CN214782181U

CN214782181U - Can reduce etching waste liquid electrolysis retrieval and utilization device that gaseous pollutants escaped

Info

Publication number: CN214782181U
Application number: CN202021020548.XU
Authority: CN
Inventors: 叶涛
Original assignee: Sihui Baoanli Chemical Co ltd
Current assignee: Sihui Baoanli Chemical Co ltd
Priority date: 2019-06-06
Filing date: 2020-06-06
Publication date: 2021-11-19
Anticipated expiration: 2030-06-06

Abstract

An etching waste liquid electrolysis recycling device capable of reducing the escape of polluted gas comprises an electrolysis regeneration tank, an electrolysis anode, an electrolysis cathode and a power supply, wherein the electrolysis regeneration tank is divided into an electrolysis anode area and an electrolysis cathode area by a partition, the electrolysis anode is arranged in the electrolysis anode area, and the electrolysis cathode is arranged in the electrolysis cathode area: the device also comprises an electrolytic catholyte storage tank and an electrolytic cathode washing liquid storage tank; the electrolytic catholyte storage tank is connected with the electrolytic cathode area and is used for temporarily storing catholyte used by the electrolytic cathode area; the electrolytic cathode washing liquid storage tank is connected with the electrolytic cathode area and used for storing cathode washing liquid, and the cathode washing liquid is used for cleaning/cooling the electrolytic cathode. The device can be used for electrolyzing the waste etching solution efficiently and recovering the copper metal, and can reduce the escape of polluted gas in the process, thereby effectively protecting the environment and ensuring the production safety.

Description

Can reduce etching waste liquid electrolysis retrieval and utilization device that gaseous pollutants escaped

Technical Field

The utility model belongs to etching waste liquid recovery field, concretely relates to can reduce etching waste liquid electrolysis retrieval and utilization device that gaseous pollutants escaped.

Background

Etching is an important step in the existing Printed Circuit Board (PCB) manufacturing process. Etching is to remove unnecessary copper on the copper-clad substrate by chemical reaction with an etching solution to form a desired circuit pattern.

The commonly used etching solutions at present include acidic copper chloride etching solutions and alkaline ammonium copper chloride etching solutions (hereinafter referred to as acidic etching solutions and alkaline etching solutions). The main components of a common acidic etching solution include copper chloride, hydrochloric acid, an optional chloride salt, and an optional additive. Besides a single copper chloride acidic etching solution, an acidic etching waste solution containing copper ions and iron ions, copper ions and nickel ions and copper ions, iron ions and nickel ions is also available in the market. The main components of the alkaline etching solution comprise copper salt, ammonium chloride, ammonia water, optional carbonate and optional additives; among them, ammonium carbonate and/or ammonium bicarbonate is generally used as the carbonate.

In actual production, in order to keep the components of the etching solution stable, a replenishment solution needs to be added continuously, so that the etching solution in the etching tank is increased continuously, and when the replenishment solution is increased to a certain extent, the etching solution inevitably overflows out of the etching tank. The etching solution overflowing the etching tank and the used etching solution are generally called etching waste solution.

For circuit board manufacturers, the etching process generates a large amount of etching waste liquid containing high-concentration copper ions every day and needs to be treated. At present, most etching manufacturers choose to sell the waste liquid to an environmental protection company for treatment, and some manufacturers also adopt electrolysis equipment to carry out regeneration treatment on the etching waste liquid in the factories so as to recover copper in the etching waste liquid.

In the prior art, the electrolytic treatment process of the etching waste liquid reduces copper ions in the electrolytic waste liquid into metallic copper by performing electrochemical reduction reaction on an electrolytic cathode. In order to collect and store the metal copper precipitated by electrolysis, the prior art technology is generally biased to form a copper sheet with a compact structure and capable of being peeled off in a whole block on the electrolysis cathode, or directly adopts a thin copper plate as the electrolysis cathode, so that the metal copper is attached to the electrolysis cathode after electrolysis to form a whole copper plate. When collecting the copper sheet or plate, the whole electrolytic cathode needs to be taken out from the electrolyte. Because the acidic etching waste liquid contains hydrochloric acid and the alkaline etching waste liquid contains ammonia water, a large amount of acid mist or ammonia gas can be brought out in the taking-out process and volatilize in a workshop, so that the environment and the health of production personnel are seriously influenced.

In particular, the working temperature of the electrolyte affects the electrolysis efficiency, and generally, the higher the temperature is, the higher the electrolysis efficiency is, so that the existing electrolytic treatment process can keep the electrolytic cathode and the etching waste liquid at a higher temperature during the working process. The existing etching waste liquid has higher concentration of acid or ammonia water, and higher temperature can accelerate the escape of acid gas or ammonia gas, thereby increasing the environmental influence when an electrolytic cathode is taken out to recover copper separated out by electrolysis.

In addition, the existing method for recycling the copper from the alkaline etching waste liquid by electrolysis mainly adopts an extraction electrolysis method, namely, firstly, an extracting agent is adopted to extract the copper in the alkaline etching waste liquid, then, sulfuric acid is used to carry out back extraction on the extraction liquid to prepare a copper sulfate solution, and then, the obtained copper sulfate solution is electrolyzed to obtain the metal copper. However, the extractant used in the process has the problems of ammonia pollution and difficult waste liquid treatment in the washing and reusing process, and meanwhile, the extractant remained in the alkaline etching waste liquid in the extraction process hinders the occurrence of etching reaction when the extractant is returned to a production line for use, so that the problems of poor production quality, slow etching rate and the like are caused.

SUMMERY OF THE UTILITY MODEL

An object of the utility model is to provide a can reduce etching waste liquid electrolysis retrieval and utilization device that gaseous pollutants escaped, the device can be used for high-efficient electrolysis etching waste liquid and retrieve metal copper, can reduce the gaseous pollutants's of in-process simultaneously effusion, effective environmental protection and guarantee production safety.

The purpose of the utility model is realized through the following technical scheme:

an etching waste liquid electrolysis recycling device capable of reducing the escape of polluted gas comprises an electrolysis regeneration tank, an electrolysis anode, an electrolysis cathode and a power supply, wherein the electrolysis regeneration tank is divided into an electrolysis anode area and an electrolysis cathode area by a partition, the electrolysis anode is arranged in the electrolysis anode area, and the electrolysis cathode is arranged in the electrolysis cathode area:

the device also comprises an electrolytic catholyte storage tank and an electrolytic cathode washing liquid storage tank;

the electrolytic catholyte storage tank is connected with the electrolytic cathode area and is used for temporarily storing catholyte used by the electrolytic cathode area;

the electrolytic cathode washing liquid storage tank is connected with the electrolytic cathode area and used for storing cathode washing liquid, and the cathode washing liquid is used for cleaning/cooling the electrolytic cathode.

The utility model discloses a theory of operation is: in the process of carrying out electrolytic recovery on the etching waste liquid, after the electrolytic work is finished, transferring the catholyte from the electrolytic cathode area to the electrolytic catholyte storage tank, introducing the cathode washing liquid in the electrolytic cathode washing liquid storage tank into the electrolytic cathode area, or carrying out cooling treatment on the electrolytic cathode through the cathode washing liquid, or diluting and even removing the concentration of acid or ammonia gas on the surface of the electrolytic cathode through the cathode washing liquid, then taking out the electrolytic cathode and recovering copper, thereby achieving the purpose of remarkably reducing the escape of the acid gas or ammonia gas. And then, the electrode washing liquid can be transferred to the electrolytic cathode washing liquid storage tank again, the electrolytic cathode is reinstalled, and the cathode liquid in the electrolytic cathode liquid storage tank is transferred to an electrolytic cathode area, so that the electrolytic recovery operation can be continued. When the cathode washing liquid contains etching waste liquid, the two steps of transferring the cathode washing liquid out of the electrolytic regeneration tank and refilling electrolytic cathode liquid into the electrolytic regeneration tank can be omitted, the liquid in the cathode area of the electrolytic regeneration tank added with the cathode washing liquid is directly used as electrolytic cathode area electrolyte for the next round of electrolytic operation, and the electrolytic cathode is reinstalled and subjected to electrolytic recovery operation.

As an embodiment of the present invention, when the composition of the cathode washing solution contains etching waste solution, the electrolytic catholyte storage tank and the electrolytic cathode washing solution storage tank are connected to each other, so that a circulation loop is formed between the electrolytic cathode region, the electrolytic catholyte storage tank and the electrolytic cathode washing solution storage tank.

When "transferring catholyte from said electrolytic cathodic compartment into said electrolytic catholyte storage tank" and "passing catholyte wash in said electrolytic catholyte wash storage tank" are performed simultaneously, the utility model provides another alternative embodiment:

the device also comprises a catholyte-catholyte washing liquid storage tank;

the catholyte-catholyte washing solution storage tank is connected with the electrolytic cathode area and forms a circulation loop, so that liquid can circularly flow between the electrolytic cathode area and the catholyte-catholyte washing solution storage tank.

When the etching waste liquid is contained in the solution component, the storage tank for the catholyte-catholyte washing liquid can be used as the catholyte and the catholyte washing liquid at the same time. Therefore, in the continuous circulation process, the liquid continuously completes heat exchange between the electrolytic cathode area and the catholyte-cathode washing liquid storage tank so as to achieve the purpose of temperature reduction.

The catholyte-catholyte washing liquid storage tank can be further provided with a temperature adjusting mechanism so as to further improve the cooling efficiency.

The separator is made of materials including but not limited to filter cloth, ceramic filter plate, PE filter plate and electrolytic diaphragm, which can separate the electrolytic regeneration tank, but can not block ions from transferring between the electrolytic anode region and the electrolytic cathode region under the action of electric field. Particularly, when the etching waste liquid treated by the utility model is acidic etching waste liquid containing more than one metal ions, the separator is a material which can not block anions from migrating under the action of an electric field; when the etching waste liquid treated by the utility model is alkaline etching waste liquid, the separator is made of a material which can not block cations from migrating under the action of an electric field.

The separator may be a single layer or a multi-layer structure, and when a multi-layer structure separator is used, different materials may be independently selected for each layer of separator. Preferably, when the waste etching solution is alkaline waste etching solution, the separator is a filter cloth which can allow cations to migrate through, can block oxygen in the electrolytic anode area and can reduce the use cost.

When the utility model is used for electrolyzing and recycling the acid etching waste liquid, the main electrochemical reaction formula in the 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⁺。

As can be seen from the above reaction formula, chlorine and copper chloride are produced in the electrolytic anode region, ferric chloride is also produced in the iron-containing acidic etching waste liquid, and metallic copper is produced on the electrolytic cathode. Since both the copper chloride and the ferric chloride are copper etching agents, the partition is used for dividing the electrolytic regeneration tank into an electrolytic anode area and an electrolytic cathode area, so that certain separation effect can be achieved on anolyte and catholyte, and the circulation of particles except anions between the electrolytic anode area and the electrolytic cathode area is blocked, so that the corrosion to copper electrodeposited by an electrolytic cathode and the consumption of the copper etching agents in the anolyte are reduced.

Use the utility model discloses when carrying out the electrolytic recovery to alkaline etching waste liquid, can remove the extraction step among the prior art from, directly carry out the electrolysis to alkaline etching waste liquid and get copper, the main electrochemical reaction formula of in-process is as follows:

anode: h₂O–e^-→2H⁺+1/2O₂；

Cathode: cu²⁺+e^-→Cu⁺；

Cu⁺+e^-→Cu。

In the electrolytic process, along with the generation of copper metal and the breaking of the complex structure of the copper-ammonia complex, the concentrations of ammonium chloride and ammonia in the solution are higher and higher, and simultaneously, the oxygen content in the solution is gradually increased along with the generation of oxygen on the anode. Under the condition, the monovalent copper ammonia complex in the etching waste liquid can react with ammonium chloride, ammonia and oxygen dissolved in the etching waste liquid to regenerate divalent copper ammonia complex capable of reacting with the metal copper, and the metal copper obtained by electrolytic precipitation is corroded back, so that the precipitation efficiency of the metal copper on the cathode is low. The chemical reaction equation of the cupric ammonia complex is as follows:

divalent copper ammonia complex regeneration reaction: 2Cu (NH)₃)₂Cl+4NH₄Cl+2NH₃+1/2O₂→ 2Cu(NH)₄Cl₂+H₂O

Back etching reaction: cu + Cu (NH)₃)₄Cl₂→2Cu(NH₃)₂Cl；

And (3) total reaction: cu +2NH₄Cl+2NH₃+1/2O₂→Cu(NH)₄Cl₂+H₂O。

The electrolytic regeneration tank is divided into an electrolytic anode area and an electrolytic cathode area by using a partition, so that oxygen generated in the electrolytic anode area can be effectively prevented from entering the electrolytic cathode area, the generation of a divalent copper ammonia complex in the electrolytic cathode area is reduced, the metal copper on an electrolytic cathode is prevented from being corroded back, and the electrolytic copper precipitation efficiency is improved.

In addition, the partition is adopted to divide the electrolytic regeneration tank into an electrolytic anode area and an electrolytic cathode area, and a copper ion concentration difference is created between the anolyte and the catholyte, so that the back corrosion can be effectively reduced and the copper precipitation efficiency can be promoted particularly when the copper ion mass concentration of the catholyte is lower than that of the anolyte.

As an embodiment of the utility model, an electrolyte circulation tank is provided, the electrolyte circulation tank and the electrolysis anode area and/or the electrolysis cathode area and the etching production line respectively form a circulating flow system, thereby making the electrolyte circulation tank become the liquid exchange center between the electrolysis regeneration tank and the etching production line. By adopting the design, the etching waste liquid formed on the etching production line can be transferred to an electrolytic regeneration tank for electrolytic treatment in real time, and the electrolytic solution (anolyte and/or catholyte) after electrolytic treatment can be transferred to the etching production line as the regenerated etching solution again to participate in the etching operation again, so that the etching waste liquid is continuously regenerated and recycled and is reused in the etching process.

Preferably, the inlet and outlet lines of the etching line are provided with a solid-liquid separator to separate solids in the liquid flowing into and out of the etching line. The solid-liquid separator can be used singly, and a two-stage or multi-stage filtering system can be formed by a plurality of solid-liquid separators so as to ensure the filtering quality of the etching solution.

Preferably, a water-oil separator is arranged between the etching production line and the electrolyte circulating tank to separate oily substances in the etching waste liquid so as to ensure the normal production and use of the electrolytic recycling device.

As another embodiment of the utility model, an etching regeneration liquid preparation tank is provided, the etching regeneration liquid preparation tank is connected with the electrolysis anode region and/or the electrolysis cathode region, is used for transferring the cathode liquid and/or the anode liquid after the electrolysis is completed to the etching regeneration liquid, and is mixed with component raw materials contained in other etching liquids to prepare the etching regeneration liquid for the cyclic use on the etching production line.

Preferably, the etching regeneration liquid preparation tank is connected with an etching production line, so that the etching regeneration liquid prepared in the etching regeneration liquid preparation tank is reused in the etching operation on the etching production line.

Preferably, the electrolytic regeneration tank and/or the etching regeneration liquid preparation tank are/is provided with a sealing cover plate and/or a gas pumping and exhausting system device so as to collect and treat gas escaping in the electrolytic process and also can prevent outside air from entering, thereby reducing the amount of the gas dissolved in the catholyte and further achieving the purpose of reducing the generation of the copper etching agent.

As an embodiment of the utility model, a tail gas absorption treatment tower is arranged, the tail gas absorption treatment tower and the sealed cover plate and/or the gas pumping and exhausting system device of the electrolytic regeneration groove and/or the etching regeneration liquid preparation groove are connected for absorbing and treating the escaped tail gas. The tail gas absorption treatment tower can adopt a gas pipeline type spraying device and/or a gas absorption jet device, so that the tail gas in the production process is discharged up to the standard. Two or more tail gas absorption treatment towers can be connected in series, so that the tail gas absorption treatment is more thorough. More preferably, the absorption liquid tank of the tail gas absorption treatment tower is connected with the electrolytic regeneration tank and/or the electrolyte circulation tank and/or the etching production line through a pipeline, and the pipeline can be further provided with a pump and/or a valve.

As an embodiment of the utility model, the etching production line and/or the etching regeneration liquid preparation tank and/or the electrolysis anode area and/or the electrolysis cathode area are/is provided with a replenishing liquid tank, so as to replenish the required components for the corresponding solution.

As an embodiment of the utility model, an etching waste liquid storage tank is arranged for temporarily storing the etching waste liquid overflowing from the etching production line.

The connection relation can be connected through a pipeline and is provided with a valve and/or a pump, so that the flow of the solution between each component is controlled.

Preferably, detection devices are arranged for one or more of the electrolytic anode area, the electrolytic cathode area, the electrolyte circulating tank, the etching regeneration liquid preparation tank, the electrolytic cathode liquid storage tank, the etching waste liquid storage tank, the replenishing liquid tank, the cathode liquid-cathode washing liquid storage tank and the etching production line, and are used for detecting corresponding parameters in corresponding parts. The detection device comprises at least one of a timer, a reduction potentiometer, a hydrometer, a pH meter, a photoelectric colorimeter, an acidimeter and a liquid level meter.

Preferably, for one or more of the electrolytic regeneration tank, the electrolytic catholyte storage tank, the electrolytic catholyte washing solution storage tank, the electrolyte circulation tank, the catholyte-catholyte washing solution storage tank and the etching regeneration solution preparation tank, a cold-hot temperature exchanger and/or a temperature detector and/or an insulating layer are/is arranged to effectively control, monitor and stabilize the temperature of the anolyte and/or the catholyte and/or the etching solution within a set working temperature range, or effectively control, adjust and monitor the temperature of the liquid in the electrolytic catholyte storage tank or the electrolytic catholyte washing solution storage tank or the electrolytic catholyte-electrolytic catholyte washing solution storage tank and/or the etching regeneration solution preparation tank.

Preferably, a flow controller is arranged between the etching regeneration liquid preparation tank and the etching production line, and the flow controller can control the flow of the regeneration liquid in the etching regeneration liquid preparation tank into the etching production line to start or stop according to the specific gravity and/or the colorimetric and/or oxidation-reduction potential and/or the pH value and/or the acidity value of the etching liquid on the etching production line so as to keep the performance of the etching liquid on the etching production line stable. The flow controller adopts a variable frequency pump and/or a flow control pump valve.

Preferably, an automatic detection controller is arranged, and the automatic detection feeding controller can:

automatically adjusting the electrolytic current and/or controlling the flow, start or end of adding the electrolytic supplementary liquid to the electrolytic regeneration tank according to the result measured by the detection device; and/or the presence of a gas in the gas,

automatically controlling the size of electrolytic current or starting and stopping according to the load change of the etching production line; and/or the presence of a gas in the gas,

automatically controlling the power regulation, the starting or the stopping of the cold-hot temperature exchanger in the electrolytic regeneration tank and/or the electrolytic catholyte storage tank and/or the electrolytic cathode washing liquid storage tank and/or the electrolyte circulation tank and/or the catholyte-catholyte washing liquid storage tank and/or the etching regeneration liquid preparation tank and/or the starting or the stopping of the pumping between the electrolytic regeneration tank and the electrolytic catholyte storage tank and/or the electrolytic cathode washing liquid storage tank and/or the electrolytic cathode liquid-electrolytic cathode washing liquid storage tank according to a time program and/or the temperature detected by the temperature detector.

The utility model discloses can also make following improvement:

the electrolytic anode section and electrolytic cathode section are interconnected using a conduit to feed the exiting catholyte into the anode section. When the alkaline etching waste liquid is recycled by electrolysis, the flowing-out catholyte is added into the electrolysis anode area, and the ammonia rich in the catholyte can effectively reduce the occurrence of copper sludge in the electrolysis anode area.

And arranging a liquid guide pipe, merging and collecting the anolyte and the catholyte which respectively flow out from the electrolysis anode area and the electrolysis cathode area, and then preparing and/or adding the etching regeneration liquid to an etching production line.

And a scraper is arranged in the electrolytic cathode area and used for scraping metal copper burrs electrically separated from the electrolytic cathode in the electrolytic process. In particular, the scraper is arranged at the space between the electrolytic cathode and the separator.

The power supply adopts a double-pulse power supply to meet the use requirement of the alkaline etching waste liquid. When the utility model is used for the electrolysis is retrieved alkaline etching waste liquid, the ammonium ion in electrolysis positive pole district can pass along with electric field force the separation disc gets into electrolysis negative pole district, causes the anolyte to have the copper mud to separate out because of lacking ammonia easily. And the double-pulse power supply can reversely lead ammonium ions in the catholyte back to the anode region in the reverse-pole phase, thereby effectively avoiding the copper sludge precipitation and the waste of electric energy caused by the increase of the pressure of the electrolytic cell due to the lack of ammonia on the electrolytic anode.

And stirring devices are arranged in the electrolysis anode region and the electrolysis cathode region, and are mechanical stirring devices and/or pump liquid flowing stirring devices. The stirring device can effectively keep the uniformity of the electrolyte in the electrolytic regeneration tank, and particularly can promote ammonia in the cathode liquid to smoothly escape in the process of electrolyzing the alkaline etching waste liquid, so that the corrosion of the cathode liquid to the metal copper precipitated on the electrolytic cathode is reduced.

The utility model discloses following beneficial effect has:

1. the utility model discloses a set up electrolysis cathode solution hold up tank, electrolysis cathode lotion hold up tank, or set up cathode solution-cathode lotion hold up tank for etching waste liquid is after the electrolysis recovery process, through the cathode lotion is right the electrolysis cathode cool down and handle, or pass through the cathode lotion is right the concentration of the acid of the liquid on electrolysis cathode surface or ammonia dilutes and gets rid of even, takes out electrolysis cathode again and carries out the recovery of copper, thereby reaches to show the mesh that reduces sour gas or ammonia and flee, reduces air environmental pollution and ensures that workman's is healthy.

2. The utility model can effectively reduce the process of electrolyzing alkaline electrolyte, separate out copper mud on the electrolytic anode to increase the pressure of the electrolytic bath, and improve the production efficiency of electrolytic copper.

3. The utility model discloses remove the extraction step from among the electrolytic process of alkaline etching waste liquid, do not introduce the extractant that can cause the inhibition in the etching solution among the etching waste liquid regeneration process, avoided making the harmful effects of quality to etching quality and etching rate because of bringing into of extractant to and produced new ammonia nitrogen pollution source when reaching in the traditional extraction technology because of washing retrieval and utilization extractant.

4. The utility model discloses at the electrolytic regeneration cyclic utilization in-process of alkaline etching waste liquid, equipment takes the special measure that prevents near electrolysis positive pole easy regeneration synthetic copper etching agent and make electrolysis negative pole copper be returned to corrode on process design, improves the electroanalysis rate of copper.

Drawings

The invention is further illustrated by the following figures and examples.

FIG. 1 is a schematic structural view of an electrolytic recycling device described in example 1.

Fig. 2 is a partial enlarged view of fig. 1.

FIG. 3 is a schematic structural view of the electrolytic recycling device in example 2.

FIG. 4 is a schematic structural view of the electrolytic recycling device in example 3.

FIG. 5 is a schematic structural view of the electrolytic recycling device according to example 4.

FIG. 6 is a schematic structural view of the electrolytic recycling device according to example 5.

FIG. 7 is a schematic structural view of the electrolytic recycling device according to example 6.

Reference numerals: 1-electrolytic regeneration tank; 2-a separator; 3-an electrolytic anode; 4-an electrolytic cathode; 5-a power supply; 6-electrolytic catholyte storage tank; 7-electrolytic cathode washing liquid storage tank; 8-etching regeneration liquid preparation tank; 9-etching waste liquid storage tank; 10-a stirring device; 11-a liquid inlet and 12-a liquid outlet; 13-a scraper; 14-sealing the cover plate; 15-a gas pumping system; 16-a tail gas absorption treatment tower; 17-a solid-liquid separator; 19-an electrolyte circulation tank; 20-a water-oil separator; 21-an insulating layer; 22-a flow controller; 23-a cold-hot temperature exchanger; 24-a replenishment bath; 25-etching production line; 26-catholyte wash reservoir; 27-a temperature detector; 28-automatic detection and feeding controller; 29-a bi-directional fluid pump valve kit; 31-electrolysis of the anode region; 41-electrolytic cathode area; ^ turning to a valve; a 1-first valve; a 2-second valve; a 3-third valve; a 4-fourth valve; p-pump.

Detailed Description

The present invention will be further described with reference to the following specific examples.

In the following examples, the temperature of the etching cylinder was set to 49 ℃ and the pressure of the etching solution nozzle of the etching machine was set to 1kg/cm during the etching operation²(ii) a In addition to those listed above, the skilled person can select other products with similar properties to those listed above according to the present invention according to routine choice, and all the objects of the present invention can be achieved.

Example 1

As shown in FIGS. 1 and 2, the apparatus for recycling the waste etching solution by electrolysis capable of reducing the emission of the polluted gas comprises an electrolytic regeneration tank 1, a partition 2, an electrolytic anode 3, an electrolytic cathode 4, a power supply 5, an electrolytic catholyte storage tank 6, and an electrolytic cathode washing solution storage tank 7, which are arranged in the electrolytic regeneration tank 1 and divide the electrolytic regeneration tank 1 into a plurality of electrolytic anode areas 31 and a plurality of electrolytic cathode areas 41.

The separator 2 is a ceramic filter plate, the electrolytic anode 3 comprises graphite and a platinized titanium net, a plurality of electrolytic anodes 3 are connected with the anode of the power supply 5 in parallel and are respectively arranged in each electrolytic anode area 31 in the electrolytic regeneration tank 1, wherein the platinized titanium net belongs to the anode plated with inert metal; the electrolytic cathodes 4 comprise copper plates and titanium plates, and a plurality of electrolytic cathodes 4 are connected with the negative electrode of the power supply 5 and are respectively arranged in each electrolytic cathode area 41 in the electrolytic regeneration tank 1. The electrolytic catholyte storage tank 6 is connected with each electrolytic cathode area 41 through a pipeline provided with a bidirectional liquid flow pump valve sleeve member 29; the electrolytic cathode wash solution reservoir 7 is connected to each electrolytic cathode zone 41 through a pipe provided with a bi-directional liquid flow pump valve kit 29.

As shown in fig. 2, the bi-directional fluid pump valve kit 29 includes a first valve a1, a second valve a2, a third valve a3, a fourth valve a4, and a pump P. The bidirectional liquid flow is shown as (r) and (c) in FIG. 2: liquid flows through a first valve a1, a pump P and a second valve a2 in sequence; ② the liquid flows through the third valve a3, the pump P and the fourth valve a4 in turn.

The alkaline waste etching solution was treated using this example: and adding a mixed solution of alkaline etching waste liquid and ammonia and ammonium salt as an anolyte into each electrolytic anode area 31 of the electrolytic regeneration tank, adding a mixed solution of the alkaline etching waste liquid and organic acid as a catholyte into each electrolytic cathode area 41, and forming a copper ion concentration difference between the anolyte and the catholyte. The power supply 5 is turned on, and the electrolytic recovery of the alkaline etching waste liquid can be started.

When the metal copper on the electrolytic cathode 4 needs to be collected, dilute hydrochloric acid solution is used as cathode washing liquid, the cathode washing liquid in the electrolytic cathode area 41 is pumped into the electrolytic cathode liquid storage tank 6, all the cathode washing liquid enters the rear electrolytic cathode liquid storage tank 6, then the cathode washing liquid in the electrolytic cathode washing liquid storage tank 7 is transferred into each electrolytic cathode area 41 to clean the electrolytic cathode 4, the electrolytic cathode 4 is taken out after the operation is completed to collect the metal copper, finally the electrolytic cathode 4 is reinstalled, the cathode washing liquid in each electrolytic cathode area 41 is pumped back into the electrolytic cathode washing liquid storage tank 7, and then the cathode liquid in the electrolytic cathode liquid storage tank 6 is pumped back to each electrolytic cathode area 4 to start a new round of electrolytic recovery process.

Example 2

As shown in FIG. 3, the apparatus for recycling the waste etching solution by electrolysis capable of reducing the escape of the polluted gas comprises an electrolytic regeneration tank 1, a partition 2, an electrolytic anode 3, an electrolytic cathode 4, a power supply 5, an electrolytic catholyte storage tank 6, and an electrolytic catholyte washing solution storage tank 7, which are arranged in the electrolytic regeneration tank 1 and divide the electrolytic regeneration tank 1 into an electrolytic anode area 31 and an electrolytic cathode area 41.

The separator 2 is filter cloth, the electrolytic anode 3 is a coating anode, the electrolytic cathode 4 is titanium, the power supply 5 is a double-pulse power supply, and the electrolytic anode 3 is connected with the positive electrode of the power supply 5 and is arranged in the electrolytic anode area 31; the electrolytic cathodes 4 are connected to the negative electrode of the power source 5 and are respectively disposed in the electrolytic cathode regions 41. The electrolytic catholyte storage tank 6 is connected with the electrolytic cathode region 41 through a pipeline provided with a pump, and forms a circulation loop; the electrolytic cathode wash reservoir 7 is connected to the electrolytic cathode section 41 by a conduit with a bi-directional flow pump valve assembly 29.

The electrolytic cathode area 41 is provided with a stirring device 10 of a pump liquid flowing type, a liquid outlet 12 and a scraper 13, and the scraper 13 is arranged in the space between the separator 2 and the electrolytic cathode 4 in the electrolytic cathode area 41. The electrolytic cathode area 41 is provided with a stirring device 10, and the stirring device 10 comprises a pump.

The electrolytic regeneration tank 1 is provided with a detection device, which comprises a detection device 18-1 for detecting the parameters of the electrolytic anode area 31 and a detection device 18-2 for detecting the parameters of the electrolytic cathode area 41; the notch of the electrolysis anode area 31 is provided with a sealing cover plate 14, the sealing cover plate 14 is provided with an air outlet and is connected with a tail gas absorption treatment tower 16, and the tail gas absorption treatment tower 16 is a gas pipeline type spraying device to treat escaped tail gas.

The detection device is connected with the automatic detection feeding controller 28, so that the detection device can control and adjust the electrolytic current of the power supply according to the detected result; the electrolytic cathode area 41 is provided with a temperature detector 27 which controls the start and stop of the pumping on the connecting pipes between the electrolytic regeneration tank 1 and the electrolytic cathode solution storage tank 6 and between the electrolytic regeneration tank 1 and the electrolytic cathode washing solution storage tank 7 according to the temperature of the electrolytic cathode area 41 by transmitting a signal to the automatic detection controller 28.

The other end of the tail gas absorption treatment tower 16 is connected with an etching regeneration liquid preparation tank 8 with a liquid inlet, the etching regeneration liquid preparation tank 8 is provided with a liquid outlet pipeline, the liquid outlet pipeline comprises a main valve, the main valve is connected with the electrolysis anode region 31 through a pipeline with a pump, and is connected with the electrolysis cathode region 41 through a pipeline with a flow controller 22. A reverse pipeline is also arranged between the etching regeneration liquid preparation tank 8 and the electrolysis anode area 31, and the pipeline is provided with a pump and a valve. A return pipeline is arranged between the etching regeneration liquid preparation tank 8 and the electrolytic cathode area 41 and is used as an overflow pipeline, so that a circulating pipeline is formed between the etching regeneration liquid preparation tank 8 and the electrolytic cathode area 41. The detection device 18-3 is provided for detecting a parameter in the etching regeneration liquid preparation tank 8.

The etching regeneration liquid preparation tank 8 is connected with an etching waste liquid storage tank 9 through a pipeline with a valve and a pump.

The alkaline waste etching solution was treated using this example: the etching waste liquid storage tank 9 is used to store the etching waste liquid overflowing from the etching line. And transferring the etching waste liquid in the etching waste liquid storage tank 9 to an etching regeneration liquid preparation tank 8 and an electrolysis anode area 31 for constant volume waste liquid treatment, namely, taking part of the alkaline etching waste liquid as the anode liquid of the electrolysis anode area 31.

In the initial electrolysis, the mixed solution of the alkaline etching waste liquid, the alkaline etching liquid and the reducing agent is added into the electrolytic cathode area 41 as the catholyte, or the mixed solution of the alkaline etching waste liquid, the alkaline etching liquid, the reducing agent and/or the organic acid is added into the electrolytic cathode area 41 as the catholyte, and the copper ion concentration difference is formed between the anolyte and the catholyte.

In the electrolysis process, the copper content of the anolyte is less and less, the metal copper is separated out on the electrolysis cathode 41, and the scraper 13 is started to scrape the burrs of the metal copper separated out on the electrolysis cathode. Meanwhile, mixed liquid of water and inorganic acid is used as absorption liquid, and tail gas generated by the electrolytic regeneration tank 1 is absorbed by a tail gas absorption treatment tower 16.

In order to keep the copper content of the catholyte required by the process, the copper content of the anolyte and the catholyte is continuously reduced in the electrolytic process, so that the catholyte needs to be added into the electrolytic cathode area 41 from the etching regeneration preparation tank 8 according to the process requirement, and overflowed catholyte flows back into the etching regeneration preparation tank 8 through a backflow pipeline.

When the metal copper on the electrolytic cathode 4 needs to be collected, the catholyte is used as cathode washing liquid and is stored in the electrolytic cathode washing liquid storage tank 7, after the electrolysis is completed and the power supply 5 is turned off, when the catholyte in the electrolytic cathode washing liquid storage tank 7 is added into the electrolytic cathode area 41, the catholyte in the electrolytic cathode area 41 overflows into the electrolytic catholyte storage tank 6, the electrolytic cathode 4 is taken out after the temperature of the liquid in the electrolytic cathode area 41 is cooled to reach the cooling temperature value set by the process for collecting the metal copper, and the electrolytic cathode 4 is reinstalled after the collection is completed to carry out the next round of electrolysis recovery operation.

After the alkaline etching waste liquid is electrolyzed to reduce the copper content, transferring the anolyte in the electrolysis anode area 31 to the etching regeneration liquid preparation tank 8, supplementing and adjusting the content of each component in the etching liquid in the etching regeneration liquid preparation tank 8, and circularly using the prepared production etching regeneration liquid on an etching production line. Then the waste liquid is pumped from the etching waste liquid storage tank 9 to the vacant etching regeneration liquid preparation tank 8 and the electrolysis anode area 31. After the treatment fluid is replaced, the power supply 5 is turned on to continue the electrolysis recovery operation after all parts of the equipment are checked to be intact.

Example 3

As shown in FIG. 4, the apparatus for recycling the waste etching solution by electrolysis capable of reducing the escape of the polluted gas comprises an electrolytic regeneration tank 1, a partition 2, an electrolytic anode 3, an electrolytic cathode 4, a power supply 5, an electrolytic catholyte storage tank 6, and an electrolytic catholyte washing solution storage tank 7, which are arranged in the electrolytic regeneration tank 1 and divide the electrolytic regeneration tank 1 into an electrolytic anode area 31 and an electrolytic cathode area 41.

The separator 2 is an anion membrane and filter cloth, the electrolytic anode 3 is a conductive carbon plate, the electrolytic cathode 4 is titanium, and the electrolytic anode 3 is connected with the positive pole of the power supply 5 and is arranged in the electrolytic anode area 31; the electrolytic cathodes 4 are connected to the negative electrode of the power source 5 and are respectively disposed in the electrolytic cathode regions 41. The electrolysis anode region 31 and the electrolysis cathode region 41 are connected through a pipeline with a pump. The electrolytic cathode solution storage tank 6 and the electrolytic cathode washing solution storage tank 7 are respectively connected with the electrolytic cathode area 41 through pipelines provided with bidirectional liquid flow pump valve suites 29.

The electrolytic anode area 31 is provided with a detection device 18-1, a sealing cover plate 14 is arranged at the notch, and the automatic detection feeding controller 28 can control the feeding of the electrolytic replenishing liquid according to the detection result of the detection device 18-1; a gas pumping and exhausting system 15 is arranged and respectively connected with the notches of the electrolysis anode area 31 and the electrolysis cathode area 41. The electrolytic cathode area 41 is provided with a detection device 18-2 and a temperature detector 27-1 for detecting real-time parameters in the electrolytic cathode area 41.

The electrolytic catholyte storage tank 6 is provided with a cold-hot temperature exchanger 23-1 and a temperature detector 27-2, the electrolytic cathode washing liquid storage tank 7 is provided with a cold-hot temperature exchanger 23-2 and a temperature detector 27-3, and the automatic detection controller 28 can respectively control the cold-hot temperature exchanger 23-1 and the cold-hot temperature exchanger 23-2 to be turned on and off according to the results detected by the temperature detector 27-2 and the temperature detector 27-3.

An electrolyte circulating tank 19 is arranged, and a gas pumping and exhausting system 15, a detection device 18-3, a temperature detector 27-4, an insulating layer 21 and a cold-heat temperature exchanger 23-3 are arranged on the electrolyte circulating tank 19.

The electrolyte circulation tank 19 is connected with the electrolysis anode region 31 through two pipelines respectively provided with a valve and a pump to form a circulation loop; the electrolyte circulation tank 19 is connected with the etching production line 25 through an outflow pipeline with a pump and a valve, and the etching production line 25 is connected with the electrolyte circulation tank 19 through a return pipeline which is sequentially connected with a first pump, a water-oil separator 20, a second pump and a solid-liquid separator 17, so that a circulation loop is formed between the electrolyte circulation tank 19 and the etching production line 25. The solid-liquid separator 17 is also provided with a branch pipe with a flow controller 22 connected to the electrolytic cathode region 41.

The replenishment liquid tank 24 is connected to the etching line 25 through a pipe having the flow controller 22, and the gas pumping system 15 is provided in the replenishment liquid tank 24.

The acidic etching waste liquid is treated by the embodiment: the etching waste liquid overflowing from the etching line 25 is first subjected to impurity filtration by the water-oil separator 20 and the solid-liquid separator 17, and then enters the electrolyte circulation tank 19. The electrolyte circulating tank 19 is used as a liquid exchange center, the acidic etching waste liquid is used as an anolyte of the electrolysis anode area 31 and is added into the electrolysis anode area 31, a mixed solution of the acidic etching waste liquid and the acidic etching sub-liquid is initially used as a catholyte of the electrolysis cathode area 41 and is added into the electrolysis cathode area 41, and a copper ion concentration difference is formed between the anolyte and the catholyte.

During the electrolysis, the anolyte in the electrolysis anode area 31 and the etching solution from the etching production line 25 are mixed and regenerated and exchanged through the electrolyte circulation tank 19, so that part of the exchanged solution flows back to the etching production line 25 for etching production. In addition, the automatic detection feeding controller 28 feeds the waste liquid overflowing from the etching production line 25 into the electrolytic cathode region 41 according to the process requirements after being subjected to oil removal filtration treatment by using a pump according to the detection result of the detection device 18-2 so as to maintain the copper ion concentration of the cathode liquid. The catholyte overflowing from the electrolytic cathode section 41 is introduced back into the electrolytic anode section 31 through a pipe. At the same time, the electrolytic replenishment solution is fed from the replenishment solution tank 24 to the etching line 25 based on the detection means 23-3 of the etching line 25. And tail gas generated by the electrolytic regeneration tank 1, the electrolyte circulating tank 19 and the replenishing liquid tank 24 is discharged through the gas pumping and discharging system 15.

When the metal copper on the electrolytic cathode 4 needs to be collected, the mixed solution of clear water and acidic etching waste liquid is used as cathode washing liquid, all the cathode liquid in the electrolytic cathode area 41 is pumped into the electrolytic cathode liquid storage tank 6, then the cathode washing liquid in the electrolytic cathode washing liquid storage tank 7 is pumped into the electrolytic cathode area 41 to clean the electrolytic cathode, and then the electrolytic cathode 4 is taken out to collect the metal copper. Finally, the electrolytic cathode 4 is reinstalled, the cathode washing liquid in the electrolytic cathode area 41 is completely pumped back to the electrolytic cathode washing liquid storage tank 7, and the cathode liquid with the original temperature in the electrolytic cathode liquid storage tank 6 is pumped back to the electrolytic cathode area 41 for the next round of electrolytic recovery operation.

Example 4

As shown in FIG. 5, the apparatus for recycling the waste etching solution by electrolysis capable of reducing the escape of the polluted gas comprises an electrolytic regeneration tank 1, a partition 2, an electrolytic anode 3, an electrolytic cathode 4, a power supply 5, an electrolytic catholyte storage tank 6, and an electrolytic catholyte washing solution storage tank 7, which are arranged in the electrolytic regeneration tank 1 and divide the electrolytic regeneration tank 1 into an electrolytic anode area 31 and an electrolytic cathode area 41.

The separator 2 is a bipolar membrane and a PE filter plate, the electrolysis anode 3 is a coating anode, the electrolysis cathode 4 is copper, and the electrolysis anode 3 is connected with the positive electrode of the power supply 5 and is arranged in the electrolysis anode area 31; the electrolytic cathodes 4 are connected to the negative electrode of the power source 5 and are respectively disposed in the electrolytic cathode regions 41. The electrolytic cathode zone 41 is provided with a gas pumping system 15. The electrolytic cathode solution storage tank 6 and the electrolytic cathode washing solution storage tank 7 are respectively connected with the electrolytic cathode area 41 through pipelines provided with bidirectional liquid flow pump valve suites 29.

The electrolysis anode area 31 is connected with a multilayer tail gas purification system formed by connecting a tail gas absorption treatment tower 16-1, a tail gas absorption treatment tower 16-2 and a tail gas absorption treatment tower 16-3 in series through an exhaust pipe, wherein the tail gas absorption treatment tower 16-1 is a gas absorption jet device, and the tail gas waste liquid spraying absorption treatment tower 16-2 and the tail gas absorption treatment tower 16-3 are pipeline type spraying devices. Meanwhile, the electrolysis anode area 31 is also connected with the tail gas absorption treatment tower 16-2 through a pipeline. Wherein the tail gas absorption treatment tower 16-2 is connected to the electrolytic cathode area 41 through a pipeline with a flow controller 22, so that the absorption liquid of the tail gas absorption treatment tower 16-2 is added into the electrolytic cathode area 41 according to the process requirement to maintain the concentration of copper ions in the cathode liquid. The electrolytic cathode area 41 is provided with an overflow port and is connected with the tail gas absorption treatment tower 16-1 through a pipeline, so that the overflowed catholyte is introduced into the tail gas absorption treatment tower 16-1.

The etching regeneration liquid preparation tank 8 is respectively connected with the electrolysis anode area 31 and the electrolysis cathode area 41 through a pipeline with a branch. The etching regeneration liquid preparation tank 8 is provided with a heat preservation layer 21, a cold-heat temperature exchanger 23 and a detection device 18-3.

The etching regeneration liquid preparation tank 8 is connected with an etching production line 25 through a pipeline with a flow controller 22, wherein the flow controller 22 is specifically flow control of a variable frequency pump and is controlled and executed by a process parameter detection feeding controller on the etching production line; the detection device 18-1 and the detection device 18-3 respectively detect the technological parameters of the solution in the anolyte and the etching regeneration solution preparation tank 8 to control the electrolytic current value of the power supply 5; the detection device 18-2 is used for detecting the copper ion concentration of the catholyte and adding the etching waste liquid according to the process requirement.

The etching line 25 is connected with the tail gas absorption treatment tower 16-2 through a pipeline with a valve and a pump, and the pump is also connected with the electrolytic anode area 31 through a pipeline. The supplementary liquid tank 24-4 is connected with the etching production line 25 through a pipeline with a valve and a pump, and can be used for supplementing the adding of an oxidant to the etching production line 25.

The replenishing liquid tank 24-1, the replenishing liquid tank 24-2 and the replenishing liquid tank 24-3 are respectively connected with the etching regeneration liquid preparation tank 8 through pipelines with valves and pumps, so that the solution in the etching regeneration liquid preparation tank 8 is replenished with raw materials required by the etching liquid such as hydrochloric acid, organic acid, chloride or oxidant in real time.

The automatic detection controller 28 can automatically adjust the magnitude of the electrolysis current output by the power supply 5 according to the real-time parameters in the electrolysis anode area 31 measured by the detection device 18-1.

The acidic etching waste liquid is treated by the embodiment: the acidic waste etching solution is used as an anolyte to be added into the electrolysis anode area 31, and a mixed solution of the acidic waste etching solution and hydrochloric acid, organic acid and chloride is used as a catholyte to be added into the electrolysis cathode area 41 at the beginning.

After the electrolysis is started, the tail gas absorption liquid from the tail gas absorption tower 16-2 is added into the electrolysis cathode area 41 according to the value detected by the detection device 18-2 arranged in the electrolysis cathode area 41, so as to maintain the concentration of copper ions in the cathode liquid to be stable, and the concentration difference of copper ions is formed between the anode liquid and the cathode liquid.

In the electrolysis process, after the etching waste liquid overflows from the etching production line 25, part of the solution of the etching waste liquid and the tail gas reaction enters the electrolysis anode area 31, and the tail gas absorption liquid of the tail gas absorption tower 16-2 and the etching waste liquid from the etching production line 25 are controlled to be added into the electrolysis cathode area 41 according to the detection result of the detection device 18-2. When the predetermined liquid levels in the electrolysis anode region 31 and the electrolysis cathode region 41 are high, the anolyte and the catholyte overflow out of the tank, are merged in the pipeline and then are conveyed into the etching regeneration liquid preparation tank 8, and the cold-hot temperature exchanger 23 performs constant temperature operation on the etching regeneration liquid preparation tank 8.

The tail gas generated in the electrolysis anode area 31 is sequentially treated by a tail gas absorption treatment tower 16-1, a tail gas absorption treatment tower 16-2 and a tail gas absorption treatment tower 16-3, the absorption liquid used by the tail gas absorption treatment tower 16-1 is catholyte electrolyzed in the electrolysis cathode area 41, the absorption liquid used by the tail gas absorption treatment tower 16-2 is a mixed liquid of acidic etching waste liquid and acidic etching liquid, and the absorption liquid used by the tail gas absorption treatment tower 16-3 is an inorganic alkali solution.

When the metal copper on the electrolytic cathode 4 needs to be collected, the mixed liquid of clear water, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate is used as cathode washing liquid, all the cathode liquid in the electrolytic cathode area 41 is pumped into the electrolytic cathode liquid storage tank 6, then the cathode washing liquid in the electrolytic cathode washing liquid storage tank 7 is pumped into the electrolytic cathode area 41, the electrolytic cathode 4 is cleaned, and then the electrolytic cathode 4 is taken out to collect the metal copper.

And after the collection is finished, the electrolytic cathode 4 is installed again, the cathode washing liquid in the electrolytic cathode area 41 is pumped back to the electrolytic cathode washing liquid storage tank 7, and the cathode liquid in the electrolytic cathode liquid storage tank 6 is pumped back to the electrolytic cathode area 41 for the next round of electrolytic recovery operation.

In addition, during the production process, according to the real-time process parameters of the etching production line 25, the solution in the etching regeneration solution preparation tank 8 can be automatically added with the components such as hydrochloric acid, organic acid, chloride salt and the like required by the etching solution through the supplementary liquid tank 24-1, the supplementary liquid tank 24-2 and the supplementary liquid tank 24-3, so that the regenerated etching solution after being supplemented and adjusted can be continuously recycled and used on the etching production line 25.

Example 5

As shown in FIG. 6, the apparatus for recycling the waste etching solution by electrolysis capable of reducing the escape of the polluted gas comprises an electrolytic regeneration tank 1, a partition 2, an electrolytic anode 3, an electrolytic cathode 4, a power supply 5, an electrolytic catholyte storage tank 6, and an electrolytic catholyte washing solution storage tank 7, which are arranged in the electrolytic regeneration tank 1 and divide the electrolytic regeneration tank 1 into an electrolytic anode area 31 and an electrolytic cathode area 41.

The separator 2 is a cationic membrane and filter cloth, the electrolytic anode 3 is a coating anode, the electrolytic cathode 4 is titanium, and the electrolytic anode 3 is connected with the positive pole of the power supply 5 and is arranged in the electrolytic anode area 31; the electrolytic cathodes 4 are connected to the negative electrode of the power source 5 and are respectively disposed in the electrolytic cathode regions 41. The gas pumping and exhausting system 15 is respectively connected with the electrolysis anode region 31 and the electrolysis cathode region 41 and is connected with the tail gas absorption treatment tower 16-1, and the tail gas absorption treatment tower 16-1 is connected with a gas absorption jet device to treat the tail gas generated by the electrolysis anode region 31 and the electrolysis cathode region 41.

The electrolysis anode area 31 is connected with the electrolysis cathode area 41 through a pipeline with a valve and a pump, so that the catholyte overflowing from the electrolysis cathode area 41 is added into the electrolysis anode area 31. The electrolytic anode area 31 is provided with a detection device 18-1, and the electrolytic cathode area 41 is provided with a detection device 18-2 and a temperature detector 27-1, which are respectively used for detecting various technical parameters in the electrolytic anode area 31 and the electrolytic cathode area 41.

The supplementary liquid tank 24-1 and the supplementary liquid tank 24-2 are respectively connected with the electrolytic anode area 31 through pipelines with valves and pumps so as to add supplementary liquid into the electrolytic anode area 31.

A circulating pipeline is connected with the electrolytic cathode area 41, the valve, the electrolytic cathode liquid storage tank 6, the valve, the pump, the electrolytic cathode washing liquid storage tank 7, the valve and the pump in sequence and then returns to the electrolytic cathode area 41, thereby forming a circulating flow loop. Wherein, the electrolytic cathode washing liquid storage tank 7 is also provided with a cold-heat temperature exchanger 23-1 and a temperature detector 27-2.

The electrolyte circulation tank 19 is connected with the liquid outlet 12 of the electrolytic anode region 31 through a liquid inlet pipe with a pump and a valve, and is connected with the liquid inlet of the electrolytic anode region 31 through a liquid outlet pipe with a pump and a valve to form a circulation loop; the other liquid outlet pipe with a pump and a valve of the electrolyte circulation groove 19 is connected with the liquid inlet 11 of the electrolytic cathode area 41. The electrolyte circulating tank 19 is provided with a detection device 18-3 and a temperature detector 27-3 for detecting various real-time parameters in the electrolyte circulating tank 19; and is provided with a cold-hot temperature exchanger 23-2 for regulating temperature. A circulating pipeline is sequentially connected with an electrolyte circulating tank 19, a solid-liquid separator 17-4, a flow controller 22, a valve, an etching production line 25, a valve, a pump, a water-oil separator 20, a valve, a pump, a solid-liquid separator 17 (a composite solid-liquid separation mechanism consisting of a PE filter plate, filter cloth and a wire-wound filter), a valve, a pump, an etching waste liquid storage tank 9, a valve and a pump, and finally returns to the electrolyte circulating tank 19, so that a circulating flow loop is formed. Wherein the etching waste liquid storage tank 9 is provided with a detection device 18-4. The flow controller 22 is controlled by a process parameter detection controller on the etching line.

An automatic detection controller 28 is arranged, and can be used for controlling the addition of the supplementary liquid in the supplementary liquid tank 24-1 and the supplementary liquid tank 24-2 into the electrolytic anode region 31 according to the detection result of the detection device 18-1, and can also be used for controlling the on and off of the pump between the electrolytic cathode washing liquid storage tank 7 and the electrolytic cathode region 41 according to the detection result of the temperature detector 27-1; the opening and the closing of the temperature exchanger 23-1 can be controlled according to the detection result of the temperature detector 27-2; the current of the power supply 5 can be controlled according to the detection results of the detection device 18-3 and the detection device 18-4; the power, the opening and the closing of the cold and hot temperature exchanger 23-2 can be controlled according to the detection result of the temperature detector 27-3.

The alkaline waste etching solution was treated using this example: the etching waste liquid overflowing from the etching production line 25 is first filtered by impurities through the water-oil separator 20 and the solid-liquid separator 17, then flows into the etching waste liquid storage tank 9 for temporary storage, and is transferred to the electrolyte circulation tank 19 according to the liquid level of the electrolyte circulation tank 19.

The solution of the electrolyte circulation tank 19 is added into the electrolysis anode area 31 as an anolyte, a mixed solution of alkaline etching waste liquid and alkaline etching sub-liquid is added into the electrolysis cathode area 41 as an initial catholyte according to the process requirements, and a copper ion concentration difference is formed between the anolyte and the catholyte.

In the electrolysis process, the electrolyte circulating tank 19 is used as a liquid exchange center of the electrolysis regeneration tank 1 and the etching production line 25, the anolyte in the electrolysis anode region 31 and the etching solution from the etching production line 25 are mixed and exchanged, the solution in the electrolyte circulating tank 19 is added into the electrolysis cathode region 41 through controllable pumping to maintain the copper ion concentration of the catholyte within the process requirement range, and meanwhile, the catholyte overflowing from the electrolysis cathode region 41 is added into the electrolysis anode region 31 through a pipeline with a valve and pumping.

Controlling the feeding of the electrolyte replenishing liquid from the replenishing liquid tank 24-1 and the replenishing liquid tank 24-2 to the electrolysis anode area 31 according to the detection result of the detection device 18-1; the tail gas generated in the electrolytic regeneration tank 1 is treated by a gas pumping and discharging system 15 and a tail gas absorption treatment tower 16-1. The absorption liquid used by the tail gas absorption treatment tower 16-1 is organic acid, and the absorption liquid after absorbing the tail gas can be reused in the etching production process after supplementing the required chemical raw materials and blending.

When the metal copper on the electrolytic cathode 4 needs to be collected, the mixed solution with the same components as the cathode washing liquid is adopted as the cathode washing liquid, the cathode washing liquid with the lower temperature in the electrolytic cathode washing liquid storage tank 7 is added into the electrolytic cathode area 41, meanwhile, the cathode washing liquid overflowing above the set liquid level in the electrolytic cathode area 41 is drained into the electrolytic cathode liquid storage tank 6, and when the temperature of the liquid in the electrolytic cathode area 41 is cooled to reach the set temperature, the electrolytic cathode 4 is taken out to collect the metal copper. After the collection is finished, the electrolytic cathode 4 is reinstalled, and the next round of electrolytic recovery operation is started.

In the process of continuing the electrolysis recovery operation, the solution is timely replenished from the electrolytic cathode storage tank 6 according to the solution storage capacity of the electrolytic cathode washing solution storage tank 7. The content of each component in the etching solution is supplemented and adjusted in the electrolytic regeneration tank 1, so that the produced etching regeneration solution is circularly used on the etching production line 25, the temperature of the cathode solution can be reduced, and the pollution of ammonia gas escaping during copper receiving is reduced.

Example 6

As shown in FIG. 7, the apparatus for recycling the waste etching solution by electrolysis capable of reducing the escape of the polluted gas comprises an electrolytic regeneration tank 1, a partition 2, an electrolytic anode 3, an electrolytic cathode 4, a power supply 5, an electrolytic catholyte storage tank 6, and an electrolytic catholyte washing solution storage tank 7, which are arranged in the electrolytic regeneration tank 1 and divide the electrolytic regeneration tank 1 into an electrolytic anode area 31 and an electrolytic cathode area 41.

The separator 2 is a cation exchange membrane and filter cloth, the electrolytic anode 3 is metal plated with gold on the surface, the electrolytic cathode 4 is a titanium plate, and the electrolytic anode 3 is connected with the positive pole of the power supply 5 and is arranged in the electrolytic anode area 31; the electrolytic cathodes 4 are connected to the negative electrode of the power source 5 and are respectively disposed in the electrolytic cathode regions 41. The electrolysis anode area 31 is provided with a gas pumping and discharging system 15-1 and is connected with a tail gas absorption treatment tower 16-1, and the tail gas absorption treatment tower 16-1 adopts a gas absorption jet device; the electrolytic cathode area 41 is provided with a gas pumping and discharging system 15-2 and is connected with a tail gas absorption treatment tower 16-2, and the absorption liquid adopts clear water; respectively used for treating the tail gas generated in the electrolysis anode area 31 and the electrolysis cathode area 41.

The electrolytic anode area 31 is provided with a detection device 18-1, and the electrolytic cathode area 41 is provided with a detection device 18-2 and a temperature detector 27-1, which are respectively used for detecting various technical parameters in the electrolytic anode area 31 and the electrolytic cathode area 41.

The tail gas absorption treatment tower 16-1 is provided with a detection device 18-4, and the electrolytic cathode region 41 is connected with the tail gas absorption treatment tower 16-1 through a pipeline with a valve and a pump, so that liquid overflowing from the electrolytic cathode region 41 is introduced into an absorption cell of the tail gas absorption treatment tower 16-1.

A catholyte-catholyte washing liquid storage tank 26 for storing catholyte or catholyte washing liquid is arranged, and the electrolytic cathode region 41 and the catholyte-catholyte washing liquid storage tank 26 are connected through a pipeline with a valve and a pump to form a circulation loop; the catholyte-catholyte washing liquid storage tank 26 is provided with an insulating layer 21, a cold-heat temperature exchanger 23-1 and a temperature detector 27-2.

An electrolyte circulation tank 19 is arranged, and a cold-heat temperature exchanger 23-2, a detection device 18-3 and a temperature detector 27-3 are arranged on the electrolyte circulation tank 19. The electrolyte circulation tank 19 is connected with the electrolytic anode area 31 and the liquid outlet 12 of the electrolytic cathode area 41 through pipelines with valves and flow controllers 22, so that the anolyte in the electrolytic anode area 31 and the catholyte in the electrolytic cathode area 41 are merged and then flow into the electrolyte circulation tank 19. And additionally arranging pipelines with pumps to connect the electrolyte circulation tank 19 with the electrolysis anode region 31 and the electrolysis cathode region 41 respectively, so that the solution in the electrolyte circulation tank 19 is led back to the electrolysis anode region 31 and the electrolysis cathode region 41.

The electrolyte circulation tank 19 is connected with the electrolysis anode region 31 through a pipeline with a valve and a pump, so that the solution in the electrolyte circulation tank 19 can be introduced into the electrolysis anode region 31; the electrolyte circulation tank 19 is connected with the tail gas absorption treatment tower 16-1 through a pipeline, so that the solution of the tail gas absorption treatment tower 16-1 after absorbing the tail gas can be introduced into the electrolyte circulation tank 19.

A circulating pipeline is sequentially connected with the electrolyte circulating tank 19, a valve, a flow controller 22, an etching production line 25, a valve, a pump, a water-oil separator 20, a valve, a pump, a solid-liquid separator 17, a valve and a pump and then returns to the electrolyte circulating tank 19 so as to form a circulating flow loop.

A make-up fluid tank 24 is provided and connected to the etching line 25 via a pipe with a valve and a pump to supply the make-up fluid to the etching line 25.

An automatic detection controller 28 is arranged, which can control the power of the cold-hot temperature exchanger 23-1 according to the parameters in the electrolytic cathode area 41 detected by the temperature detector 27-1 and control the pumping between the electrolytic cathode area 41 and the catholyte-catholyte lotion storage tank 26, thereby controlling the flow rate of the feeding solution from the catholyte-catholyte lotion storage tank 26 to the electrolytic cathode area 41 and further controlling the catholyte temperature of the electrolytic cathode area 41 within the process requirement range; the size of the electrolytic current output by the power supply 5 can also be controlled and adjusted according to the detection results of the detection device 18-3 and the temperature detector 27-3.

The alkaline waste etching solution was treated using this example: the waste etching solution overflowing from the etching production line 25 is firstly filtered by impurities through the water-oil separator 20 and the solid-liquid separator 17 and then enters the electrolyte circulating tank 19, the acidic waste etching solution is mixed in the electrolyte circulating tank 19 to form a solution, the solution is used as an anolyte and is added into the electrolysis anode area 31, the mixed solution of the acidic waste etching solution and the acidic etchant is used as an initial catholyte and is added into the electrolysis cathode area 41, and a copper ion concentration difference is formed between the anolyte and the catholyte. During the electrolysis process, the copper ion concentration difference is detected by the detection device 18-2 and regulated and controlled by the automatic detection feeder 28 according to the process requirements.

In the electrolytic production process, the electrolyte circulating tank 19 is used as a solution exchange center in the electrolytic regeneration tank 1 and the etching production line 25, the anolyte in the electrolytic anode region 31 and the etching solution from the etching production line 25 are mixed and exchanged, and the pump is controlled according to the data measured by the detection device 18-2 to feed the solution in the electrolyte circulating tank 19 into the electrolytic cathode region 41 so as to maintain the stability of the concentration of the copper ions in the catholyte.

The catholyte overflowing from the electrolytic cathode section 41 and the anolyte flowing out from the electrolytic anode section 31 are joined in the electrolyte circulation tank 19. The automatic detection feeder 28 feeds the etching replenishment solution from the replenishment solution tank 24 to the etching line 25 based on the detection device 18-3 or based on real-time data installed on the etching line 25. The gas pumping system 15-2 arranged on the electrolytic cathode area 41 pumps the tail gas generated in the electrolytic cathode area 41 and carries out absorption treatment by the tail gas absorption treatment tower 16-2.

When the metal copper on the electrolytic cathode 4 needs to be collected, a solution with the same composition as the catholyte is used as a cathode washing liquid, the cathode washing liquid with lower temperature in the catholyte-cathode washing liquid storage tank 26 is added into the electrolytic cathode area 41, and meanwhile, the solution overflowing from the electrolytic cathode area 41 flows back to the catholyte-cathode washing liquid storage tank 26 to form a heat exchange process of circular flow. When the temperature in the electrolytic cathode area 41 reaches the set temperature, the electrolytic cathode 4 is taken out for collecting the metal copper. After the collection is finished, the electrolytic cathode 4 is reinstalled, and the next round of electrolytic recovery operation is started.

It should be noted that the above-mentioned embodiments are only illustrative and not restrictive, and that modifications or improvements which do not depart from the principle of the present invention and are made by those skilled in the art are deemed to be within the scope of the present invention.

Claims

1. The utility model provides an etching waste liquid electrolysis retrieval and utilization device that can reduce polluted gas and escape, includes electrolysis regeneration tank, electrolysis positive pole, electrolysis negative pole and power, electrolysis regeneration tank pass through the divider and separate into electrolysis positive pole district and electrolysis negative pole district, electrolysis positive pole arrange in electrolysis positive pole district, electrolysis negative pole arrange in electrolysis negative pole district, characterized by:

2. An apparatus for the electrolytic recycling of waste etching solution capable of reducing the escape of polluted gas as claimed in claim 1, wherein said electrolytic catholyte storage tank and electrolytic cathodic washing solution storage tank are connected to each other, so that a circulation loop is formed among said electrolytic cathode region, electrolytic catholyte storage tank and electrolytic cathodic washing solution storage tank.

3. The utility model provides an etching waste liquid electrolysis retrieval and utilization device that can reduce polluted gas and escape, includes electrolysis regeneration tank, electrolysis positive pole, electrolysis negative pole and power, electrolysis regeneration tank pass through the divider and separate into electrolysis positive pole district and electrolysis negative pole district, electrolysis positive pole arrange in electrolysis positive pole district, electrolysis negative pole arrange in electrolysis negative pole district, characterized by:

the device also comprises a catholyte-catholyte washing liquid storage tank;

4. The apparatus for electrolyzing and recycling an etching waste liquid capable of reducing the escape of a polluted gas according to any one of claims 1 to 3, wherein the partition is made of a material capable of partitioning the electrolytic regeneration tank without blocking the migration of ions between the electrolytic anode region and the electrolytic cathode region under the action of an electric field.

5. The apparatus for electrolyzing and recycling etching waste liquid capable of reducing the escape of polluted gas as claimed in claim 4, wherein an electrolyte circulation tank is provided, and the electrolyte circulation tank, the electrolysis anode region, the electrolysis cathode region and the etching production line respectively form a circulating flow system, so that the electrolyte circulation tank becomes a liquid exchange center between the electrolysis regeneration tank and the etching production line.