode with conductive oil and then performing electrolysis operation. However, this method results in contamination of the electrolyte at the electrolytic cathode with conductive oil, which affects the production rate and etching quality when it is recycled to the etching line.
SUMMERY OF THE UTILITY MODEL
An object of the utility model is to provide a plating bath in advance for acid etching waste liquid electrolysis regeneration technology, should plate the groove in advance and be used for cooperating the present electrolytic cathode on after the copper layer of plating in advance, carry out electrolytic acid etching waste liquid electrolysis regeneration technology again, can reach the effect of good recovery copper.
The purpose of the utility model is realized through the following technical scheme:
a pre-plating tank for an acid etching waste liquid electrolysis regeneration process comprises a power supply, a pre-plating anode, a pre-plating cathode and a pre-plating tank body, wherein an insulating material frame is fixedly arranged on the edge of the pre-plating cathode in a surrounding mode.
The corresponding acid etching waste liquid electrolysis regeneration process of the utility model comprises the following steps:
(1) in the pre-plating tank, pre-plating by taking non-copper metal as a pre-plating cathode so as to pre-plate a layer of metal copper on the pre-plating cathode; (2) taking out the pre-plating cathode, placing the pre-plating cathode in an electrolytic bath as an electrolytic cathode, and carrying out electrolytic regeneration treatment on the acidic etching waste liquid with the copper ion concentration of 1-200 g/L and the acidity of 0.5-4M to precipitate metal copper on the surface of the electrolytic cathode; (3) and after the electrolytic regeneration is finished, taking out the electrolytic cathode, stripping and collecting the copper sheet on the surface of the electrolytic cathode.
The utility model discloses enclose on the preplating cathode and set firmly the frame that sets up insulating material and make, can make step (2) acid etching waste liquid be in the electrolysis process the metal copper layer that appears and form on preplating cathode two sides can not the edge of preplating cathode bonds integrative to can follow the copper layer simply conveniently in step (3) the preplating cathode on realize peeling off.
As a preferred embodiment of the present invention, the frame made of insulating material is a plastic frame.
Preferably, the present invention may further include an acid corrosion prevention layer on an edge of the pre-plated cathode, and/or a periphery of the electrical conductor, and/or a gas-liquid interface at the pre-plated cathode, wherein the electrical conductor is a conductor for connecting the pre-plated cathode and the power supply cathode. The acid corrosion-resistant layer can reduce the corrosion of the pre-plating solution to the electric conductor and the pre-plated cathode under the condition of ensuring good heat dissipation conditions, prolong the service life and better strip a copper block electrically precipitated on the cathode. The acid corrosion-resistant layer is made of materials with stable properties in an acid environment, such as titanium, platinum, gold, silver, plastic and the like.
As an implementation mode of the utility model, the utility model also comprises a cathode cleaning liquid groove for storing the cathode cleaning liquid. And the cathode cleaning liquid tank is used for containing cathode cleaning liquid to clean the cathode after the pre-plating in the step (1) is finished so as to avoid influencing subsequent electrolytic regeneration. Preferably, an ultrasonic cleaning device is arranged in the pre-plating tank body and/or the cathode cleaning liquid tank to better clean the pre-plating cathode.
As a preferred embodiment of the utility model, the device also comprises a preplating liquid transfer tank, and the cathode cleaning liquid tank and the preplating liquid transfer tank are respectively connected with the preplating tank body. In the using process, when the pre-plated cathode is to be cleaned after pre-plating, the pre-plating solution is transferred to the pre-plating solution transfer tank, and then the cathode cleaning solution is transferred from the cathode cleaning solution tank to the pre-plating tank body for cleaning; and after the cleaning is finished, the cathode cleaning solution is moved back to the cathode cleaning solution tank, and finally the pre-plating solution is moved back to the pre-plating bath body from the pre-plating solution transfer tank to perform the next pre-plating operation, so that the automation degree is improved. Preferably, a pump and/or a valve are respectively arranged between the pre-plating liquid transfer tank and the pre-plating tank body and between the cathode cleaning liquid tank and the pre-plating tank body.
As an embodiment of the present invention:
the pre-plating tank is provided with a stirring device which is a mechanical stirring device and/or a pump liquid flowing type stirring device so as to stir the pre-plating liquid.
The pre-plating tank is provided with a detection device, and the detection device comprises one or two or more of a timer, a specific gravity detector, a photoelectric colorimetric detector, an oxidation-reduction potential detector, a pH value detector, an acidimeter, a thermometer and a liquid level detector so as to detect various parameters in the pre-plating tank in real time. Preferably, in order to maintain the components of the pre-plating solution stable in the pre-plating process, an automatic detection feeding controller is arranged. The automatic detection feeding controller can automatically control the feeding of the pre-plating solution to the pre-plating tank to supplement raw materials or stop feeding according to the detection result of the detection device.
The pre-plating tank is provided with a cold and hot temperature exchanger for controlling the temperature of the pre-plating tank, so that the temperature of pre-plating operation can be kept in a proper range.
The pre-plating tank is provided with a filtering device, and the filtering device is connected with the pre-plating tank body through a pipeline and a return pipe which are provided with a pump to form a circulation loop for filtering pre-plating liquid in the pre-plating tank body. And a pump and/or a valve are/is also arranged between the filtering device and the tank body.
The pre-plating tank is provided with a scraper which is arranged below the liquid level of the pre-plating tank body and is close to the pre-plating cathode so as to remove overlong burrs possibly formed on the surface of the pre-plating cathode in the pre-plating process.
The pre-plating tank is provided with a cathode protection tank for containing reducing solution to protect the pre-plating cathode in a non-working state and prevent oxidation.
Compared with the prior art, the utility model discloses following beneficial effect has:
the utility model discloses simple structure can implement very conveniently the pre-plating process among the acid etching waste liquid electrolysis regeneration technology, equipment cost is low, easy operation, through the copper layer that acid etching waste liquid electrolysis regeneration technology retrieved complete, the easy collection.
Drawings
The present invention will be further described with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of a structure of a pre-plating bath for an electrolytic regeneration process of acidic waste etching solution in example 1.
FIG. 2 is a schematic diagram of the structure of a pre-plating bath used in the electrolytic regeneration process of the acidic waste etching solution in example 2.
FIG. 3 is a schematic diagram of the structure of a pre-plating bath used in the electrolytic regeneration process of the acidic waste etching solution in example 3.
FIG. 4 is a schematic diagram of the structure of a pre-plating bath used in the electrolytic regeneration process of the acidic waste etching solution described in example 4.
FIG. 5 is a schematic view of the structure of a pre-plating bath used in the electrolytic regeneration process of the acidic waste etching solution in example 5.
FIG. 6 is a schematic diagram of the structure of a pre-plating bath used in the electrolytic regeneration process of the acidic waste etching solution in example 6.
Reference numerals: 1-preplating a tank body; 2-preplating an anode; 3-preplating a cathode; 4-a power supply; 5-a liquid inlet; 6-a liquid outlet; 7-a stirring device; 8-a detection device; 9-automatically detecting a feeding controller; 10-a cathode cleaning liquid tank; 11-a cold-hot temperature exchanger; 12-a preplating liquid transfer tank; 13-a filtration device; 14-a scraper; 15-cathode protection cell; 16-ultrasonic cleaning device; 17-a border of insulating material; 18-an electrical conductor; 19-an acid corrosion protection layer; p-pumping; ^ turning to a valve.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
As shown in figure 1, the pre-plating tank of the acid etching waste liquid electrolysis regeneration process comprises a pre-plating tank body 1, a pre-plating anode 2, a pre-plating cathode 3 and a power supply 4, wherein the edge of the pre-plating cathode 3 is surrounded by an inherent insulating material frame 17, and the pre-plating anode 2 and the pre-plating cathode 3 are respectively connected with the anode and the cathode of the power supply 4 and are arranged in the pre-plating tank body 1.
In the pre-plating operation, the power supply 4 is started to electrify the pre-plating anode 2 and the pre-plating cathode 3, and an electroplated copper layer is formed on the surface of the pre-plating cathode 3 along with the advance of the pre-plating.
Example 2
As shown in fig. 2, embodiment 2 differs from embodiment 1 in that:
the preplating tank body 1 is provided with a liquid inlet 5 and a liquid outlet 6 which are respectively used for injecting and discharging preplating liquid; the preplating tank body 1 is provided with a stirring device 7 consisting of a pump and a circulating pipeline, a detection device 8 for detecting real-time parameters of the preplating liquid in the preplating tank, and a scraper 14 which is arranged close to the preplating cathode 3 and can be used for removing overlong burrs possibly formed on the surface 3 of the preplating cathode in the preplating process.
In the pre-plating operation, the power supply 4 is started to electrify the pre-plating anode 2 and the pre-plating cathode 3, the stirring device 7 is started to make the pre-plating solution circularly flow to form stirring, and an electroplated copper layer is formed on the surface of the pre-plating cathode 3 along with the advance of the pre-plating.
Example 3
As shown in fig. 3, embodiment 3 differs from embodiment 1 in that:
the preplating tank body 1 is provided with a liquid inlet 5 and a liquid outlet 6 which are respectively used for injecting and discharging preplating liquid; the pre-plating tank body 1 is provided with a stirring device 7 and a detection device 8 for detecting real-time parameters of pre-plating liquid in the pre-plating tank, wherein the stirring device 7 is a mechanical stirring device.
The detection device 8 is connected with the automatic detection feeding controller 9, and the automatic detection feeding controller 9 can add supplementary raw materials of the pre-plating solution into the pre-plating bath body 1 according to the detection result of the detection device 8 so as to maintain the stability of the components of the pre-plating solution; a cold and hot temperature exchanger 11 is arranged, and the cold and hot temperature exchanger 11 is arranged by a cold and hot exchanging device and a circulating pipeline, so that the temperature of the preplating operation can be kept in a proper range; and a cathode cleaning liquid tank 10 is further arranged and used for containing cathode cleaning liquid so as to clean the pre-plated cathode 3 after the pre-plating is finished, and the cathode cleaning liquid tank 10 can be directly connected with the pre-plating tank body 1 through a pipeline or transfer the cathode cleaning liquid between the pre-plating tank body 1 and the cathode cleaning liquid tank 10 through other adding devices.
Example 4
As shown in fig. 4, example 4 differs from example 3 in that:
an ultrasonic cleaning device 16 is arranged in the cathode cleaning liquid tank 10, and in the arrangement mode, after the pre-plating is finished, the pre-plated cathode 3 is transferred into the cathode cleaning liquid tank 10, and the pre-plated cathode 3 is better cleaned by combining the ultrasonic cleaning device 16; the periphery of the conductor 18 connecting the power supply 4 and the pre-plated cathode 3 is coated with an acid corrosion-proof layer 19 to prevent the conductor 18 from being corroded to affect the service life.
Example 5
As shown in fig. 5, embodiment 5 differs from embodiment 1 in that:
the preplating tank body 1 is provided with a liquid inlet 5 and a liquid outlet 6 which are respectively used for injecting and discharging preplating liquid; the pre-plating tank body 1 is provided with a stirring device 7 and a detection device 8 for detecting real-time parameters of pre-plating liquid in the pre-plating tank, wherein the stirring device 7 is a mechanical stirring device.
The edge of the pre-plating cathode 3 is also provided with an acid corrosion prevention layer 19 to prevent the pre-plating solution from corroding the pre-plating cathode 3 and prolong the service life of the pre-plating cathode.
The filtering device 13 is connected with the pre-plating tank body 1 through a pipeline with a pump, and forms a circulating pipeline to filter the pre-plating liquid in the pre-plating tank body 1.
The cathode cleaning liquid tank 10 is connected with the pre-plating tank body 1 through a pipeline with a pump, and a circulating pipeline is formed; the pre-plating liquid transfer tank 12 is connected with the pre-plating tank body 1 through a pipeline with a pump and a valve, and forms a circulating pipeline.
In the using process, when the pre-plated cathode 3 is to be cleaned, the pre-plating solution is transferred from the pre-plating tank body 1 to the pre-plating solution transfer tank 12, and then the cathode cleaning solution is transferred from the cathode cleaning solution tank 10 to the pre-plating tank body 1 for cleaning; and after the cleaning is finished, the cathode cleaning solution is moved back to the cathode cleaning solution tank 10, and finally the pre-plating solution is moved back to the pre-plating tank body 1 from the pre-plating solution transfer tank 12 for the next pre-plating operation, so that the automation degree is improved.
Example 6
As shown in fig. 6, example 6 differs from example 5 in that:
an ultrasonic cleaning device 16 is arranged in the pre-plating tank body 1 to better clean the pre-plated cathode 3 after the pre-plating is finished;
the anti-acid corrosion layer 19 is arranged on the gas-liquid interface at the pre-plating cathode 3;
the cathode cleaning liquid tank 10 and the pre-plating liquid transfer tank 12 are respectively connected with the pre-plating tank body 1 through backflow prevention pipelines as shown in the figure so as to prevent the solution from reflowing in the transfer process.
The utility model discloses when using:
the pre-plated anode is graphite and/or phosphor copper and/or metal plated with inert metal and/or coating anode and/or phosphor copper; when the pre-plated anode is metallic, alternative materials include, but are not limited to: copper, platinum, gold, silver; when the pre-plating anode is a metal plated with an inert metal on the surface, the metal includes but is not limited to copper, titanium, iron, platinum, gold, silver, nickel, zinc, aluminum and alloys of the above metals, and the inert metal is a metal stable in the pre-plating solution, including but not limited to platinum, gold, silver. When the graphite and/or the phosphor copper and/or the metal are in small blocks and/or powder, the pre-plating anode also comprises a conductive titanium basket for containing the small blocks and/or the powder of the graphite and/or the phosphor copper and/or the metal.
The electroplating cathode is a titanium and/or iron-containing electrode, and the iron-containing electrode comprises stainless steel and/or iron alloy and/or alloy steel.
The electrical conductor comprises stainless steel and/or iron alloy and/or alloy steel.
The material of the acid corrosion prevention layer includes but is not limited to: titanium, platinum, gold, silver, plastic.
The detection device comprises one or two or more of a timer, a specific gravity detector, a photoelectric colorimetric detector, an oxidation-reduction potential detector, a pH value detector, an acidimeter and a liquid level detector.
The raw materials added by the automatic detection feeding controller comprise metallic copper and/or phosphor copper and/or copper oxide and/or pre-plating solution raw materials.
The reducing substance in the cathodic protection cell is a compound effective in preventing oxidation of iron in water, including, but not limited to, sulfite, thiosulfate, hydroxylamine sulfate, hydroxylamine hydrochloride, hydrazine hydrate, oxalic acid or a salt thereof, formic acid or a salt thereof, citric acid or a salt thereof, glucose, ascorbic acid, tartaric acid, phosphite, or hypophosphite.
It should be noted that the above-mentioned embodiments are only illustrative and not restrictive, and any modifications or changes within the meaning and range of equivalents of the technical solution of the present invention by those skilled in the art should be considered as included in the protection scope of the present invention.

Claims (10)

1. A pre-plating tank for an acid etching waste liquid electrolysis regeneration process comprises a power supply, a pre-plating anode, a pre-plating cathode and a pre-plating tank body, and is characterized in that an insulating material frame is fixedly arranged on the edge of the pre-plating cathode in a surrounding mode.
2. The pre-plating bath for the electrolytic regeneration of acidic etching waste liquid according to claim 1, wherein an acid corrosion prevention layer is provided on the edge of the pre-plated cathode, and/or on the periphery of the electrical conductor, and/or on the gas-liquid interface at the pre-plated cathode, and the electrical conductor is a conductor for connecting the pre-plated cathode and the power supply cathode.
3. The pre-plating tank for the electrolytic regeneration process of acidic etching waste liquid according to claim 1, further comprising a cathode cleaning liquid tank for storing a cathode cleaning liquid.
4. The pre-plating bath for the electrolytic regeneration process of acidic etching waste liquid as claimed in claim 3, further comprising a pre-plating solution transfer bath, wherein the cathode cleaning solution bath and the pre-plating solution transfer bath are respectively connected with the pre-plating bath body.
5. The pre-plating tank for the electrolytic regeneration process of the acidic etching waste liquid as claimed in claim 4, wherein a pump and/or a valve is respectively arranged between the pre-plating liquid transfer tank and the pre-plating tank body and between the cathode cleaning liquid tank and the pre-plating tank body.
6. The pre-plating bath for the acidic etching waste liquid electrolytic regeneration process as claimed in claim 1, wherein the pre-plating bath is provided with a stirring device, and the stirring device is a mechanical stirring device and/or a pump liquid flowing type stirring device.
7. The pre-plating bath for the acidic etching waste liquid electrolytic regeneration process as claimed in claim 1, wherein the pre-plating bath is provided with a detection device, the detection device comprises one or two or more of a timer, a specific gravity detector, a photoelectric colorimetric detector, an oxidation-reduction potential detector, a pH value detector, an acidimeter, a thermometer and a liquid level detector, so as to detect various parameters in the pre-plating bath in real time.
8. The pre-plating bath for the acidic etching waste liquid electrolysis regeneration process as claimed in claim 7, wherein an automatic detection feeding controller is provided, and the automatic detection feeding controller can automatically control the feeding of the pre-plating liquid replenishing raw material to the pre-plating bath or the stopping of the feeding according to the detection result of the detection device.
9. The pre-plating bath for the electrolytic regeneration process of the acidic etching waste liquid as claimed in claim 1, wherein the pre-plating bath is provided with a filtering device, and the filtering device is connected with the pre-plating bath body through a pipeline and a return pipe which are provided with a pump to form a circulation loop for filtering the pre-plating liquid in the pre-plating bath body; and a pump and/or a valve are/is also arranged between the filtering device and the tank body.
10. The pre-plating bath for the electrolytic regeneration process of acidic etching waste liquid as claimed in claim 1, wherein the pre-plating bath is provided with a cathode protection bath for containing a reducing solution to protect the pre-plating cathode from oxidation in a non-working state.
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