CN111304657A - Method for electrolyzing and recycling alkaline etching waste liquid - Google Patents
Method for electrolyzing and recycling alkaline etching waste liquid Download PDFInfo
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- CN111304657A CN111304657A CN202010088635.7A CN202010088635A CN111304657A CN 111304657 A CN111304657 A CN 111304657A CN 202010088635 A CN202010088635 A CN 202010088635A CN 111304657 A CN111304657 A CN 111304657A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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Abstract
A method for electrolyzing and recycling alkaline etching waste liquid comprises the following steps: (1) adding alkaline etching waste liquid or a mixed solution of the alkaline etching waste liquid and a reducing agent as an anolyte into the anode area; adding a mixed solution of alkaline etching waste liquid and a reducing agent serving as a cathode electrolyte into the cathode area; (2) starting the electrolytic power supply to carry out electrolysis operation, and precipitating metal copper on the electrolytic cathode; (3) according to a specific alkaline etching process, one or more of ammonium chloride, ammonia, water and other components contained in the alkaline etching solution are added into the anolyte and/or catholyte after the electrolysis operation in the step (2) to prepare regenerated alkaline etching sub-solution which can be reused on an alkaline etching production line. The method can improve the efficiency of electroanalysis to obtain copper, and the waste liquid can be prepared into regenerated alkaline etching sub-liquid which can keep ideal etching effect after being electrolyzed and recycled.
Description
Technical Field
The invention belongs to the technical field of post-treatment of etching waste liquid, and particularly relates to a method for electrolyzing and recycling alkaline etching waste liquid.
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 solution for the circuit board production at present comprises an acidic copper chloride etching solution and an alkaline copper ammonium chloride etching solution (hereinafter referred to as alkaline etching solution). The main components of the alkaline etching solution are copper salt, ammonium chloride, ammonia water, optional carbonate and optional additives; among them, ammonium carbonate and ammonium bicarbonate are generally used as the carbonate. In an actual production process, each component in the alkaline etching solution is continuously consumed as etching proceeds. In order to keep the components of the alkaline etching solution stable, it is necessary to add an etching replenishment solution and/or ammonia water continuously, and therefore, the alkaline etching solution in the etching bath inevitably increases and overflows the outside of the etching bath. The main component of the etching replenishment solution is an optional additive, which is also called etching sub-solution in the industry. The etching solution overflowing out of the etching bath or the used etching solution is generally called etching waste solution, the main components of the alkaline etching waste solution comprise copper ammonium chloride, cuprous ammonium chloride, ammonium chloride and ammonia water, and some alkaline etching waste solutions also contain ammonium carbonate, ammonium bicarbonate, organic ammonium salts, organic amine and the like.
In a circuit board manufacturing plant using an alkaline etching process, a large amount of alkaline etching waste liquid containing high concentration of copper ions is generated every day. At present, in addition to selling the waste liquid to an environmental protection company for treatment, some manufacturers also use electrolysis equipment to electrolyze the waste liquid in factories for copper recovery and reuse. In the prior art, the method for recycling the copper from the alkaline etching waste liquid mainly comprises an extraction electrolysis combination method and a direct electrolysis method. Wherein, the electrochemical reaction formula of the direct electrolysis method is as follows:
anode: h2O–e-→2H++1/2O2
Cathode: cu2++e-→Cu+
Cu++e-→Cu
The prior direct electrolysis process has the following technical problems:
firstly, the solid metal copper electrically precipitated on the cathode in the electrolytic process can be quickly corroded back by the electrolyte to form copper ions which are dissolved back into the electrolyte, so that the collecting efficiency of the electrodeposited copper is reduced, and is only about 60-70%. This is due to: the existing direct electrolysis process directly adopts alkaline etching waste liquid as electrolyte, and copper ammonia complex Cu (NH) is added in the electrolysis process3)4Cl2And Cu (NH)3)2The complex structure of Cl is broken and converted into metal copper, ammonium chloride and ammonia, the concentration of the ammonium chloride and the ammonia in the electrolyte is higher and higher, and the oxygen content in the solution is increased along with the generation of oxygen on the anode. The univalent copper ammonia complex in the etching waste liquid can react with ammonium chloride, ammonia and oxygen dissolved in the etching waste liquid to generate a bivalent copper ammonia complex which can react with the metal copper, and the metal copper obtained by electrolysis is corroded back. According to the principle that the concentration of the reactant is in direct proportion to the reaction rate, the higher the concentration of the reactant is, the higher the speed of generating the divalent copper ammonia complex in the electrolyte is, and the more obvious the corrosion back effect on the metal copper precipitated on the cathode is. The chemical reaction equations of the regeneration of the cupric ammonia complex and the back etching of copper are as follows:
divalent copper ammonia complex regeneration reaction:
2Cu(NH3)2Cl+4NH4Cl+2NH3+1/2O2→2Cu(NH3)4Cl2+H2O
back etching reaction: cu + Cu (NH)3)4Cl2→2Cu(NH3)2Cl；
And (3) total reaction: cu +2NH4Cl+2NH3+1/2O2→Cu(NH3)4Cl2+H2O。
Secondly, ammonia water is easy to volatilize and become ammonia gas to escape, and ammonium ions of the electrolyte move to the cathode under the influence of electric field attraction in the electrolysis process, so that the ammonium ions are gathered near the cathode to cause the local ammonia concentration of the electrolyte to rise, and the temperature of the electrolyte rises to a certain extent compared with the room temperature in the electrolysis process, thereby further promoting the volatilization of ammonia and the consumption of raw materials. Therefore, the electrolyte near the anode is easy to have low ammonia water content, so that insufficient ammonia and copper ions in the electrolyte near the anode carry out complex reaction, soluble copper ammonia complex is difficult to form, partial copper ions can be precipitated at the bottom of the electrolytic cell in the form of copper mud or slurry is stuck on the anode, and the resistance of the electrolytic cell is increased. In this case, electrolysis is performed, which increases the electrolysis voltage required between the cathode and the anode, and wastes electric energy.
Thirdly, the electrolytic solution after electrolysis is returned to the alkaline etching production line for use, which affects the etching quality: because the existing direct electrolysis method usually adopts large current to electrolyze and take copper in order to adapt to large-scale production, the situation that the metal copper separated out from the cathode is seriously corroded back can cause the copper surface separated out by electrolysis to be very uneven, the peak current effect is aggravated, the current is unstable, and the separated metal copper layer is rough, loose and easy to fall off.
Fourthly, in order to solve the problem that the precipitated metal copper layer is rough, loose and easy to fall off in the prior art, a leveling agent is added into the electrolyte in the electrolysis process so as to ensure that a smoother copper sheet or copper plate is electrodeposited on an electrolysis cathode. The action principle of the flattening agent is that an adsorption layer is formed on the interface between the blocked surface and the solution by utilizing the characteristic that the flattening agent can retard the discharge of metal ions in the solution, so that the cathode polarization effect is improved, the metal ions can be deposited at a place with lower current density, and the concave part on the surface of a workpiece can be flattened. However, the electrolyzed electrolyte contains a leveling agent, and the leveling agent can adsorb metal ions in the etching working solution in the etching process to hinder the etching reaction, so that the etching speed is reduced; therefore, if the etching solution is returned to the alkaline etching production line, the etching rate is reduced, and the etching production quality is affected.
Therefore, the application of the existing alkaline etching waste liquid direct electrolysis method is still difficult to popularize and popularize at present, and no enterprises adopt the direct electrolysis method to regenerate the alkaline etching liquid.
Disclosure of Invention
The invention aims to provide a method for electrolyzing and recycling alkaline etching waste liquid, which can improve the efficiency of electroanalysis of copper and can prepare regenerated alkaline etching sub-liquid capable of keeping ideal etching effect after the waste liquid is electrolyzed and recycled.
The purpose of the invention is realized by the following technical scheme:
a method for electrolyzing and recycling alkaline etching waste liquid comprises the step of using an electrolytic cell consisting of an electrolytic bath, an electrolytic power supply, an electrolytic anode and an electrolytic cathode, wherein the electrolytic bath is divided into an anode area and a cathode area by a partition, and the method comprises the following steps:
(1) adding alkaline etching waste liquid or a mixed solution of the alkaline etching waste liquid and a reducing agent as an anolyte into the anode area; adding a mixed solution of alkaline etching waste liquid and a reducing agent serving as a cathode electrolyte into the cathode area;
(2) starting the electrolytic power supply to carry out electrolysis operation, and precipitating metal copper on the electrolytic cathode;
(3) according to a specific alkaline etching process, adding one or more of ammonium chloride, ammonia, water and other components contained in the alkaline etching solution into the anolyte and/or catholyte after the electrolysis operation in the step (2) to prepare regenerated alkaline etching sub-solution which can be reused on an alkaline etching production line;
the alkaline etching waste liquid is characterized in that the concentration of copper ions is 20-200 g/L, pH, and the value of copper ions is 7-10.3.
The liquid formed by the anolyte after electrolysis in the anode area is anolyte, and the liquid formed by the catholyte after electrolysis in the cathode area is catholyte. Namely, the anolyte and the catholyte are respectively formed by the components of anolyte and catholyte after chemical reaction change in the electrolytic process.
The inventor experiments show that the reducing agent and the alkaline etching waste liquid are mixed to prepare the electrolyte, and the reducing agent can generate oxidation-reduction reaction with an oxidizing agent (oxygen), so that the oxygen in the electrolyte is effectively consumed. Along with the reduction of the oxygen concentration, the generation speed of the divalent copper ammonia complex in the electrolyte is reduced, so that the condition that the metal copper precipitated on the cathode is corroded is reduced, and the aim of improving the recovery rate of the metal copper is fulfilled.
The mass percentage content of the reducing agent in the cathode electrolyte is 0.01-15%, preferably 0.01-13%, and more preferably 1-13%; if the anolyte is a mixed solution of alkaline etching waste liquid and a reducing agent, the mass percentage of the reducing agent is also 0.01-15%, preferably 0.01-13%, and more preferably 1-13%.
Repeated tests prove that the situation that the metal copper electrolyzed on the electrolytic cathode is corroded back can be well improved and alleviated when the content of the reducing agent in the cathode electrolyte of the cathode area of the electrolytic cell is 0.01-15%; meanwhile, when the anolyte of the anode area of the electrolytic cell contains a reducing agent, the content of the reducing agent is not more than 15%: when the content of the reducing agent in the catholyte is less than 0.01%, the effect of reducing the back corrosion of the electrodeposited metal copper on the cathode is not obvious; when the content of the reducing agent in the anolyte and/or the catholyte is more than 15%, more reducing agent usually remains in the anolyte and/or the catholyte after electrolysis, and the production etching speed of the alkaline etching working solution can be reduced when the regenerated alkaline etchant is prepared and reused on an alkaline etching production line.
The reducing agent is a reducing substance which can react with oxygen in the aqueous solution to consume the oxygen, and includes but is not limited to one or more of sulfite, thiosulfate, hydroxylamine sulfate, hydroxylamine hydrochloride, hydrazine hydrate, oxalic acid and oxalate, formic acid and formate, citric acid and citrate, glucose, vitamin C, tartaric acid, phosphite and hypophosphite, and the reducing agents are not limited in proportion to each other when mixed.
Preferably, the reducing agent is one or more of sulfite, thiosulfate, hydroxylamine sulfate, hydroxylamine hydrochloride, hydrazine hydrate, oxalic acid and oxalate, and there is no ratio limitation between the above reducing agents when they are mixed.
More preferably, the reducing agent is an acidic reducing agent to reduce the volatilization of ammonia gas from the electrolyte by complexing and consuming free ammonia in the electrolyte, and the acidic reducing agent comprises at least one of hydroxylamine hydrochloride, hydroxylamine sulfate and oxalic acid, and the ratio of the reducing agents is not limited when the reducing agents are mixed.
In addition, after the method is adopted, the situation that the metal copper on the electrolytic cathode is corroded back is reduced, so that the structure of the precipitated metal copper layer is more compact, the peak current effect is small, and a flattening agent does not need to be added in the electrolytic process. Therefore, when the regenerated alkaline etching solution prepared after the electrolytic treatment is returned to the alkaline etching production line for use, the etching speed and the quality are not influenced. In addition, the invention adopts the separator to divide the electrolytic bath into the anode area and the cathode area, thereby further reducing or even avoiding the oxygen generated on the electrolytic anode from approaching the electrolytic cathode, greatly reducing the condition of generating the cupric ammonia complex near the electrolytic cathode, and further reducing the return corrosion of the electrolytic copper on the electrolytic cathode.
The separator of the invention can adopt filter cloth, ceramic filter plate, PE filter plate, electrolytic diaphragm and other materials which can effectively prevent oxygen generated on the electrolytic anode from approaching the electrolytic cathode but allow partial/or all ions to migrate between the two electrodes, thereby dividing the electrolytic cell into an anode area and a cathode area.
The design proportion of each component of the alkaline etching solution is different according to different production equipment parameters and different etching requirements. In addition, even after the electrolysis operation, the regenerated alkaline etchant may still contain part of copper ions, but when the regenerated alkaline etchant is prepared and reused on the production line, the etching operation is not negatively affected. Therefore, the components and the concentration of the regenerated alkaline etching solution in the step (3) except the copper ions can be adjusted according to the components and the concentration of the ammonia nitrogen, the chloride ions and the like of the common etching solution.
Preferably, the electrolytic cell is a sealed electrolytic cell, and gas is pumped out, so that oxygen generated on the electrolytic anode is discharged out of the electrolytic cell in time, and the content of oxygen dissolved in the anolyte is reduced.
In the process of the electrolysis operation, the anolyte and/or the alkaline etching waste liquid and/or the reducing agent and/or the catholyte can be supplemented into the anode region, and the catholyte and/or the alkaline etching waste liquid and/or the reducing agent can be supplemented into the cathode region, namely the catholyte is directly supplemented or each component in the catholyte is supplemented respectively, so that the components of the anolyte and/or the catholyte are stabilized and higher electrolysis efficiency is maintained.
When the anode area is supplemented with the anolyte and/or the alkaline etching waste liquid and/or the reducing agent, and/or the cathode area is supplemented with the catholyte and/or the alkaline etching waste liquid and/or the reducing agent, real-time parameters of the oxidation-reduction potential, the pH value, the specific gravity value, the colorimetric value and the liquid level of the anolyte and/or the catholyte can be set and/or carried out according to time in the electrolysis process, and the parameters are added through a manual or automatic feeding controller, so that the concentration of copper ions and the concentration of ammonia in the anode area and the cathode area are stabilized, or the preset process parameter values are controlled, and the occurrence of the situation that copper metal separated out on the electrolytic cathode is corroded back and polluted is reduced. In addition, the anolyte containing alkaline etching waste liquid is supplemented to the anode region in the electrolysis process, and the ammonia content in the anolyte can be increased so as to prevent copper sludge from precipitating in the anolyte.
When adopting the electrolysis in-process to the anode space when replenishing catholyte, can the cathode space set up the overflow mouth, just the overflow mouth is not less than predetermineeing the liquid level in the anode space, thereby make to when replenishing catholyte and/or alkaline etching waste liquid and/or reductant in the cathode space, if the actual liquid level in cathode space exceeds predetermineeing the liquid level, then exceed the part of predetermineeing the liquid level and can pass through the overflow mouth follow the cathode space overflow to the anode space in, thereby realize automatically adding catholyte to the anode space in.
Preferably, the overflow port is arranged higher than the liquid level in the anode region. Especially when the separator allows cations to pass through, ammonium ions in the anolyte will migrate towards the electrolytic cathode under the influence of electric field forces; meanwhile, copper-ammonia complex in the catholyte reduces copper ions into metal copper through electrochemical reaction and releases ammonium ions, so that the ammonia content of the metal copper is higher than that of the anolyte, and the catholyte rich in ammonia is added into the anode area, so that the ammonium ion content in the anolyte can be supplemented, copper sludge precipitation on the electrolytic anode is avoided, and the pressure between the anolyte and the catholyte can be balanced.
The anode region and the cathode region can be connected through a pipeline with a controllable pump, and the catholyte can be added into the anode region under the control of an automatic feeding controller according to preset time and/or one or more parameters of the anolyte such as specific gravity, pH value, oxidation-reduction potential and the like.
Preferably, the electrolytic power supply employs a double pulsed power supply when the separator allows cations to pass therethrough. In the electrolytic process, ammonium ions in the anolyte can penetrate through the partition to enter the cathode region along with the attraction of an electric field, so that the phenomenon that copper sludge is separated out due to ammonia deficiency in the anode region is easily caused. And the double-pulse power supply can reversely lead the ammonium ions in the cathode region back to the anode region in the reverse phase, thereby effectively avoiding the problems that copper sludge is separated out due to the lack of ammonia on the electrolytic anode and the metal copper separated out on the electrolytic cathode is quickly corroded due to the large amount of ammonia in the catholyte.
Preferably, the liquid level in the cathode region is maintained higher than the liquid level in the anode region, so that the specific gravity balance of the solution between the anode region and the cathode region is achieved. Because the electrolytic bath is divided into an anode area and a cathode area, if the separator can allow cations to pass through, the ammonium ions in the anode area can continuously pass through the separator to enter the cathode area under the influence of the electric field attraction in the electrolytic process, so that the specific gravity difference between the anolyte and the catholyte is larger and larger, and the separator is deformed and damaged due to the overlarge pressure difference caused by the specific gravity difference of the solutions on the two sides. The liquid level in the cathode region is kept higher than that in the anode region, so that the pressure on two sides of the separator can be effectively balanced, and deformation damage of the separator and liquid permeation between the anode region and the cathode region are reduced.
After the step (2) is finished, the solid-liquid separation can be carried out firstly, and then the step (3) is carried out.
The invention can be further improved as follows: adding an ammonia source into the anode area through manual and/or automatic equipment before and/or during the electrolysis operation in the step (2), wherein the ammonia source is liquid ammonia and/or ammonia water and/or ammonium carbonate and/or ammonium bicarbonate. Therefore, enough ammonia contained in the anolyte can be effectively ensured to be complexed with copper ions to form a soluble copper ammonia complex, and the electrolytic efficiency is prevented from being influenced by copper sludge caking formed by basic copper chloride, copper hydroxide, copper ammonium chloride and the like bonded on the electrolytic anode. Preferably, the ammonia source is dosed prior to and/or during the electrolysis operation such that the anolyte and/or the anolyte in the anodic compartment has a pH of not less than 6.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the prior art that the alkaline etching waste liquid is recovered by a direct electrolysis method, the method can reduce the generation speed of the divalent copper ammonia complex in the cathode region of the waste liquid in the electrolysis process, and achieves the effect of obviously improving the recovery efficiency of electrolytic precipitation of the metal copper by controlling the concentration of oxygen and the divalent copper ammonia complex which have the effect of back etching on the metal copper in the electrolyte, wherein the recovery rate can reach 90 percent or more;
2. the method has small corrosion resistance to the copper separated out by electrolysis, so that a compact copper layer can be obtained without adding a flattening agent into the electrolyte, and the anolyte and/or catholyte generated after the waste liquid is electrolyzed by the method can be prepared into regenerated alkaline etching liquid capable of keeping an ideal etching effect and can be reused on an alkaline etching production line, so that the problem that the etching quality of the regenerated etching sub-liquid is influenced by the corrosion inhibition effect of the flattening agent in the prior art, and the alkaline etching liquid cannot be regenerated is solved, the efficient recycling of the alkaline etching waste liquid is realized, and meanwhile, the pollution to the environment caused by the discharge of the alkaline etching waste liquid is greatly reduced;
3. when the acid reducing agent is adopted, the invention can reduce the escape amount of ammonia gas, improve the ammonia pollution and improve the production environment; the separator also reduces ammonia evolution if it allows cations to pass through and when catholyte is replenished to the anodic compartment during electrolysis operations;
4. when alkaline etching waste liquid and/or ammonia source and/or catholyte are supplemented into the anolyte or a double-pulse power supply is adopted, the phenomenon that copper mud is separated out from an anode region can be effectively inhibited, and the effect of reducing electrolysis energy consumption is achieved;
5. the invention has less corrosion to the copper separated out by electrolysis, therefore, the copper layer separated out on the electrolytic cathode is more compact than the copper layer separated out in the prior art under the condition of not using a flattening agent, on one hand, the surface area of the copper surface exposed in the air is smaller, and the storage and the transportation are more convenient;
Detailed Description
The present invention will be further described below with reference to specific embodiments.
In the embodiment of the invention, the used ammonia water is preferably a commercially available ammonia water solution with the concentration of 20% or 25%, and the used liquid ammonia is a commercially available 40L bottled liquid ammonia product with a pressure reducing valve; the etching line used is preferably an etching line produced by Koger PCB Equipment factory, and during the etching operation, the temperature of the etching cylinder is set to 49 deg.C, and the pressure of the etching solution nozzle of the etching machine is set to 1kg/cm2(ii) a In addition to those enumerated above, those skilled in the art can select other products having similar properties to those enumerated above in the present invention according to routine selection, and can achieve the objects of the present invention.
The detection of copper ion concentration is mentioned as a technique well known in the art.
The main components of the alkaline etching waste liquid are ammonia water, ammonium chloride and copper ammonia complex.
Testing of etching Effect: taking pure copper with the size of 500 multiplied by 300mm multiplied by 1.5mm to etchThe etching rate test board is placed in an etching cylinder for spray etching to test the etching rate; the double-sided circuit board with the size of 620 multiplied by 540mm, the copper thickness of 1oz and the development line width and line distance of 50.8 mu m is used for spray corrosion to test the etching factor and the stability of the electrolytic recycling regeneration process system. The etching rate, the etching factor K and the electrolytic current efficiency were calculated by methods known in the art (printed circuit technology, Li Ming, department of industry and informatization, center for the guidance of professional skills in the electronics industry, fifth edition, p387-389, theory and application of Metal Corrosion, Weibaoming, chemical industry Press, p5-7, method for calculating shallow etching factor, Ding Ling, etc., printed circuit information 2007No.12, p 55-56).
Example 1
(1) An electrolytic cell consisting of an electrolytic bath, an electrolytic power supply, an electrolytic anode and an electrolytic cathode is used, and the electrolytic bath is divided into an anode area and a cathode area by overlapping a ceramic filter plate and filter cloth;
preparing an anolyte and a catholyte according to the components and the proportion in the following table-1, and respectively adding the anolyte and the catholyte into the anode region and the cathode region;
(2) starting the electrolytic power supply to carry out electrolysis operation, and precipitating metal copper on the electrolytic cathode;
(3) after 2h of electrolysis operation, the anolyte and the catholyte are mixed, 5% of water is added according to the weight ratio, and then the pH value is adjusted to 11 by using liquid ammonia, so that regenerated alkaline etching sub-solution is formed and is recycled on an etching production line.
Example 2
(1) An electrolytic cell consisting of a sealed electrolytic cell, an electrolytic power supply, an electrolytic anode and an electrolytic cathode is used, and the electrolytic cell is divided into an anode area and a cathode area by a PE filter plate;
preparing an anolyte and a catholyte according to the components and the proportion in the following table-1, and respectively adding the anolyte and the catholyte into the anode region and the cathode region;
(2) starting the electrolytic power supply to carry out electrolysis operation, simultaneously pumping and discharging gas generated in the electrolytic cell, separating out metal copper on the electrolytic cathode, and manually replenishing anolyte and catholyte with the volume of 5% of the preset liquid level to the anode region and the cathode region respectively every half hour;
(3) after 2 hours of electrolysis, the anolyte and the catholyte are mixed and subjected to solid-liquid separation, and then the pH value is adjusted to 11 by using liquid ammonia, so that regenerated alkaline etchant is formed and is recycled on an etching production line.
Example 3
(1) An electrolytic cell consisting of a sealed electrolytic cell, an electrolytic power supply, an electrolytic anode and an electrolytic cathode is used, and the electrolytic cell is divided into an anode area and a cathode area by an anion membrane;
preparing an anolyte and a catholyte according to the components and the proportion in the following table-1, and respectively adding the anolyte and the catholyte into the anode region and the cathode region;
(2) starting the electrolytic power supply to carry out electrolysis operation, simultaneously pumping and discharging gas generated in the electrolytic cell, precipitating metal copper on the electrolytic cathode, supplementing alkaline etching waste liquid into the anode area by the automatic detection and feeding control machine according to the real-time pH value of anode liquid in the anode area, adding a reducing agent into the anode area by the automatic detection and feeding control machine according to the real-time oxidation-reduction potential of the anode liquid, supplementing alkaline etching liquid into the cathode area by the automatic detection and feeding control machine according to the real-time colorimetric value of the cathode liquid, adding the reducing agent into the cathode area by the automatic detection and feeding control machine according to the real-time oxidation-reduction potential of the cathode liquid, and directly returning the anode liquid overflowing from the anode area to an etching production line;
(3) after 2h of electrolysis, the pH of the catholyte was adjusted to 11.5 using liquid ammonia to form a regenerated alkaline etchant, which was recycled to the etching line.
Example 4
(1) An electrolytic cell consisting of a sealed electrolytic cell, an electrolytic power supply, an electrolytic anode and an electrolytic cathode is used, the electrolytic cell is divided into an anode area and a cathode area by filter cloth, and the anode area and the cathode area are connected by a pipeline with a controllable pump;
preparing an anolyte and a catholyte according to the components and the proportion in the following table-1, and respectively adding the anolyte and the catholyte into an anode region and a cathode region, wherein the alkaline etching waste liquid also contains an etching additive;
(2) adjusting the pH value of the anolyte to 6, starting the electrolytic power supply to carry out electrolysis operation, simultaneously pumping and discharging gas generated in the electrolytic cell, separating out copper metal on the electrolytic cathode, supplementing catholyte into the anode region by the automatic detection switching machine according to the real-time specific gravity value of the anolyte in the anode region, supplementing reducing agent into the anode region by the automatic detection switching machine according to the real-time oxidation-reduction potential of the anolyte, and supplementing catholyte into the cathode region by the automatic detection switching machine according to the real-time specific gravity value of the catholyte;
(3) after 2h of electrolysis operation, the anolyte overflowing the anode region and the etching sub-solution additive are mixed until the pH value is 10.5, so that regenerated alkaline etching sub-solution is formed and is recycled on an etching production line.
Example 5
(1) The electrolytic cell consists of an electrolytic bath, a double-pulse type electrolytic power supply, an electrolytic anode and an electrolytic cathode, the electrolytic bath is divided into an anode area and a cathode area by a cation membrane, a sealing cover plate is arranged at the top of the electrolytic bath, a gas pumping and discharging system and a feeding port are arranged on the electrolytic bath, a stirring device, an overflow port and an oxidation-reduction potential and pH detection device are respectively arranged in the anode area and the cathode area, and the anode area and the cathode area are connected through a pipeline with a controllable pump;
preparing an anolyte and a catholyte according to the components and the proportion in the following table-1, and respectively adding the anolyte and the catholyte into the anode region and the cathode region;
(2) keeping the liquid level in the cathode region higher than that in the anode region, starting the electrolytic power supply to perform electrolysis operation, simultaneously pumping gas generated in the electrolytic cell, reversely electrifying the electrolytic power supply for 1 minute after each forward electrification for 5 minutes, separating out metal copper on the electrolytic cathode, supplementing alkaline etching waste liquid into the anode region by an automatic detection and control machine according to the real-time specific gravity value of the anode liquid in the cathode region, supplementing a reducing agent into the cathode region by the automatic detection and control machine according to the real-time oxidation-reduction potential of the cathode liquid, and enabling part of the cathode liquid higher than the preset liquid level to overflow into the anode region;
(3) after 2h of electrolysis operation, the anolyte overflowing from the anode region and the catholyte in the cathode region are mixed, and then the pH value is adjusted to 11.5 by using liquid ammonia, so that regenerated alkaline etching sub-solution is formed and is recycled on an etching production line.
Example 6
(1) An electrolytic cell consisting of a sealed electrolytic cell, an electrolytic power supply, an electrolytic anode and an electrolytic cathode is used, the electrolytic cell is divided into an anode area and a cathode area by filter cloth, and the anode area and the cathode area are connected by a pipeline with a controllable pump;
preparing an anolyte and a catholyte according to the components and the proportion in the following table-1, and respectively adding the anolyte and the catholyte into the anode region and the cathode region;
(2) keeping the liquid level in the cathode region higher than that in the anode region, starting the electrolytic power supply to perform electrolysis operation, simultaneously pumping and discharging gas generated in the electrolytic cell, reversely electrifying the electrolytic power supply for 1 minute after each forward electrification for 5 minutes, separating out metal copper on the electrolytic cathode, supplementing catholyte into the anode region by an automatic detection switching machine according to the real-time pH value and the oxidation-reduction potential of the anolyte in the anode region and the timing setting, and supplementing catholyte into the cathode region by the automatic detection switching machine according to the real-time oxidation-reduction potential of the catholyte;
(3) after 2h of electrolysis operation, the anolyte overflowing from the anode area and the catholyte in the cathode area are mixed, 1% of sodium chlorate and 5% of water are added according to the weight ratio, and then the pH value is adjusted to 11.5 by using liquid ammonia, so that regenerated alkaline etching sub-liquid is formed and is recycled on an etching production line.
Comparative example 1
(1) Using an electrolytic cell consisting of an electrolytic cell, an electrolytic power supply, an electrolytic anode and an electrolytic cathode;
preparing electrolyte according to the components and the proportion in the following table-1, adding the electrolyte into an electrolytic cell, and adding 1mol/L of thiourea serving as a leveling agent;
(2) starting the electrolytic power supply to carry out electrolysis operation, and precipitating metal copper on the electrolytic cathode;
(3) after 2h of electrolysis operation, adding 5% of water by weight into the electrolyzed solution, and then adjusting the pH value to 11 by using liquid ammonia to form regenerated alkaline etching sub-solution which is recycled on an etching production line.
Comparative example 2
(1) Using an electrolytic cell consisting of an electrolytic cell, an electrolytic power supply, an electrolytic anode and an electrolytic cathode;
preparing electrolyte according to the components and the proportion in the following table-1, adding the electrolyte into an electrolytic cell, and adding 1mol/L of thiourea serving as a leveling agent;
(2) starting the electrolytic power supply to carry out electrolysis operation, and precipitating metal copper on the electrolytic cathode;
(3) and adding a sub-solution additive into the electrolyzed solution after 2 hours of electrolysis operation to adjust the pH value to 10.5, thereby forming regenerated alkaline etching sub-solution which is recycled on an etching production line.
TABLE-1
Remarking: in Table-1, "etching rate and/or etching factor when the regenerated alkaline etchant is not used" is understood to mean that the etching rate and/or etching factor when the original alkaline etchant is used alone is the same as when the regenerated alkaline etchant is not used.
The etching speed and the etching quality are influenced by the performance of the etching solution, and also vary with factors such as the temperature of the etching solution and the spraying pressure of the etching equipment. Therefore, all test conditions except the recovery method need to be kept consistent to obtain results for comparison.
From the results in table-1, it is understood that comparative examples 1 and 2 are the conventional solutions in which the alkaline etching waste solution is directly electrolyzed, the electrowinning copper current efficiencies are only 60% and 64%, and the etching rates of the solutions after electrolysis are reduced by 47.5% and 43.3%, respectively, when the regenerated alkaline etchant is prepared and reused, and the etching quality is also reduced. The electrowinning copper current efficiency of the embodiments 1 to 6 is improved by at least 53.3 percent compared with the prior art, and the electrolyzed solution is prepared into the regenerated alkaline etching sub-solution for reuse, so that the etching speed and the etching quality are not obviously influenced.
It should be noted that the above-mentioned embodiments are only illustrative and not restrictive, and any modifications or changes within the meaning and range of equivalents to the technical solutions of the present invention by those skilled in the art should be considered to be included in the protection scope of the present invention.
Claims (10)
1. A method for electrolyzing and recycling alkaline etching waste liquid comprises the use of an electrolytic cell consisting of an electrolytic bath, an electrolytic power supply, an electrolytic anode and an electrolytic cathode, wherein the electrolytic bath is divided into an anode area and a cathode area by a partition, and is characterized by comprising the following steps:
(1) adding alkaline etching waste liquid or a mixed solution of the alkaline etching waste liquid and a reducing agent as an anolyte into the anode area; adding a mixed solution of alkaline etching waste liquid and a reducing agent serving as a cathode electrolyte into the cathode area;
(2) starting the electrolytic power supply to carry out electrolysis operation, and precipitating metal copper on the electrolytic cathode;
(3) according to a specific alkaline etching process, adding one or more of ammonium chloride, ammonia, water and other components contained in the alkaline etching solution into the anolyte and/or catholyte after the electrolysis operation in the step (2) to prepare regenerated alkaline etching sub-solution which can be reused on an alkaline etching production line;
the alkaline etching waste liquid is characterized in that the concentration of copper ions is 20-200 g/L, pH, and the value of copper ions is 7-10.3.
2. The method for electrolyzing and recycling the alkaline etching waste liquid as claimed in claim 1, wherein the mass percentage of the reducing agent in the catholyte is 0.01-15%; and if the anolyte is a mixed solution of alkaline etching waste liquid and a reducing agent, the mass percent of the reducing agent is 0.01-15%.
3. The method for electrolyzing and recycling the alkaline etching waste liquid as claimed in claim 2, wherein the mass percentage of the reducing agent in the catholyte is 0.01-13%; and if the anolyte is a mixed solution of alkaline etching waste liquid and a reducing agent, the mass percent of the reducing agent is 0.01-13%.
4. The method for electrolyzing and recycling the alkaline etching waste liquid as claimed in claim 3, wherein the mass percentage of the reducing agent in the catholyte is 1-13%; and if the anolyte is a mixed solution of alkaline etching waste liquid and a reducing agent, the mass percent of the reducing agent is 1-13%.
5. The method for recycling alkaline etching waste liquid by electrolysis according to any one of claims 1 to 4, wherein the reducing agent is one or more of sulfite, thiosulfate, hydroxylamine sulfate, hydroxylamine hydrochloride, hydrazine hydrate, oxalic acid and oxalate, formic acid and formate, citric acid and citrate, glucose, vitamin C, tartaric acid, phosphite and hypophosphite, and there is no ratio limitation when the reducing agents are mixed.
6. The method for the electrolytic recycling of alkaline etching waste liquid according to claim 5, wherein during the electrolysis operation, the anolyte and/or the alkaline etching waste liquid and/or the reducing agent and/or the catholyte are supplemented to the anode region, and the catholyte and/or the alkaline etching waste liquid and/or the reducing agent are supplemented to the cathode region, i.e. the catholyte is directly supplemented or each component in the catholyte is separately supplemented, so as to stabilize the components of the anolyte and/or the catholyte and maintain higher electrolysis efficiency.
7. The method for the electrolytic recycling of alkaline etching waste liquid according to claim 6, when the anode area is supplemented with anolyte and/or alkaline etching waste liquid and/or reducing agent, and/or when the cathode region is replenished with a catholyte and/or an alkaline etching waste liquid and/or a reducing agent, setting and/or real-time parameters of oxidation-reduction potential, pH value, specific gravity value, colorimetric value and liquid level of the anolyte and/or the catholyte according to time in the electrolysis process, the copper ion concentration and the ammonia concentration in the anode area and the cathode area are stabilized by adding through a manual or automatic feeding controller, or the process parameters are controlled to be preset, so that the situation that the copper metal precipitated on the electrolytic cathode is corroded back and polluted is reduced.
8. The method according to claim 6, wherein when the catholyte is replenished to the anode region during the electrolysis process, an overflow port is provided in the cathode region, and the overflow port is not lower than a preset liquid level in the anode region, so that when the catholyte and/or the alkaline waste etching solution and/or the reducing agent is replenished to the cathode region, if an actual liquid level in the cathode region exceeds the preset liquid level, a part exceeding the preset liquid level overflows from the cathode region to the anode region through the overflow port, thereby automatically adding the catholyte to the anode region.
9. The method for recycling alkaline etching waste liquid by electrolysis according to claim 6, characterized in that the anode region and the cathode region are connected by a pipeline with controllable pump, and the feeding of the catholyte into the anode region is controlled by an automatic feeding controller according to a preset time and/or one or more parameters of the anolyte such as specific gravity, pH value, oxidation-reduction potential, etc.
10. The method for the electrolytic recycling of alkaline etching waste liquid according to claim 9, wherein an ammonia source is added into the anode region by manual and/or automatic equipment before and/or during the electrolysis in step (2), and the ammonia source is liquid ammonia and/or ammonia water and/or ammonium carbonate and/or ammonium bicarbonate. Therefore, enough ammonia contained in the anolyte can be effectively ensured to be complexed with copper ions to form a soluble copper ammonia complex, and the electrolytic efficiency is prevented from being influenced by copper sludge caking formed by basic copper chloride, copper hydroxide, copper ammonium chloride and the like bonded on the electrolytic anode.
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