CN109161895B - Copper recovery and regeneration system and method for acidic copper chloride etching solution - Google Patents
Copper recovery and regeneration system and method for acidic copper chloride etching solution Download PDFInfo
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- CN109161895B CN109161895B CN201810979851.3A CN201810979851A CN109161895B CN 109161895 B CN109161895 B CN 109161895B CN 201810979851 A CN201810979851 A CN 201810979851A CN 109161895 B CN109161895 B CN 109161895B
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23F1/46—Regeneration of etching compositions
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- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
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Abstract
The invention provides a copper recycling system and a copper recycling method for acidic copper chloride etching solution, and relates to the technical field of etching solution recycling. The acid copper chloride etching solution copper recovery and regeneration system comprises an etching solution regeneration system, a waste gas treatment system positioned at the downstream of the etching solution regeneration system, and a molten iron washing solution treatment system; the method for recycling the copper in the acidic copper chloride etching solution effectively solves the problems of high energy consumption, low recycling rate, high cathode copper impurity content, secondary chlorine pollution to the environment and the like of the conventional acidic copper chloride etching solution recycling process, and provides technical support for the comprehensive application of the electrolytic recycling process of the acidic copper chloride etching solution.
Description
Technical Field
The invention relates to the technical field of etching solution recycling, in particular to a system and a method for recycling copper in an acidic copper chloride etching solution.
Background
Printed circuit boards are the basic components of various electronic products, and an important part of the production process is to chemically etch away excess copper (typically 60-70%) beyond what is needed for the circuitry on the copper foil plates. The acidic copper chloride and alkaline copper chloride etching solution are the most used etching agents at present, wherein the acidic copper chloride etching solution is particularly suitable for printed circuit board products with high etching precision requirements due to the characteristics of small side etching and the like, and is increasingly used by a large number of printed circuit board factories. The chemical reaction during etching is that one bivalent copper ion in the etching solution oxidizes one metal copper atom on the copper foil plate to generate two univalent copper ions. Therefore, as the etching proceeds, the total copper and monovalent copper ion concentration in the etching solution increases, which will cause the etching capability to gradually decrease. In order to maintain the desired etching capacity, it is common practice to chemically regenerate a portion of the etching solution by adding a chemical oxidizing agent to the etching solution to oxidize monovalent copper to divalent copper. The etching solution after chemical regeneration is reused, and the other part of the non-regenerated etching solution becomes etching waste liquid. The copper content of 2-2.5L generated by etching one square meter of printed circuit board is 100-150g.L-1The etching waste liquid of (4).
The waste copper etching liquid generated in the printed circuit board factory is generally sent to a waste liquid treatment factory to treat and recover copper by chemical methods such as neutralization precipitation, replacement, extraction and the like. However, these treatment methods recover copper from the waste liquid in the form of compounds, which have low product value and consume a large amount of chemicals 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 discharged into the environment, which causes environmental pollution.
At present, the units for researching and developing copper chloride etching solution electrolysis recovery copper at home and abroad are not few, and the researched and developed equipment has different problems in the using process, so that the equipment cannot be put into industry for use, such as: the etching solution after the copper is extracted by electrolysis cannot be recycled, so that not only is the environment polluted, but also chemical raw materials are wasted; another technical problem is that the anodes have a chlorine evolution during electrolysis, which, according to a theoretical calculation, gives 111.6kg of chlorine per 100kg of copper electrolytically deposited at the anode, the standard volume of which is about 35.26m3However, the cost and equipment complexity are increased by properly treating the large amount of chlorine gas generated and the residual waste liquid without causing secondary pollution to the environment.
Therefore, the development of a copper recovery and regeneration system and a recovery and regeneration method for the acidic copper chloride etching solution is particularly important for the recovery and reuse of copper.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a system and a method for recovering and regenerating copper in an acidic copper chloride etching solution.
In order to achieve the above purpose, the technical scheme of the invention is realized by the following technical scheme:
a copper recovery and regeneration system for an acidic copper chloride etching solution comprises an etching solution regeneration 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 regeneration 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 comprises a dissolving absorption cylinder, a molten iron washing tower, an alkali liquor absorption tower and an exhaust port which are connected in sequence, wherein the upstream of the waste gas treatment system is respectively connected with an electrolytic cell anode region, an electrolytic cell cathode region and an environmental exhaust pipe, the electrolytic cell anode region is connected with the dissolving absorption cylinder, and gas in the electrolytic cell anode region sequentially enters the dissolving absorption cylinder, the molten iron washing tower, the alkali liquor absorption tower and the exhaust port through pipelines to 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 sequentially enters the molten iron washing tower, the alkali liquor absorption tower and the exhaust port through pipelines to complete waste gas treatment); and the environment exhaust pipe is connected with the alkali liquor absorption tower.
Further, the recovery regeneration method comprises etching solution regeneration, 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.
Further, the content of copper ions in the cathode area of the electrolytic cell is controlled to be 30-70g/L, the electrolytic current of the electrolytic cell is 1000-3000A, and the mass concentration of the copper ions in the electrolyte in the cathode area of the electrolytic cell is always less than that of the electrolyte in the anode area.
Further, sampling and analyzing the copper ion content once every four hours in the cathode area of the electrolytic cell, controlling the copper ion content to be 30-50g/L in the normal electrolytic process, controlling the electrolytic current of the electrolytic cell to be 1800 ion/2400A, and supplementing the etching waste liquid when the copper ion content is less than 30 g/L.
Furthermore, an electrolytic diaphragm is arranged in the electrolytic cell.
Further, the chlorine treatment is as follows: 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.
Further, the molten iron washing liquid treatment process sequentially comprises the following steps: 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.
Further, the waste gas treatment process comprises the following steps: 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.
The invention provides a copper recovery and regeneration system and a recovery and regeneration method for an acidic copper chloride etching solution, and compared with the prior art, the copper recovery and regeneration system and the recovery and regeneration method have the advantages that:
the system and the method for recycling the copper in the acidic copper chloride etching solution effectively solve the problems of high energy consumption, low recycling rate, high cathode copper impurity content, secondary chlorine gas pollution to the environment and the like of the conventional acidic copper chloride etching solution recycling process, and provide technical support for the comprehensive application of the electrolytic recycling technology of the acidic copper chloride etching solution;
the electrolytic current of the invention has high efficiency, can effectively save production cost, save energy, improve copper recovery efficiency, and ensure that the whole recovery and regeneration process has higher stability, safety and economic benefit; the copper recovery and regeneration system and the recovery and regeneration method for the acidic copper chloride etching solution ensure that etching and electrolysis can smoothly and synchronously run. In addition, the copper metal obtained by electrolysis is automatically collected by a machine, the start and stop of the electrolysis are automatically controlled, the overall automation degree of the process is high, and the human input is reduced. Chlorine generated in electrolysis can be used as an oxidant to oxidize monovalent copper ions and ferrous ions in the electrolyte, so that the use of a liquid oxidant in the regeneration process of the etching solution is saved;
the copper recovery and regeneration system and the recovery and regeneration method for the acid copper chloride etching solution have high purity of the recovered copper, and can be directly reused without further purification treatment; the copper recovery and regeneration system and the recovery and regeneration method for the acid copper chloride etching solution can effectively absorb and consume chlorine generated by electrolysis, most of the chlorine generated by electrolysis can be immediately consumed through the redox reaction of the electrolyte, and the rest of the chlorine can be quickly dissolved in the electrolyte and can be reused as an oxidant in subsequent working procedures; the waste gas treatment process can effectively avoid the pollution of toxic waste gas to the environment, and the safety of the whole process is ensured.
Drawings
FIG. 1 is a flow chart of the regeneration process of the etching solution according to the present invention;
FIG. 2 is a chlorine treatment scheme according to the present invention;
FIG. 3 is a flow chart of the molten iron washing liquid treatment according to the present invention;
FIG. 4 is a flow chart of the waste gas treatment according to the present invention.
Detailed Description
In order to make the objects, 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, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the examples, the addition time of the etching waste liquid was controlled so that the electrolytic bath cathode region Cu was2+The concentration is controlled to be 30-70 g/L;
note that: when the copper ions are low, large current is not suitable to be opened, copper spurs which are easy to fall off are easy to generate, and collection is not facilitated and the quality of copper is influenced; when the machine is shut down, the machine can be shut down only by adjusting the current to be about 500A so as to protect the anode plate and the fire cattle; when the system is temporarily suspended, the current needs to be reduced to about 500A to reduce the speed of separating copper from the solution and protect the cathode copper from being corroded by the etching solution, and the current cannot be interrupted after the electrolysis is started so as to prevent the electrolyzed copper from being corroded; the system does not operate for a long time, the etching waste liquid in the electrolytic bath is discharged to a waste liquid storage barrel through the medicine discharge pipe, and the electrolytic bath is cleaned by clear water, so that the corrosion of the etching waste liquid to equipment and a polar plate is reduced; when the copper ions in the cathode region are higher than 50g/L and lower than 70g/L, closing the etching solution inlet pump, electrolyzing to the parameter control range by 2400-3000A current, and then starting to feed the solution; when the concentration is higher than 70g/L, adding a regeneration liquid or water to reduce copper ions; when a certain part of the system is abnormal, the corresponding 'automatic' switch is urgently stopped (if an emergency occurs, the 'emergency stop switch' is immediately pressed).
Electrolytic maintenance and copper discharging of the electrolytic cell:
electric unlocking cylinder
Scrubbing contact points of copper strips and titanium light plates of the electrolytic cell by using 1% dilute sulfuric acid to prevent poor conduction and heating; placing a titanium light plate, checking whether the surface of the titanium light plate is oxidized (blackened and dark) when the titanium light plate is placed, polishing the oxidized part by using a steel wire brush wheel, screwing screws of the titanium light plate and a copper bar, checking whether the titanium light plate is vertically downward, and twisting a copper bar to correct the bending radian when the titanium light plate is deviated; opening a waste liquid adding pipeline ball valve and a pump, after adding about 1/4-1/3 volume of the electrolytic bath, closing a waste liquid pump, and adding a regeneration liquid or water to supplement the liquid level (starting a cathode circulating pump to pump the liquid medicine in the cathode chamber into the electrolytic bath in the liquid medicine adding process, and paying attention to the liquid level in the cathode chamber to prevent the circulating pump from pumping out); starting a cathode circulating pump, and adding an acidity copper brightener; starting a tail gas absorption device, then starting a rectifier, electrolyzing for 1-2H at 1000-1500A to ensure that bottom copper is well combined with a cathode plate, analyzing the content of copper ions in an electrolytic bath, adjusting current according to the concentration of the copper ions, and measuring whether the current is uniform or not by using a clamp meter (cleaning a contact point between a titanium plate and square copper when the current is not uniform);
maintenance in electrolytic process
In the electrolysis process, the regenerated etching solution continuously flows out of the anode chamber, the liquid level of the cathode chamber is noticed at any time, the cathode circulating pump is prevented from being pumped out, and the regenerated solution adding pump is started to supplement the liquid level when the liquid level is low; sampling and analyzing the copper ion content once in a cathode circulating cylinder every four hours, adjusting the current according to copper ions, controlling the copper ion content to be 30-50g/L in the normal electrolysis process, and supplementing the waste liquid when the copper ions are less than 30 g/L; extracting a copper plate every time, checking the copper bonding condition on the surface of the copper plate, and controlling the current to be too high if the surface of the copper plate is powdered; the copper plate surface has serious copper prick, and the copper plating additive amount is increased; after one day of electrolysis, the copper pricks on the cathode plate must be knocked off by a PP stick in each shift so as to prevent the copper pricks from propping the anode diaphragm or causing short circuit of the cathode and the anode; recording analysis and detection data in the electrolytic process in each shift, electrolyzing each batch of negative plates for 4-7 days, and taking out copper after each copper plate weighs 10-15 KG;
electrolytic copper production
Adding waste liquid is stopped one day before copper is discharged, the copper ions in the existing liquid medicine are reduced to be below 5g/L so as to be conveniently discharged to a wastewater station for treatment, the etching liquid medicine is prevented from swelling, and when the copper content is reduced through electrolysis, the current is regulated; when the copper ions in the cathode chamber are lower than 5g/L, the cathode circulating pump is closed, the current is adjusted to 500A or the rectifier is closed, and the etching solution in the electrolytic bath is discharged to a regeneration solution barrel or a sewage treatment station through a discharge pipe (the rectifier is closed when the solution is discharged to a half); the cover of the electrolytic bath is opened, and the cathode plate and the anode box are washed once by water, so that a large amount of hydrochloric acid smoke is prevented from being generated; taking down the negative plate, stripping the copper plates on two sides of the negative plate, and soaking in a copper washing tank for one day; and fishing out the copper plate in the copper washing cylinder, neatly stacking the copper plate on the clamping plate, draining water and weighing.
Opening and replacing the molten iron absorption cylinder:
cleaning a molten iron cylinder and a molten iron absorption cylinder;
the new open run point requires the infusion of FeCl2 solution with iron: adding 1/2 water into the iron dissolving cylinder, adding iron and hydrochloric acid, controlling the concentration of hydrochloric acid at 1-2N, continuously adding iron into the iron dissolving cylinder, keeping iron in the iron dissolving cylinder, and soaking for about 3-4 days until the content of Fe2+ in the solution is 20-50 g/L;
adding 2/3 water into the iron absorption tank, circulating the solution in the iron dissolution tank and the iron absorption tank, adding water and hydrochloric acid when the liquid level is reduced, and controlling the acidity at 0.3-0.8N;
starting a jet pump of an iron absorption cylinder, starting an electrolytic cell, electrolyzing molten iron by using low current when the cylinder is just opened, gradually increasing the current, and paying attention to detect whether the tail gas treatment reaches the standard at any time;
iron (iron is always kept in the iron dissolving cylinder) and hydrochloric acid (acidity is controlled to be 0.3-0.8) are added in the molten iron circulation process in an intentional manner, and when the specific gravity reaches 1.5, the molten iron needs to be replaced.
Replacing molten iron washing liquid: when the specific gravity of the molten iron reaches 1.5, discharging 80% of the molten iron washing liquid, and preparing according to the steps of 7.1-7.5, wherein the molten iron needs to be discharged into an environment-friendly pool or a special storage barrel.
Example 1:
the acid copper chloride etching solution copper recovery and regeneration system comprises an etching solution regeneration 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 regeneration 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;
an environment exhaust pipe is arranged on the etching production line and is connected with a waste gas treatment system through a pipeline,
the waste gas treatment system comprises a dissolving absorption cylinder, a molten iron washing tower, an alkali liquor absorption tower and an exhaust port which are connected in sequence, wherein the upstream of the waste gas treatment system is respectively connected with an electrolytic cell anode region, an electrolytic cell cathode region and an environmental exhaust pipe, the electrolytic cell anode region is connected with the dissolving absorption cylinder, and gas in the electrolytic cell anode region sequentially enters the dissolving absorption cylinder, the molten iron washing tower, the alkali liquor absorption tower and the exhaust port through pipelines to 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 sequentially enters the molten iron washing tower, the alkali liquor absorption tower and the exhaust port through pipelines to complete waste gas treatment); the environment exhaust pipe is connected with the alkali liquor absorption tower;
the method for recycling the copper in the acidic copper chloride etching solution comprises etching solution regeneration, 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.
Sampling and analyzing the copper ion content once every four hours in the cathode area of the electrolytic cell, controlling the copper ion content to be 50-70g/L in the normal electrolytic process, wherein the electrolytic current of the electrolytic cell is 2400-3000A, and the copper ion mass concentration of the electrolyte in the cathode area of the electrolytic cell is always less than that of the electrolyte in the anode area; an electrolytic diaphragm is arranged inside the electrolytic cell;
the chlorine treatment comprises the following steps: 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; the molten iron washing liquid treatment process sequentially comprises the following steps: 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 waste gas treatment process comprises the following steps: 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.
Example 2:
the acid copper chloride etching solution copper recovery and regeneration system comprises an etching solution regeneration 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 regeneration 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;
an environment exhaust pipe is arranged on the etching production line and is connected with a waste gas treatment system through a pipeline,
the waste gas treatment system comprises a dissolving absorption cylinder, a molten iron washing tower, an alkali liquor absorption tower and an exhaust port which are connected in sequence, wherein the upstream of the waste gas treatment system is respectively connected with an electrolytic cell anode region, an electrolytic cell cathode region and an environmental exhaust pipe, the electrolytic cell anode region is connected with the dissolving absorption cylinder, and gas in the electrolytic cell anode region sequentially enters the dissolving absorption cylinder, the molten iron washing tower, the alkali liquor absorption tower and the exhaust port through pipelines to 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 sequentially enters the molten iron washing tower, the alkali liquor absorption tower and the exhaust port through pipelines to complete waste gas treatment); the environment exhaust pipe is connected with the alkali liquor absorption tower;
the method for recycling the copper in the acidic copper chloride etching solution comprises etching solution regeneration, 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.
Sampling and analyzing the copper ion content once every four hours in the cathode area of the electrolytic cell, controlling the copper ion content to be 30-50g/L in the normal electrolytic process, wherein the electrolytic current of the electrolytic cell is 1800-2400A, and the copper ion mass concentration of the electrolyte in the cathode area of the electrolytic cell is always less than that of the electrolyte in the anode area; an electrolytic diaphragm is arranged inside the electrolytic cell;
the chlorine treatment comprises the following steps: 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; the molten iron washing liquid treatment process sequentially comprises the following steps: 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 waste gas treatment process comprises the following steps: 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.
Example 3:
the acid copper chloride etching solution copper recovery and regeneration system comprises an etching solution regeneration 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 regeneration 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;
an environment exhaust pipe is arranged on the etching production line and is connected with a waste gas treatment system through a pipeline,
the waste gas treatment system comprises a dissolving absorption cylinder, a molten iron washing tower, an alkali liquor absorption tower and an exhaust port which are connected in sequence, wherein the upstream of the waste gas treatment system is respectively connected with an electrolytic cell anode region, an electrolytic cell cathode region and an environmental exhaust pipe, the electrolytic cell anode region is connected with the dissolving absorption cylinder, and gas in the electrolytic cell anode region sequentially enters the dissolving absorption cylinder, the molten iron washing tower, the alkali liquor absorption tower and the exhaust port through pipelines to 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 sequentially enters the molten iron washing tower, the alkali liquor absorption tower and the exhaust port through pipelines to complete waste gas treatment); the environment exhaust pipe is connected with the alkali liquor absorption tower;
the method for recycling the copper in the acidic copper chloride etching solution comprises etching solution regeneration, 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.
Sampling and analyzing the copper ion content once every four hours in the cathode area of the electrolytic cell, controlling the copper ion content to be 15-30g/L in the normal electrolytic process, wherein the electrolytic current of the electrolytic cell is 1000-1800A, and the copper ion mass concentration of the electrolyte in the cathode area of the electrolytic cell is always less than that of the electrolyte in the anode area; an electrolytic diaphragm is arranged inside the electrolytic cell;
the chlorine treatment comprises the following steps: 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; the molten iron washing liquid treatment process sequentially comprises the following steps: 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 waste gas treatment process comprises the following steps: 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.
It should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding 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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| CN109881199A (en) * | 2019-04-10 | 2019-06-14 | 深圳市铿东科技有限公司 | A kind of regenerating alkaline etching liquid and its copper recovery system |
| CN109881200B (en) * | 2019-04-10 | 2021-05-11 | 深圳市铿东科技有限公司 | Regeneration of alkaline etching solution and copper recovery method thereof |
| CN110453225B (en) * | 2019-08-29 | 2021-07-30 | 深圳市祺鑫环保科技有限公司 | Method for treating acidic waste etching solution |
| CN111101157A (en) * | 2019-12-27 | 2020-05-05 | 合肥恒力装备有限公司 | Zero-emission treatment process for PCB etching waste liquid |
| CN111394725A (en) * | 2020-04-24 | 2020-07-10 | 深圳市京中康科技有限公司 | Device for recovering chlorine gas by acid etching copper recovery system |
| CN111560615B (en) * | 2020-04-24 | 2022-09-16 | 励福(江门)环保科技股份有限公司 | Method for on-line recovery of copper and chlorine from acidic etching waste liquid and regeneration of etching liquid |
| CN111394728A (en) * | 2020-04-24 | 2020-07-10 | 深圳市京中康科技有限公司 | Method for further treating chlorine in acid etching copper recovery system |
| CN111733419A (en) * | 2020-08-05 | 2020-10-02 | 上海毅蓝电子科技有限公司 | Acidic etching solution and device and method for recycling electrolytic copper extraction |
| CN113088722A (en) * | 2021-03-17 | 2021-07-09 | 磨名言 | Method for electrolytically recovering copper from copper sulfide ore |
| CN113564638A (en) * | 2021-07-12 | 2021-10-29 | 天水华洋电子科技股份有限公司 | Recyclable and recyclable etching liquid medicine process |
| TW202308947A (en) * | 2021-08-19 | 2023-03-01 | 葉濤 | A method and a device for copper recycling via precipitation and regenerating via electrolysis from acidic cupric chloride etchant waste |
| CN114318372B (en) * | 2022-01-18 | 2022-07-12 | 广东德同环保科技有限公司 | Device and method for absorbing chlorine by circularly electrolyzing ferric trichloride |
| CN114481221A (en) * | 2022-01-26 | 2022-05-13 | 昆山华拓环保科技有限公司 | Copper extraction method of recyclable acidic etching solution |
| CN115537816B (en) * | 2022-10-08 | 2024-06-07 | 青岛理工大学 | Rotational flow electrolysis system and method for regenerating acidic copper chloride etchant and recycling copper |
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| CN104152905B (en) * | 2014-06-24 | 2017-02-15 | 深圳市新锐思环保科技有限公司 | Acidic copper chloride etching liquid electrolytic regeneration recycling and copper plate recovery device and method |
| CN104911596A (en) * | 2015-06-01 | 2015-09-16 | 深圳中能润德环保有限公司 | Device and method for cyclic regeneration and copper extraction of etching liquid |
| CN105177583B (en) * | 2015-09-09 | 2018-05-08 | 成都虹华环保科技股份有限公司 | A kind of zero-emission acidic etching waste liquid circulation regeneration method and system |
| CN206570410U (en) * | 2017-01-06 | 2017-10-20 | 深圳市新锐思环保科技有限公司 | A kind of recovery and processing system of acidic etching waste liquid |
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