CN112813268A - PCB (printed circuit board) copper electroplating and acid etching copper resource recycling method - Google Patents
PCB (printed circuit board) copper electroplating and acid etching copper resource recycling method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
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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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/18—Regeneration of process solutions of electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
A PCB copper electroplating and acid etching copper resource recycling method comprises the steps of firstly pretreating acid etching waste liquid, then separating copper chloride in the acid etching waste liquid by using an extracting agent A to obtain a loaded organic phase A and a raffinate A, then reversely extracting the loaded organic phase A by using pure water to obtain a copper chloride solution, then extracting the copper chloride solution by using an extracting agent B to obtain a loaded organic phase B and a raffinate B, mixing the raffinate A and the raffinate B to prepare a regenerated etching solution for recycling a circuit board etching production line, recycling high-copper electroplating liquid medicine obtained by reversely extracting the loaded organic phase B by using the copper electroplating liquid medicine to an electroplating production line, and avoiding the risk of secondary environment pollution caused by outward transportation and disposal of the etching waste liquid, has good ecological environment and economic benefit.
Description
Technical Field
The invention relates to the technical field of copper resource recycling in the PCB manufacturing process, in particular to a PCB copper electroplating and acid etching copper resource recycling method.
Background
In the life of people, all automatically controlled products, such as spacecrafts, airplanes, high-speed rails, automobiles and steamships, computers, mobile phones and even pedometers carried by a plurality of people, need to be transmitted by a circuit board (PCB) to achieve automatic control. The PCB is a support body of electronic product components and is the most basic hardware carrier of the current information society, the PCB industry is the pillar industry of the Chinese electronic information industry, and the growth rate of the PCB industry is the same as that of the electronic information industry. PCB production processes have improved greatly over decades of PCB production practices. The method for preparing the circuit diagram of the PCB still uses a subtractive process, namely the copper-clad plate is manufactured into the circuit diagram through the working procedures of cutting, pasting, pattern transferring, developing, inner layer etching, film stripping and the like, and then the circuit board production is completed through the working procedures of pressing, drilling, copper electroplating, outer layer manufacturing and the like. In the inner layer etching step, an acid etching method is adopted, the oxidation-reduction potential and the copper ion concentration in the etching solution are kept in a certain area, the etching rate is maintained, an oxidant and hydrochloric acid are continuously added in the etching process, meanwhile, the overflowing etching solution is changed into etching waste liquid, the main components of the acid etching waste liquid are copper chloride and hydrochloric acid (containing about 10% of copper), according to the fact that environmental protection workers consider the facts that the situation is equal to 2018, in 3 months, in volume 8, 2 of environmental engineering journal, a paper, namely, current situation and management strategy research of treating and utilizing industry of copper-containing etching waste liquid in Jiangsu province is published, and a PCB enterprise only in Jiangsu province in 2016 is claimed to generate 52 million tons of PCB copper-containing etching waste liquid. The annual production amount of the copper-containing waste liquid of the PCB in China is more than million tons, the copper-containing waste liquid is more than 10 million tons, and on the other hand, the annual demand amount of the electrolytic copper of the domestic circuit board (PCB) industry for phosphor copper balls, copper oxide and copper sulfate is more than 10 million tons compared with that of metal copper.
At present, PCB copper-containing waste liquid is generally sold to enterprises with hazardous waste treatment qualification by circuit board enterprises at a lower price for treatment, the hazardous waste treatment enterprises comprehensively recycle the collected etching waste liquid and use copper in the etching waste liquid to prepare copper salt products, and the waste water is subjected to harmless treatment and then is discharged after reaching the standard. The invention CN103693673B granted by Chinese patent discloses a method for producing electroplating-grade copper sulfate by using acidic copper-containing etching waste liquid, the method generates high-purity copper oxide by reacting clear water or copper oxide production mother liquid or the copper sulfate production mother liquid with the acidic copper-containing etching waste liquid and mixed alkali liquor, the temperature of a reaction system is controlled to be 70-90 ℃, the pH value is 8.5-9, the mixed alkali liquor is formed by mixing strong base, weak acid salt and strong base, and the mass ratio is 1:6-1: 8; and adding the prepared high-purity copper oxide and concentrated sulfuric acid into clear water or plating-grade copper sulfate production mother liquor, and controlling the pH value of the reaction to be 0.1-3 to prepare plating-grade copper sulfate. The method has the advantages of simple process and low cost, the product reaches the electroplating level, the continuous production can be realized, ammonia nitrogen is not introduced, and the subsequent treatment processes are reduced, but compared with the prior art that the acidic etching waste liquid is neutralized by ammonia water, ammonia nitrogen is not introduced, the electroplating-level copper sulfate can be prepared (high-purity copper sulfate still needs to be further purified and treated to reduce impurities such as sodium ions), but a large amount of high-salt waste water (sodium chloride) still needs to be discharged in the process, and the environmental pollution can be caused by improper treatment. In view of the influence of the traditional process on the environment, the on-line recycling and regenerating process of the acidic etching waste liquid is developed in the industry in recent years.
Chinese granted utility model patent CN202492581U discloses a device for recycling acidic etching solution for printed circuit boards, which comprises an etching waste liquid storage tank, a composite diaphragm electrolytic tank, an etching solution transfer tank and a regenerated etching solution preparation tank, wherein the composite diaphragm electrolytic tank is divided into an anode chamber and a cathode chamber by a composite diaphragm; one end of the etching solution transfer groove is communicated with the etching cylinder, and the other end of the etching solution transfer groove is communicated with the cathode chamber; one end of the etching waste liquid storage tank is communicated with the etching cylinder, and the other end of the etching waste liquid storage tank is communicated with the cathode chamber; wherein the anode chamber is communicated with the etching cylinder by a regenerative etching solution tank. The device solves the technical problem that an oxidant is additionally added to oxidize cuprous ions in the prior art, reduces the generation cost, does not add impurities into the regenerated etching solution, and ensures the consistency of the regenerated etching solution and the fresh etching solution; the device can recycle cathode copper with high purity, no waste water is discharged, clean production of an etching process is realized, the device can recycle acidic etching solution, but chlorine generated in an anode chamber of a diaphragm electrolytic cell is difficult to be completely absorbed, a common treatment method at present uses liquid caustic soda for absorption, the cost of the liquid caustic soda is high, even though the chlorine is absorbed by multiple stages, the chlorine still has a leakage risk, the cathode copper recycled by the device has high purity but poor physical performance, can reach the standard of industrial application after being treated by a smelting furnace again, and the selling price of the cathode copper is low.
The electro-coppering in the Process of Circuit Board (PCB) mainly comprises full-board electro-coppering and pattern electro-coppering, the purpose of the full-board electro-coppering is to protect the thin chemical copper which is just deposited and prevent the chemical copper from being corroded by acid after being oxidized, the purpose of the pattern electro-coppering is to thicken the chemical copper to a certain degree by electroplating to meet the rated current load of each circuit, the electro-coppering mainly adopts a copper sulfate liquid medicine system at present, the copper ion source in the liquid medicine is the dissolution of a phosphor copper ball anode, or the copper oxide powder (the anode adopts an insoluble noble metal coating titanium anode) is supplemented, the phosphor copper ball and the copper oxide are deep processing products of the metal copper, the energy consumption in the production process is high, the environmental pollution is large, for example, the control method of the impurity content in the phosphor copper ball in Chinese patent CN105112695B and the production method of the phosphor copper ball and the production method of the high-purity electro, but the product is high in selling price, and correspondingly, the copper-containing raw material cost of circuit board enterprises is high.
Disclosure of Invention
In order to solve the problems, the invention provides a method for recycling PCB (printed circuit board) copper electroplating and acid etching copper resources, which adopts electroplating liquid medicine of an electroplating copper production line to regenerate etching waste liquid overflowing from the acid etching production line, avoids chlorine generated in the regeneration process of the acid etching waste liquid, has low selling price of by-product copper products, and can save the high-price purchase cost of the electroplating copper production line for phosphorus copper balls, copper oxide and the like, and comprises the following steps:
the invention aims to provide a PCB (printed Circuit Board) copper electroplating and acid etching copper resource recycling method, which is technically characterized in that: the method comprises the following steps:
step one, pretreatment of acidic etching waste liquid: filtering the etching waste liquid overflowing from the printed circuit board etching line, collecting the etching waste liquid to an oxidant destruction reactor, and adding low-valence copper to perform a reaction for reducing the oxidation-reduction potential of the etching waste liquid to obtain pretreated etching waste liquid with acidity of 2.0-2.5 mol/L;
step two, separating copper chloride in the acidic etching waste liquid: adding an extractant A into the solution obtained in the first step for carrying out copper chloride extraction reaction to obtain a raffinate A with copper ion content of 5-10g/L and a loaded organic phase A, carrying out back extraction on the loaded organic phase A by using pure water to obtain a copper chloride solution and the extractant A, wherein the volume ratio of the extractant A to the etching waste liquid is (2-3): 1, the extractant A is a mixture of pyridine carboxylic ester and sulfonated kerosene, and the volume fraction of the pyridine carboxylic ester is 10-35%;
step three, separating copper ions in the copper chloride solution: mixing the copper chloride solution obtained in the second step with an extractant B to perform copper extraction reaction to obtain a loaded organic phase B and a raffinate B with the copper ion content of 5-10g/L, wherein the volume ratio of the extractant B to the raffinate A is (2-3): 1, the extracting agent B is a mixture of an ester-modified aldoxime substance and one of ketoxime substances and sulfurized kerosene, and the volume fraction of the ester-modified aldoxime substance and one of ketoxime substances is 10-35%;
step four, preparing acidic etching regeneration liquid: mixing the raffinate B obtained in the step three with the raffinate A obtained in the step two, supplementing additives, and blending to prepare a regenerated acidic etching solution for recycling to an acidic etching production line;
step five, blending of the electrolytic copper plating liquid medicine: and (3) mixing the load organic phase B obtained in the step three after cleaning with overflow liquid medicine of a printed circuit board copper electroplating production line to perform a copper back-extraction reaction, and obtaining an extracting agent B and a copper sulfate solution after back-extraction.
In an embodiment of the invention, in the first step of the method for recycling resources of PCB electro-coppering and acidic etching copper, the low-valence copper is one of copper metal powder, copper metal sheet and cuprous chloride.
In an embodiment of the invention, in the first step of the method for recycling resources of copper electroplating and acid etching of PCB, the oxidation-reduction potential of the etching waste solution after pretreatment is 450-500 mV.
In an embodiment of the invention, in the first step of the method for recycling resources of copper electroplating and acid etching for PCB, the filtering treatment is performed by using one of a folded filter element, a cotton core and a silicon carbide filter element with a pore size of 0.1-5 μm.
In an embodiment of the invention, in the fourth step of the method for recycling resources of copper electroplating and acid etching of PCB, the additive is a mixture of sodium chloride and hydrogen peroxide, and the content of the sodium chloride is 100-200 g/L.
In an embodiment of the invention, the oxidation-reduction potential of the regenerated acidic etching solution in the fourth step of the method for recycling the PCB copper electroplating and acidic etching copper resources is 500-550 mV.
In an embodiment of the invention, the content of chloride ions in the loaded organic phase B cleaned in the fifth step of the method for recycling the resources of the electroplated copper and the etched copper of the PCB is 35-70 mg/L.
In an embodiment of the invention, in the fifth step of the method for recycling resources of copper electroplating and acid etching of PCB, the content of copper ions in the overflow liquor of the copper electroplating production line of the printed circuit board is 15-50g/L, and the content of sulfuric acid is 150-220 g/L.
In an embodiment of the invention, in the step five of the method for recycling the copper electroplating and acid etching resources of the PCB, the content of copper ions in the copper sulfate solution is 50-80g/L, and the content of sulfuric acid is 90-160 g/L.
Compared with the prior art, the invention has the beneficial effects that:
the invention relates to a method for recycling PCB (printed circuit board) copper-electroplating and acidic etched copper resources, which is characterized in that two extracting agents are adopted to extract copper ions in solution in a segmented manner, raffinate after two-stage copper extraction is mixed with a supplementary additive and then prepared into regenerated etching solution for recycling a circuit board etching production line, copper ions carried by a load organic phase at the second stage are subjected to back extraction by using electroplating solution to obtain high-copper electroplating solution for recycling to the electroplating production line, the electroplating production line does not need to purchase a large amount of expensive phosphorus copper balls or copper oxide powder, the etching production line does not need to purchase hydrochloric acid, the recycling of the copper resources of the electroplating production line and the acidic etching production line is realized, the risk of secondary environment pollution caused by transporting and disposing the etching waste solution is avoided, and the method has good ecological environment and economic benefits.
Drawings
FIG. 1 is a flow chart of the PCB copper electroplating and acid etching resource recycling method of the present invention.
Detailed Description
A method for recycling PCB copper electroplating and acid etching copper resources comprises the following steps:
step one, pretreatment of acidic etching waste liquid: the waste etching solution overflowing from the printed circuit board etching line is filtered and collected to an oxidant breaking reactor, and the filtering treatment is carried out by adopting one mode of a folding filter element with the aperture of 0.1-5 mu m, a cotton core and a silicon carbide filter element. Adding low-valence copper (metal copper powder, metal copper sheet and cuprous chloride), performing reaction for reducing oxidation-reduction potential of the etching waste liquid to obtain pretreated etching waste liquid with acidity of 2.0-2.5mol/L, wherein the oxidation-reduction potential of the pretreated etching waste liquid is 450-500mV, and the purpose of reducing the oxidation-reduction potential is to prevent residual oxidant in the etching waste liquid from damaging the extractant to cause emulsification, and the purpose of filtering is to prevent organic phase and water phase from being difficult to delaminate when membrane residue and other pollution extractants in the etching waste liquid occur.
Step two, separating copper chloride in the acidic etching waste liquid: adding an extractant A into the solution obtained in the first step for carrying out copper chloride extraction reaction to obtain a raffinate A with copper ion content of 5-10g/L and a loaded organic phase A, carrying out back extraction on the loaded organic phase A by using pure water to obtain a copper chloride solution and the extractant A, wherein the volume ratio of the extractant A to the etching waste liquid is (2-3): 1, the extractant A is a mixture of pyridine carboxylic ester and sulfonated kerosene, the volume fraction of the pyridine carboxylic ester is 10-35%, and the pyridine carboxylic ester is preferably AcorgaDS5443(CLX 50).
Step three, separating copper ions in the copper chloride solution: mixing the copper chloride solution obtained in the step two with an extracting agent B for copper extraction reaction to obtain a loadThe organic phase B and raffinate B with the copper ion content of 5-10g/L, and the volume ratio of the extractant B to the raffinate A is (2-3): 1, the extractant B is an ester modified aldoxime substance (
M5640 and SIOMEX N902) with ketoximes (A), (B), (C), (
984N) and sulfurized kerosene, the volume fraction of the ester-modified aldoxime substance to the one ketoxime substance being 10-35%.
Step four, preparing acidic etching regeneration liquid: and mixing the raffinate B obtained in the third step with the raffinate A obtained in the second step, adding an additive to prepare a regenerated acidic etching solution, and recycling the regenerated acidic etching solution to an acidic etching production line, wherein the additive is a mixture of sodium chloride and hydrogen peroxide, the addition of hydrogen peroxide is judged by the oxidation-reduction potential of the acidic etching solution, the content of the sodium chloride is 100-550 g/L, and the oxidation-reduction potential of the regenerated acidic etching solution is 500-550 mV.
Step five, blending of the electrolytic copper plating liquid medicine: the method comprises the steps of cleaning a loading organic phase B with the chloride ion content of 35-70mg/L and the copper ion content of 15-50g/L, cleaning the loading organic phase B to reduce chloride ions carried in the loading organic phase so as to ensure that the chloride ions in the copper electroplating liquid are stabilized at 35-70mg/L and the overflow liquid medicine of the printed circuit board copper electroplating production line with the sulfuric acid content of 150-220g/L is mixed to carry out copper back extraction reaction, and obtaining an extracting agent B with the copper ion content of 50-80g/L and a copper sulfate solution with the sulfuric acid content of 90-160g/L after the copper back extraction.
The technical solutions in the embodiments of the present invention will be clearly and completely described below so that those skilled in the art can better understand the advantages and features of the present invention, and thus the scope of the present invention will be more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.
In the method for recycling the PCB electrolytic copper plating and acid etching copper resources, the sulfuric acid solution used in the method is prepared from 98% concentration analytical pure sulfuric acid and pure water, the acid etching waste liquid is the production waste liquid used for PCB etching procedures of PCB circuit board production enterprises, the copper content of the acid etching waste liquid is 160g/L, and the hydrochloric acid content is 2.0-2.5 mol/L.
Example 1
Step one, pretreatment of acidic etching waste liquid: filtering the etching waste liquid obtained by overflowing a circuit board etching line (DES), collecting the etching waste liquid to an oxidant breaking reactor, adding a certain amount of metal copper powder until the oxidation-reduction potential is reduced to 450mV, and filtering by using a folding filter element filter with the pore diameter of 0.5 mu m to obtain the pretreated acidic etching waste liquid with the acidity of 2.5 mol/L;
step two, separating copper chloride in the acidic etching waste liquid: adding a sulfonated kerosene mixture (extractant A) with the volume fraction of 35 percent of pyridine carboxylate AcorgaDS5443(CLX50) to perform copper chloride extraction reaction, wherein the volume ratio of the sulfonated kerosene mixture (extractant A) of pyridine carboxylate AcorgaDS5443(CLX50) to the etching waste liquid is 3: 1, after extraction reaction for a certain time, entering an oil-water separation system to obtain raffinate A loaded with an organic phase A and copper ion content of 10g/L, and performing back extraction on the loaded organic phase A with pure water to obtain a copper chloride solution and sulfonated kerosene mixture (extractant A) of pyridine carboxylate AcorgaDS5443(CLX 50);
step three, separating copper ions in the copper chloride solution: adding 35% by volume of copper chloride solution
The mixture of M5640 and sulfurized kerosene (extractant B) is used for extracting copper,
the volume ratio of the mixture of M5640 and sulfurized kerosene (extractant B) to raffinate a was 3: 1, carrying out oil-water separation after extraction reaction for a certain time to obtain a loaded organic phase B and raffinate B with the copper ion content of 10 g/L;
step four, preparing acidic etching regeneration liquid: mixing raffinate A and raffinate B, adding sodium chloride and hydrogen peroxide to obtain regenerated acidic etching solution, recycling the regenerated acidic etching solution to an acidic etching production line (DES), adding the regenerated acidic etching solution and the hydrogen peroxide to the acidic etching production line through a metering pump, and keeping the ORP (oxidation reduction potential) of the acidic etching production line at 500-550mV and the acidity of 2.0-2.5 mol/L;
step five, blending of the electrolytic copper plating liquid medicine: washing the loaded organic phase B by pure water to reduce chloride ions carried in the loaded organic phase B, then adding the washed loaded organic phase B into electroplating liquid medicine (the copper content is 15g/L, the sulfuric acid is 220g/L) overflowing from an electroplating copper production line to perform copper stripping, wherein the volume ratio of the loaded organic phase B to the electroplating liquid medicine is 3: 1, back-extracting for a certain time, then feeding the solution into an oil-water separator to obtain an extractant B and a copper sulfate solution (the copper content is 80g/L and the sulfuric acid content is 120g/L), adding the copper sulfate solution into an electroplating copper production line by using a metering pump, and keeping the copper ion content of the electroplating copper production line at 15g/L and the chloride ion content at 35mg/L according to the current size and the copper ion consumption speed of the electroplating production line.
Example 2
Step one, pretreatment of acidic etching waste liquid: filtering the etching waste liquid obtained by overflowing a circuit board etching line (DES), collecting the etching waste liquid to an oxidant breaking reactor, adding a certain amount of metal copper sheets until the oxidation-reduction potential is reduced to 480mV, and filtering by using a cotton core filter with the pore diameter of 1 mu m to obtain the pretreated acidic etching waste liquid with the acidity of 2.0 mol/L;
step two, separating copper chloride in the acidic etching waste liquid: adding a mixture (extracting agent A) of 10 percent of pyridine carboxylic ester AcorgaDS5443(CLX50) and sulfurized kerosene to extract copper chloride, wherein the volume ratio of the mixture (extracting agent A) of pyridine carboxylic ester AcorgaDS5443(CLX50) and sulfurized kerosene to the etching waste liquid is 2.5: 1, after extraction reaction for a certain time, entering an oil-water separation system to obtain raffinate A with the content of loaded organic phase A and copper ions being 5g/L, wherein the acidity of the raffinate A is 0.1mol/L, and carrying out back extraction on the organic phase A by using pure water to obtain a mixture (extractant A) of a copper chloride solution, pyridine carboxylic ester AcorgaDS5443(CLX50) and sulfurized kerosene;
step three, separating copper ions in the copper chloride solution: adding a mixture (extracting agent B) of SIOMEX N902 and vulcanized kerosene with the volume fraction of 10% into the copper chloride solution to extract copper, wherein the volume ratio of the mixture (extracting agent B) of SIOMEX N902 and vulcanized kerosene to raffinate A is 2.5: 1, carrying out oil-water separation after extraction reaction for a certain time to obtain a loaded organic phase B and raffinate B with the copper ion content of 5 g/L;
step four, preparing acidic etching regeneration liquid: mixing raffinate A and raffinate B, adding sodium chloride and hydrogen peroxide to obtain regenerated acidic etching solution, recycling the regenerated acidic etching solution to an acidic etching production line (DES), adding the regenerated acidic etching solution and the hydrogen peroxide to the acidic etching production line through a metering pump, and keeping the ORP (oxidation reduction potential) of the acidic etching production line at 500-550mV and the acidity of 2.0-2.5 mol/L;
step five, blending of the electrolytic copper plating liquid medicine: washing the loaded organic phase B by pure water to reduce chloride ions carried in the loaded organic phase B, then adding the washed loaded organic phase B into electroplating liquid medicine (the copper content is 30g/L, the sulfuric acid content is 190g/L) overflowing from an electroplating copper production line to perform copper stripping, wherein the volume ratio of the loaded organic phase B to the electroplating liquid medicine is 2.5: 1, back-extracting for a certain time, then feeding the solution into an oil-water separator to obtain an extractant B and a copper sulfate solution (the copper content is 60g/L and the sulfuric acid content is 145g/L), adding the copper sulfate solution into an electroplating copper production line by using a metering pump, and keeping the copper ion content of the electroplating copper production line at 30g/L and the chloride ion content at 50mg/L according to the current size and the copper ion consumption speed of the electroplating production line.
Example 3
Step one, pretreatment of acidic etching waste liquid: filtering the etching waste liquid obtained by overflowing a circuit board etching line (DES), collecting the etching waste liquid to an oxidant breaking reactor, adding a certain amount of cuprous chloride strips until the oxidation-reduction potential is reduced to 500mV, and filtering by using a silicon carbide filter element filter with the pore diameter of 5 mu m to obtain the pretreated acidic etching waste liquid with the acidity of 2.2 mol/L;
step two, separating copper chloride in the acidic etching waste liquid: adding a mixture (extracting agent A) of 20 percent of pyridine carboxylic ester AcorgaDS5443(CLX50) and sulfurized kerosene to extract copper chloride, wherein the volume ratio of the mixture (extracting agent A) of pyridine carboxylic ester AcorgaDS5443(CLX50) and sulfurized kerosene to the etching waste liquid is 2: 1, after extraction reaction for a certain time, entering an oil-water separation system to obtain raffinate A with the content of a loaded organic phase A and copper ions being 7g/L, wherein the acidity of the raffinate A is 0.5mol/L, and carrying out back extraction on the organic phase A by using pure water to obtain a mixture (an extractant A) of a copper chloride solution, pyridine carboxylic ester AcorgaDS5443(CLX50) and sulfurized kerosene;
step three, separating copper ions in the copper chloride solution: adding copper chloride solution with volume fraction of 20%
984N and sulfurized kerosene (extractant B),
the volume ratio of the mixture of 984N and sulfurized kerosene (extractant B) to raffinate a was 2: 1, carrying out oil-water separation after extraction reaction for a certain time to obtain a loaded organic phase B and raffinate B with the copper ion content of 7 g/L;
step four, preparing acidic etching regeneration liquid: mixing raffinate A and raffinate B, adding sodium chloride and hydrogen peroxide to obtain regenerated acidic etching solution, recycling the regenerated acidic etching solution to an acidic etching production line (DES), adding the regenerated acidic etching solution and the hydrogen peroxide to the acidic etching production line through a metering pump, and keeping the ORP (oxidation reduction potential) of the acidic etching production line at 500-550mV and the acidity of 2.0-2.5 mol/L;
step five, blending of the electrolytic copper plating liquid medicine: washing the loaded organic phase B by pure water to reduce chloride ions carried in the loaded organic phase B, then adding the washed loaded organic phase B into electroplating liquid medicine (copper content is 50g/L, sulfuric acid is 150g/L) overflowing from an electroplating copper production line to perform copper stripping, wherein the volume ratio of the loaded organic phase B to the electroplating liquid medicine is 2: 1, back-extracting for a certain time, then feeding the solution into an oil-water separator to obtain an extractant B and a copper sulfate solution (the copper content is 70g/L and the sulfuric acid content is 120g/L), adding the copper sulfate solution into an electroplating copper production line by using a metering pump, and keeping the copper ion content of the electroplating copper production line at 50g/L and the chloride ion content at 70mg/L according to the current size and the copper ion consumption speed of the electroplating production line.
Finally, 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 protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. A PCB copper electroplating and acid etching copper resource recycling method is characterized in that: the method comprises the following steps:
step one, pretreatment of acidic etching waste liquid: filtering the etching waste liquid overflowing from the printed circuit board etching line, collecting the etching waste liquid to an oxidant destruction reactor, and adding low-valence copper to perform a reaction for reducing the oxidation-reduction potential of the etching waste liquid to obtain pretreated etching waste liquid with acidity of 2.0-2.5 mol/L;
step two, separating copper chloride in the acidic etching waste liquid: adding an extractant A into the solution obtained in the first step for carrying out copper chloride extraction reaction to obtain a raffinate A with copper ion content of 5-10g/L and a loaded organic phase A, carrying out back extraction on the loaded organic phase A by using pure water to obtain a copper chloride solution and the extractant A, wherein the volume ratio of the extractant A to the etching waste liquid is (2-3): 1, the extractant A is a mixture of pyridine carboxylic ester and sulfonated kerosene, and the volume fraction of the pyridine carboxylic ester is 10-35%;
step three, separating copper ions in the copper chloride solution: mixing the copper chloride solution obtained in the second step with an extractant B to perform copper extraction reaction to obtain a loaded organic phase B and a raffinate B with the copper ion content of 5-10g/L, wherein the volume ratio of the extractant B to the raffinate A is (2-3): 1, the extracting agent B is a mixture of an ester-modified aldoxime substance and one of ketoxime substances and sulfurized kerosene, and the volume fraction of the ester-modified aldoxime substance and one of ketoxime substances is 10-35%;
step four, preparing acidic etching regeneration liquid: mixing the raffinate B obtained in the step three with the raffinate A obtained in the step two, supplementing additives, and blending to prepare a regenerated acidic etching solution for recycling to an acidic etching production line;
step five, blending of the electrolytic copper plating liquid medicine: and (3) mixing the load organic phase B obtained in the step three after cleaning with overflow liquid medicine of a printed circuit board copper electroplating production line to perform a copper back-extraction reaction, and obtaining an extracting agent B and a copper sulfate solution after back-extraction.
2. The method for recycling PCB copper electroplating and acid etching resources as claimed in claim 1, wherein the method comprises the following steps: the low-valence copper in the first step is one of metal copper powder, metal copper sheet and cuprous chloride.
3. The method for recycling PCB copper electroplating and acid etching resources as claimed in claim 1, wherein the method comprises the following steps: the oxidation-reduction potential of the etching waste liquid pretreated in the first step is 450-500 mV.
4. The method for recycling PCB copper electroplating and acid etching resources as claimed in claim 1, wherein the method comprises the following steps: the filtration treatment in the first step is carried out by adopting one mode of a folding filter element with the aperture of 0.1-5 mu m, a cotton core and a silicon carbide filter element.
5. The method for recycling PCB copper electroplating and acid etching resources as claimed in claim 1, wherein the method comprises the following steps: the additive in the fourth step is a mixture of sodium chloride and hydrogen peroxide, and the content of the sodium chloride is 100-200 g/L.
6. The method for recycling PCB copper electroplating and acid etching resources as claimed in claim 1, wherein the method comprises the following steps: the oxidation-reduction potential of the regenerated acidic etching solution in the fourth step is 500-550 mV.
7. The method for recycling PCB copper electroplating and acid etching resources as claimed in claim 1, wherein the method comprises the following steps: and after the washing in the fifth step, the content of chloride ions in the loaded organic phase B is 35-70 mg/L.
8. The method for recycling PCB copper electroplating and acid etching resources as claimed in claim 1, wherein the method comprises the following steps: in the fifth step, the content of copper ions in the overflow liquid medicine of the printed circuit board copper electroplating production line is 15-50g/L, and the content of sulfuric acid is 150-220 g/L.
9. The method for recycling PCB copper electroplating and acid etching resources as claimed in claim 1, wherein the method comprises the following steps: and in the step five, the copper ion content of the copper sulfate solution is 50-80g/L, and the sulfuric acid content is 90-160 g/L.
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| CN114032394A (en) * | 2021-11-08 | 2022-02-11 | 昆山华拓环保科技有限公司 | Regeneration copper extraction method of alkaline etching solution |
| CN114395789A (en) * | 2021-12-31 | 2022-04-26 | 广东鑫菱环境科技有限公司 | Method for recycling copper in PCB electroplating process |
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