CN109161895B - Acid copper chloride etching solution copper recovery and regeneration system and recovery and regeneration method - Google Patents

Abstract

The invention provides an acid copper chloride etching solution copper recovery and regeneration system and a recovery and regeneration method, which relate to the technical field of etching solution recycling and regeneration. The acid copper chloride etching solution copper recovery and regeneration system of the invention includes an etching solution regeneration system and a waste gas treatment system located downstream of the etching solution regeneration system, and also includes a molten iron washing solution treatment system; the acid copper chloride etching solution copper recovery and regeneration method of the invention is effective Solve the problems of high energy consumption, low recycling rate, high content of cathode copper impurities, secondary pollution of the environment by chlorine gas, etc. of the existing acid cupric chloride etching solution regeneration cycle, and provide technology for the comprehensive application of the acid cupric chloride etching solution electrolytic regeneration cycle technology support.

Description

Acid copper chloride etching solution copper recovery and regeneration system and recovery and regeneration method

technical field

The invention relates to the technical field of cyclic regeneration of etching solution, in particular to an acid copper chloride etching solution copper recovery and regeneration system and a recovery and regeneration method.

Background technique

Printed circuit boards are the basic components of various electronic products. An important part of the production process is to chemically etch away the excess copper (usually 60-70%) that is not required for circuits on the copper foil board. Acidic cupric chloride and alkaline cupric chloride etchants are currently the most used etchants. Among them, acid cupric chloride etchants are especially suitable for printed circuit board products with high etching accuracy due to their small side etching. Printed circuit board factories are increasingly used. The chemical reaction that occurs during the etching process is that a copper divalent ion in the etching solution oxidizes a metal copper atom on the copper foil to generate two monovalent copper ions. Therefore, with the progress of etching, the concentration of total copper and monovalent copper ions in the etching solution increases, which will cause the etching ability to gradually decrease. In order to maintain the ideal etching ability, the usual practice is to chemically regenerate a part of the etching solution, that is, adding a chemical oxidant to the etching solution to oxidize the monovalent copper to divalent copper. The chemically regenerated etching solution is reused, and the other part of the unregenerated etching solution becomes the etching waste solution. About 2-2.5L of etching waste liquid with copper content of 100-150g.L ^-1 is produced for each square meter of printed circuit board etched.

The copper etching waste liquid produced in the printed circuit board factory is generally sent to the waste liquid treatment plant to process and recover copper by chemical methods such as neutralization precipitation method, replacement method and extraction method. However, the copper recovered from the waste liquid by these treatment methods is in the form of compounds, the product value is low, and a large amount of chemicals are consumed in the treatment process. In addition, due to the technical limitations of each chemical recovery method, a considerable part of copper is not recovered, but is discharged into the environment, causing environmental pollution.

At present, there are many domestic and foreign companies that research and develop copper chloride etching solution electrolytic recovery of copper. The developed equipment has different problems during use, which makes it impossible to use in the industry. For example, the etching solution cannot be recycled after electrolytic copper extraction. , not only pollutes the environment, but also leads to waste of chemical raw materials; another technical problem is that chlorine gas will be precipitated in the anode during the electrolysis process. According to theoretical calculations, for every 100kg of copper deposited by electrolysis, 111.6kg of chlorine gas will be precipitated in the anode accordingly. , its volume in the standard state is about 35.26m ³ , how to properly handle the large amount of chlorine gas and residual waste liquid produced without causing secondary pollution to the environment will undoubtedly increase the cost and complicate the equipment.

Therefore, the development of an acid copper chloride etching solution copper recovery and regeneration system and recovery and regeneration method is particularly important for the recovery and reuse of copper.

SUMMARY OF THE INVENTION

Aiming at the deficiencies of the prior art, the present invention provides an acid copper chloride etching solution copper recovery and regeneration system and a recovery and regeneration method.

To achieve the above purpose, the technical scheme of the present invention is achieved through the following technical schemes:

An acid copper chloride etching solution copper recovery and regeneration system, the acid copper chloride etching solution copper recovery and regeneration system comprises an etching solution regeneration system and a waste gas treatment system located downstream of the etching solution regeneration system, and also includes a molten iron washing solution treatment system, The etching solution regeneration system includes an etching production line, a waste liquid storage barrel, an electrolytic cell, and a regeneration liquid storage barrel, which are connected in sequence. The communication, the jet device and the etching production line are connected in sequence;

The molten iron washing liquid processing system includes a molten iron tank, a molten iron absorption tank, and a molten iron washing tower connected in sequence; wherein, the processing flow of the molten iron washing liquid is sequentially: molten iron tank - molten iron absorption tank - molten iron washing tower; The iron cylinder contains ferric dichloride, elemental iron and hydrogen chloride; the molten iron absorption cylinder contains ferric dichloride containing impurities; the molten iron washing tower contains pure ferric dichloride.

The etching production line is provided with an environmental ventilation pipe, and the environmental ventilation pipe is connected to the exhaust gas treatment system through a pipeline,

The waste gas treatment system includes a dissolving absorption cylinder, a molten iron absorption cylinder, a molten iron washing tower, an lye absorption tower, and an exhaust port, which are connected in sequence. The air duct is connected, the anode area of the electrolytic cell is connected with the dissolution and absorption cylinder, (the gas in the anode area of the electrolytic cell enters the dissolution absorption cylinder, the molten iron absorption cylinder, the molten iron washing tower, the lye absorption tower, and the exhaust port in turn through the pipeline, Complete waste gas treatment); the cathode area of the electrolytic cell is connected with the molten iron washing tower (the gas in the cathode area of the electrolytic cell enters the molten iron washing tower, the lye absorption tower, and the exhaust port in turn through the pipeline to complete the waste gas treatment); the environment The suction pipe is connected with the alkali liquor absorption tower.

Further, the recovery and regeneration method includes etching solution regeneration, chlorine gas treatment, molten iron washing solution treatment, and waste gas treatment; the etching solution regeneration is: introducing the etching waste liquid into an electrolytic cell as an electrolyte solution for electrolysis, and under the action of electrolysis , When the electrolyte is electrolyzed, metal copper is produced on the cathode plate, and chlorine gas is generated on the anode plate. The copper ions in the etching waste solution are reduced to copper powder at the cathode to reduce the copper ion concentration, and at the same time, the strong oxidizing product chlorine gas in the anode Under the oxidative effect of , the ORP increases, so that the regeneration of the etching waste liquid reaches the standard of the effective etching solution, and then the regenerated etching solution is introduced into the etching production line and recycled.

Further, the copper ion content in the cathode area of the electrolytic cell is controlled at 30-70g/L, the electrolysis current of the electrolytic cell is 1000-3000A, and the copper ion mass concentration of the electrolyte in the cathode area of the electrolytic cell is always < the electrolysis in the anode area. The copper ion mass concentration of the liquid.

Further, the content of copper ions is sampled and analyzed once every four hours in the cathode area of the electrolytic cell, and the content of copper ions is controlled at 30-50 g/L in the normal electrolysis process. When the ion is less than 30g/L, add the etching waste liquid.

Further, an electrolytic diaphragm is provided inside the electrolytic cell.

Further, the chlorine treatment is as follows: the oxidizing gas chlorine generated in the anode chamber enters the dissolution absorption cylinder, and is reused to the etching production line through the jet device, thereby achieving cyclic regeneration.

Further, the processing flow of the molten iron washing solution is sequentially: molten iron tank-hot metal absorption tank-hot metal washing tower, wherein the molten iron tank contains ferric chloride, elemental iron, and hydrogen chloride; the molten iron absorption tank contains ferric chloride, elemental iron, and hydrogen chloride. Impurity ferric chloride; in the molten iron washing tower is pure ferric chloride.

Further, the waste gas treatment process is as follows: electrolytic cell anode gas-dissolution absorption cylinder-hot metal absorption cylinder-hot metal washing tower-alkali washing tower-discharge; electrolytic cell cathode gas-hot metal absorption cylinder-hot metal washing tower-alkali washing Tower - Discharge; Environmental Exhaust Duct - Lye Scrubber - Discharge.

The invention provides an acid copper chloride etching solution copper recovery and regeneration system and a recovery and regeneration method, and compared with the prior art, the advantages are:

The acid copper chloride etching solution copper recovery and regeneration system and the recovery and regeneration method of the invention effectively solve the problems of high energy consumption, low recycling rate, high content of cathode copper impurities, secondary pollution of the environment by chlorine gas and the like of the existing acid copper chloride etching solution regeneration cycle. , to provide technical support for the comprehensive application of the electrolytic regeneration cycle technology of acid copper chloride etching solution;

The present invention has high electrolysis current efficiency, can effectively save production cost, save energy, and improve copper recovery efficiency, so that the entire recovery and regeneration process has higher stability, safety and higher economic benefits; the acid copper chloride of the present invention The etching solution copper recovery and regeneration system and the recovery and regeneration method ensure that etching and electrolysis can run smoothly and synchronously. In addition, using the machine to automatically collect the metal copper obtained by electrolysis and automatically control the start and stop of the electrolysis, the overall automation of the process is high, and the labor input is reduced. The chlorine gas generated in the electrolysis can be used as an oxidant to oxidize the monovalent cupric ions and ferrous ions in the electrolyte, thereby saving the use of liquid oxidants in the regeneration process of the etching sub-liquid;

The copper recovered by the acid copper chloride etching solution copper recovery and regeneration system and the recovery and regeneration method of the present invention has high purity, and can be directly reused without further purification treatment; the acid copper chloride etching solution copper recovery and regeneration system of the present invention and The recovery and regeneration method process can effectively absorb and consume the chlorine generated by electrolysis, most of the chlorine generated by electrolysis can be consumed immediately by the oxidation-reduction reaction of the electrolyte, and a small part of the remaining chlorine can be quickly dissolved in the electrolyte. The waste gas can be reused as an oxidant; the waste gas treatment process can effectively avoid toxic waste gas polluting the environment and ensure the safety of the whole process.

Description of drawings

Fig. 1 is etching solution regeneration process flow chart of the present invention;

Fig. 2 is the chlorine treatment flow chart of the present invention;

Fig. 3 is the processing flow chart of molten iron washing liquid of the present invention;

FIG. 4 is a flow chart of waste gas treatment according to the present invention.

Detailed ways

In order to make the purposes, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention. , not all examples. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

In the embodiment, the addition time of the etching waste liquid is controlled, so that the ^Cu concentration in the cathode area of the electrolytic cell is controlled at 30-70g/L;

Matters needing attention: When the copper ion is low, it is not suitable to open a large current, it is easy to generate copper thorns that are easy to fall off, which is not conducive to the collection and affects the quality of copper; when shutting down, the current should be reduced to about 500A before shutting down to protect the anode plate and the fire bull. ; When the system is suspended for a short time, the current needs to be reduced to about 500A to reduce the rate of copper precipitation in the solution and protect the cathode copper from being etched back by the etching solution. ; The system does not run for a long time, and the etching waste liquid in the electrolytic cell is discharged to the waste liquid storage tank through the discharge pipe, and the electrolytic cell is cleaned with water to reduce the corrosion of the equipment and the electrode plate by the etching waste liquid; when the copper ion in the cathode area is higher than When 50g/L is lower than 70g/L, turn off the etchant feed pump, electrolyze with 2400-3000A current to the parameter control range, and then start feeding; when it is higher than 70g/L, add regeneration solution or water to reduce copper ions; When an abnormality occurs in a certain part of the system, the corresponding "automatic" switch should be stopped urgently (in case of emergency, the "emergency stop switch" should be pressed immediately).

Electrolytic cell maintenance and copper output:

Electrolysis open cylinder

Scrub the contact points of the square copper of the electrolytic cell and the copper strip of the titanium light plate with 1% dilute sulfuric acid to prevent poor conductivity and heat; put the titanium light plate, and check whether the surface of the titanium light plate is oxidized (black and dark). Use a wire brush wheel to polish off the oxidized area, tighten the screws of the titanium light plate and the copper bar, and check whether the titanium light plate is vertically downward. If there is any deviation, it is necessary to twist the bending radian of the copper strip; open the ball valve and pump of the waste liquid adding pipeline. , after adding about 1/4-1/3 volume of the electrolytic cell, turn off the waste liquid pump, add regeneration liquid or water to make up the liquid level (during the process of adding liquid medicine, turn on the cathode circulation pump to pump the liquid medicine in the cathode chamber into the electrolytic cell, Pay attention to the liquid level of the cathode chamber to prevent the circulating pump from being evacuated); turn on the cathode circulating pump, and add acidity copper brightener; after turning on the exhaust gas absorption equipment, turn on the rectifier, first electrolyze at 1000-1500A for 1-2H, to ensure that the bottom copper is combined with the cathode plate Well, analyze the copper ion content in the electrolytic cell, then adjust the current according to the copper ion concentration, and use a clamp meter to measure whether the current is uniform (clean the contact point between the titanium plate and the square copper when the current is uneven);

Maintenance during electrolysis

During the electrolysis process, regenerative etching solution continuously flows out of the anode chamber. Pay attention to the liquid level of the cathode chamber at any time to prevent the cathode circulating pump from being evacuated. When the liquid level is low, turn on the regeneration liquid adding pump to replenish the liquid level; take samples in the cathode circulating cylinder every four hours for analysis The copper ion content at one time, and the current is adjusted according to the copper ions. During the normal electrolysis process, the copper ion content is controlled at 30-50g/L. When the copper ion is less than 30g/L, the waste liquid will be added; a copper plate will be extracted for each shift to check If the surface of the copper plate is powdered, the current control is too high; the copper thorns on the surface of the copper plate are serious, and the amount of copper plating additives should be increased; after one day of electrolysis, the copper thorns on the cathode plate must be knocked off with PP sticks in each shift. In order to avoid copper thorns piercing through the anode diaphragm or causing short circuit between the cathode and anode; the analysis and testing data during the electrolysis process are recorded in each shift, each batch of cathode plates is electrolyzed for 4-7 days, and each copper plate weighs 10-15KG, and copper can be produced. ;

electrolytic copper

One day before copper production, it is necessary to stop adding waste liquid, and reduce the copper ions in the existing liquid medicine to less than 5g/L, so as to facilitate the discharge to the waste water station and prevent the expansion of the etching liquid. When the copper content is reduced by electrolysis, pay attention to adjusting the current; When the copper ion in the cathode chamber is lower than 5g/L, turn off the cathode circulating pump, adjust the current to 500A or turn off the rectifier, and discharge the etching solution in the electrolytic cell to the regeneration liquid barrel or sewage treatment station through the medicine discharge pipe (when the medicine is discharged to half The rectifier must be closed); open the electrolytic cell cover and rinse the cathode plate and anode box with water once to prevent the generation of a large amount of hydrochloric acid fumes; remove the cathode plate, peel off the copper plates on both sides of the cathode plate, and put them in a copper washing tank for one day; The middle copper plate is taken out, placed neatly on the card board, and the water is drained and weighed.

Opening and replacement of molten iron absorption tank:

Clean the molten iron tank and molten iron absorption tank;

The operating point of the newly opened line needs to use iron to make FeCl2 solution: add 1/2 of water to the iron-dissolving tank, add iron and hydrochloric acid, and control the concentration of hydrochloric acid at 1-2N, and continuously add iron to the iron-dissolving tank to keep the iron-dissolving tank There is always iron in the solution, and it takes about 3-4 days to soak, and the Fe2+ content in the solution is 20-50g/L;

Add 2/3 of water to the iron suction cylinder, circulate the solution in the iron melting cylinder and the iron absorption cylinder, add water and hydrochloric acid when the liquid level drops, and control the acidity to 0.3-0.8N concentration;

Turn on the jet pump of the iron absorption cylinder, and then turn on the electrolytic tank. When the molten iron is first opened, the current should be electrolyzed with a small current, and then the current should be gradually increased. Pay attention to check whether the exhaust gas is treated up to the standard at any time;

In the process of molten iron circulation, pay attention to adding iron (iron should always be kept in the molten iron tank) and hydrochloric acid (acidity should be controlled at 0.3-0.8). When the specific gravity reaches 1.5, the molten iron needs to be replaced.

Replacement of molten iron washing liquid: When the specific gravity of molten iron reaches 1.5, discharge 80% of the molten iron washing liquid, and then prepare according to the steps of 7.1 to 7.5. Note that the molten iron needs to be discharged into the environmental protection pool or special storage bucket.

Example 1:

The acid copper chloride etching solution copper recovery and regeneration system in this embodiment includes an etching solution regeneration system and a waste gas treatment system located downstream of the etching solution regeneration system, and also includes a molten iron washing solution treatment system. The etching solution regeneration system includes sequentially connected etching production line, waste gas treatment system Liquid storage tank, electrolytic cell, regeneration liquid storage tank, the downstream of regeneration liquid storage tank is connected with the etching production line, the anode area of the electrolytic cell is connected with the dissolution absorption tank, the jet device and the etching production line are connected in turn;

The molten iron washing liquid treatment system includes a molten iron tank, a molten iron absorption tank, and a molten iron washing tower connected in sequence;

The etching production line has an environmental exhaust pipe, which is connected to the exhaust gas treatment system through a pipeline.

The waste gas treatment system includes a dissolving absorption cylinder, a molten iron absorption cylinder, a molten iron washing tower, an alkali liquor absorption tower, and an exhaust port, which are connected in sequence. The anode area of the electrolytic cell is connected to the dissolving absorption cylinder, (the gas in the anode area of the electrolytic cell enters the dissolving absorption cylinder, the molten iron absorption cylinder, the molten iron washing tower, the lye absorption tower, and the exhaust port in turn through the pipeline to complete the waste gas treatment); the cathode of the electrolytic cell The area is connected with the molten iron washing tower (the gas in the cathode area of the electrolytic cell enters the molten iron washing tower, the lye absorption tower, and the exhaust port in turn through the pipeline to complete the waste gas treatment); the environmental exhaust pipe is connected with the lye absorption tower;

The method for recovering and regenerating copper in the acid cupric chloride etching solution in this embodiment includes etching solution regeneration, chlorine gas treatment, molten iron washing solution treatment, and waste gas treatment; the etching solution regeneration is as follows: the etching waste solution is introduced into an electrolytic cell as an electrolyte solution for carrying out Electrolysis, under the action of electrolysis, when the electrolyte is electrolyzed, metallic copper is generated on the cathode plate, and chlorine gas is generated on the anode plate. Under the oxidation of the extremely strong oxidizing product chlorine gas, the ORP increases, so that the regeneration of the etching waste liquid reaches the standard of the effective etching solution, and then the regenerated etching solution is introduced into the etching production line and recycled.

The content of copper ions in the cathode area of the electrolytic cell is sampled and analyzed once every four hours. During the normal electrolysis process, the content of copper ions is controlled at 50-70 g/L. The electrolytic current of the electrolytic cell is 2400-3000 A. The mass concentration of copper ions is always < the mass concentration of copper ions in the electrolyte in the anode area; the electrolytic cell is provided with an electrolytic diaphragm;

The chlorine treatment is as follows: the oxidizing gas chlorine generated in the anode chamber enters the dissolution and absorption tank, and then is reused to the etching production line through the jet device, so as to achieve cyclic regeneration; the treatment process of the molten iron washing liquid is as follows: molten iron tank - molten iron absorption tank - molten iron The washing tower contains ferric dichloride, elemental iron and hydrogen chloride in the molten iron cylinder; the iron dichloride containing impurities is in the molten iron absorption cylinder; the pure iron dichloride is in the molten iron washing tower; the waste gas is The treatment process is: electrolytic cell anode gas-dissolution absorption tank-hot metal absorption tank-hot metal washing tower-alkali washing tower-discharge; electrolytic cell cathode gas-hot metal absorption tank-hot metal washing tower-alkali washing tower-discharge; environmental pumping Duct - lye scrubber - discharge.

Example 2:

The acid copper chloride etching solution copper recovery and regeneration system in this embodiment includes an etching solution regeneration system and a waste gas treatment system located downstream of the etching solution regeneration system, and also includes a molten iron washing solution treatment system. The etching solution regeneration system includes sequentially connected etching production line, waste gas treatment system Liquid storage tank, electrolytic cell, regeneration liquid storage tank, the downstream of regeneration liquid storage tank is connected with the etching production line, the anode area of the electrolytic cell is connected with the dissolution absorption tank, the jet device and the etching production line are connected in turn;

The molten iron washing liquid treatment system includes a molten iron tank, a molten iron absorption tank, and a molten iron washing tower connected in sequence;

The etching production line has an environmental exhaust pipe, which is connected to the exhaust gas treatment system through a pipeline.

The waste gas treatment system includes a dissolving absorption cylinder, a molten iron absorption cylinder, a molten iron washing tower, an alkali liquor absorption tower, and an exhaust port, which are connected in sequence. The anode area of the electrolytic cell is connected to the dissolving absorption cylinder, (the gas in the anode area of the electrolytic cell enters the dissolving absorption cylinder, the molten iron absorption cylinder, the molten iron washing tower, the lye absorption tower, and the exhaust port in turn through the pipeline to complete the waste gas treatment); the cathode of the electrolytic cell The area is connected with the molten iron washing tower (the gas in the cathode area of the electrolytic cell enters the molten iron washing tower, the lye absorption tower, and the exhaust port in turn through the pipeline to complete the waste gas treatment); the environmental exhaust pipe is connected with the lye absorption tower;

The method for recovering and regenerating copper in the acid cupric chloride etching solution in this embodiment includes etching solution regeneration, chlorine gas treatment, molten iron washing solution treatment, and waste gas treatment; the etching solution regeneration is as follows: the etching waste solution is introduced into an electrolytic cell as an electrolyte solution for carrying out Electrolysis, under the action of electrolysis, when the electrolyte is electrolyzed, metallic copper is generated on the cathode plate, and chlorine gas is generated on the anode plate. Under the oxidation of the extremely strong oxidizing product chlorine gas, the ORP increases, so that the regeneration of the etching waste liquid reaches the standard of the effective etching solution, and then the regenerated etching solution is introduced into the etching production line and recycled.

The content of copper ions in the cathode area of the electrolytic cell is sampled and analyzed once every four hours. During the normal electrolysis process, the content of copper ions is controlled at 30-50 g/L. The electrolytic current of the electrolytic cell is 1800-2400 A. The mass concentration of copper ions is always < the mass concentration of copper ions in the electrolyte in the anode area; the electrolytic cell is provided with an electrolytic diaphragm;

The chlorine treatment is as follows: the oxidizing gas chlorine generated in the anode chamber enters the dissolution and absorption tank, and then is reused to the etching production line through the jet device, so as to achieve cyclic regeneration; the treatment process of the molten iron washing liquid is as follows: molten iron tank - molten iron absorption tank - molten iron The washing tower contains ferric dichloride, elemental iron and hydrogen chloride in the molten iron cylinder; the iron dichloride containing impurities is in the molten iron absorption cylinder; the pure iron dichloride is in the molten iron washing tower; the waste gas is The treatment process is: electrolytic cell anode gas-dissolution absorption tank-hot metal absorption tank-hot metal washing tower-alkali washing tower-discharge; electrolytic cell cathode gas-hot metal absorption tank-hot metal washing tower-alkali washing tower-discharge; environmental pumping Duct - lye scrubber - discharge.

Example 3:

The acid copper chloride etching solution copper recovery and regeneration system in this embodiment includes an etching solution regeneration system and a waste gas treatment system located downstream of the etching solution regeneration system, and also includes a molten iron washing solution treatment system. The etching solution regeneration system includes sequentially connected etching production line, waste gas treatment system Liquid storage tank, electrolytic cell, regeneration liquid storage tank, the downstream of regeneration liquid storage tank is connected with the etching production line, the anode area of the electrolytic cell is connected with the dissolution absorption tank, the jet device and the etching production line are connected in turn;

The molten iron washing liquid treatment system includes a molten iron tank, a molten iron absorption tank, and a molten iron washing tower connected in sequence;

The etching production line has an environmental exhaust pipe, which is connected to the exhaust gas treatment system through a pipeline.

The waste gas treatment system includes a dissolving absorption cylinder, a molten iron absorption cylinder, a molten iron washing tower, an alkali liquor absorption tower, and an exhaust port, which are connected in sequence. The anode area of the electrolytic cell is connected to the dissolving absorption cylinder, (the gas in the anode area of the electrolytic cell enters the dissolving absorption cylinder, the molten iron absorption cylinder, the molten iron washing tower, the lye absorption tower, and the exhaust port in turn through the pipeline to complete the waste gas treatment); the cathode of the electrolytic cell The area is connected with the molten iron washing tower (the gas in the cathode area of the electrolytic cell enters the molten iron washing tower, the lye absorption tower, and the exhaust port in turn through the pipeline to complete the waste gas treatment); the environmental exhaust pipe is connected with the lye absorption tower;

The method for recovering and regenerating copper in the acid cupric chloride etching solution in this embodiment includes etching solution regeneration, chlorine gas treatment, molten iron washing solution treatment, and waste gas treatment; the etching solution regeneration is as follows: the etching waste solution is introduced into an electrolytic cell as an electrolyte solution for carrying out Electrolysis, under the action of electrolysis, when the electrolyte is electrolyzed, metallic copper is generated on the cathode plate, and chlorine gas is generated on the anode plate. Under the oxidation of the extremely strong oxidizing product chlorine gas, the ORP increases, so that the regeneration of the etching waste liquid reaches the standard of the effective etching solution, and then the regenerated etching solution is introduced into the etching production line and recycled.

The content of copper ions in the cathode area of the electrolytic cell is sampled and analyzed once every four hours. During the normal electrolysis process, the content of copper ions is controlled at 15-30 g/L. The electrolytic current of the electrolytic cell is 1000-1800 A. The mass concentration of copper ions is always < the mass concentration of copper ions in the electrolyte in the anode area; the electrolytic cell is provided with an electrolytic diaphragm;

The chlorine treatment is as follows: the oxidizing gas chlorine generated in the anode chamber enters the dissolution and absorption tank, and then is reused to the etching production line through the jet device, so as to achieve cyclic regeneration; the treatment process of the molten iron washing liquid is as follows: molten iron tank - molten iron absorption tank - molten iron The washing tower contains ferric dichloride, elemental iron and hydrogen chloride in the molten iron cylinder; the iron dichloride containing impurities is in the molten iron absorption cylinder; the pure iron dichloride is in the molten iron washing tower; the waste gas is The treatment process is: electrolytic cell anode gas-dissolution absorption tank-hot metal absorption tank-hot metal washing tower-alkali washing tower-discharge; electrolytic cell cathode gas-hot metal absorption tank-hot metal washing tower-alkali washing tower-discharge; environmental pumping Duct - lye scrubber - discharge.

It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that it can still be used for The technical solutions described in the foregoing embodiments are modified, or some technical features thereof are equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (8)

1. The system for recycling the copper in the acidic copper chloride etching solution is characterized by comprising an etching solution recycling system, a waste gas treatment system and a molten iron washing solution treatment system, wherein the waste gas treatment system is positioned at the downstream of the etching solution recycling system;

the molten iron washing liquid treatment system comprises an iron dissolving cylinder, a molten iron absorption cylinder and a molten iron washing tower which are connected in sequence; wherein, the molten iron washing liquid treatment process comprises the following steps in sequence: the method comprises the following steps of (1) dissolving an iron cylinder, a molten iron absorption cylinder and a molten iron washing tower, wherein the dissolving iron cylinder contains iron dichloride, simple substance iron and hydrogen chloride; iron dichloride containing impurities is filled in the molten iron absorption cylinder; pure iron dichloride is filled in the molten iron washing tower;

the etching production line is provided with an environment exhaust pipe which is connected with the waste gas treatment system through a pipeline,

the waste gas treatment system is including the dissolution absorption jar, molten iron scrubbing tower, alkali lye absorption tower, the gas vent that connect gradually, the upper reaches of waste gas treatment system is connected with electrolysis trough anode region, electrolysis trough cathode region, environment exhaust column respectively, electrolysis trough anode region with the dissolution absorption jar is connected, electrolysis trough cathode region with the molten iron scrubbing tower is connected, the environment exhaust column with the alkali lye absorption tower is connected.

2. The method for recycling the copper in the acidic copper chloride etching solution according to claim 1, wherein the recycling method comprises etching solution recycling, chlorine treatment, molten iron washing solution treatment, and waste gas treatment; the regeneration of the etching solution is as follows: the etching waste liquid is introduced into an electrolytic tank to be used as electrolyte for electrolysis, under the electrolysis action, when the electrolyte is electrolyzed, metal copper is generated on a cathode plate, chlorine gas is generated on an anode plate, copper ions in the etching waste liquid are reduced into copper powder simple substance at a cathode, so that the concentration of the copper ions is reduced, and simultaneously, under the oxidation action of the anode strong oxidation product chlorine gas, ORP is increased, so that the regeneration of the etching waste liquid reaches the standard of effective etching liquid, and the regenerated etching liquid is introduced into an etching production line for recycling.

3. The recycling method as claimed in claim 2, wherein the copper ion content in the cathode region of the electrolytic cell is controlled to be 30-70g/L, the electrolytic current of the electrolytic cell is 1000-3000A, and the copper ion mass concentration of the electrolyte in the cathode region of the electrolytic cell is always less than that of the electrolyte in the anode region.

4. The recovery regeneration method as claimed in claim 3, wherein the cathode region of the electrolytic cell is sampled and analyzed once every four hours for copper ion content, the copper ion content is controlled to be 30-50g/L in the normal electrolysis process, the electrolysis current of the electrolytic cell is 1800-2400A, and when the copper ion content is less than 30g/L, the etching waste liquid is supplemented.

5. The recycling method according to claim 2, characterized in that: an electrolytic diaphragm is arranged in the electrolytic cell.

6. The recovery regeneration process of claim 2, wherein the chlorine treatment is: oxidizing gas chlorine generated by the anode chamber enters a dissolution absorption cylinder and is recycled to an etching production line through a jet device, so that cyclic regeneration is achieved.

7. The recycling and regenerating method according to claim 2, characterized in that the molten iron washing liquid treatment process comprises the following steps in sequence: the method comprises the following steps of (1) dissolving an iron cylinder, a molten iron absorption cylinder and a molten iron washing tower, wherein the dissolving iron cylinder contains iron dichloride, simple substance iron and hydrogen chloride; iron dichloride containing impurities is filled in the molten iron absorption cylinder; pure iron dichloride is filled in the molten iron washing tower.

8. The recovery and regeneration method according to claim 2, wherein the off-gas treatment process is: the method comprises the following steps of (1) discharging anode gas of an electrolytic cell, a dissolution absorption cylinder, a molten iron washing tower, an alkali liquor washing tower; electrolytic bath cathode gas-molten iron absorption cylinder-molten iron washing tower-alkali liquor washing tower-discharging; an environmental exhaust pipe, an alkali liquor washing tower and discharge.

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