CN112695345A - Method for recovering brownification waste liquid of printed circuit board - Google Patents
Method for recovering brownification waste liquid of printed circuit board Download PDFInfo
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- CN112695345A CN112695345A CN202011451395.9A CN202011451395A CN112695345A CN 112695345 A CN112695345 A CN 112695345A CN 202011451395 A CN202011451395 A CN 202011451395A CN 112695345 A CN112695345 A CN 112695345A
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
The invention belongs to the technical field of heavy metal waste liquid recovery methods, and provides a method for recovering brownification waste liquid of a printed circuit board, wherein an oxidant is adopted for pretreatment, so that part of organic matters which are difficult to degrade can be decomposed into micromolecular organic matters, the treatment difficulty of pre-electrolysis is reduced, and the addition amount of the oxidant is small, and the effect is good; the chlorine salt is added in the pre-electrolysis before the electroplating, and the chlorine generated by the anode can not only oxidize organic matters, but also reduce the problem of low anode efficiency caused by the attachment of the organic matters on the anode; after the organic matter is degraded through decomplexation and the organic matter is oxidized through pre-electrolysis twice, the influence of the organic matter on copper deposition during cathode copper deposition is solved, and an electrolysis additive is added, so that the copper plating effect in the electrolysis process is better, the electroplated copper can be effectively crystallized into blocks and is easy to strip, the copper yield is increased, the copper yield is improved, the copper yield is simpler and easier to relax, the COD (chemical oxygen demand) of the solution after electric cleaning is low, the heavy metal content is low, and the treatment difficulty and the treatment cost of treating the browning waste liquid in a comprehensive waste water station are reduced.
Description
Technical Field
The invention belongs to the technical field of heavy metal waste liquid recovery methods, and particularly relates to a method for recovering brownification waste liquid of a printed circuit board.
Background
The browning technology is an indispensable process for the inner layer board of the PCB. With the demand for high precision, high density integrated circuits, printed circuit board manufacturing technology is moving towards more sophisticated multilayer circuit boards. Thereby increasing the consumption of the browning liquid and the generation of the browning waste liquid.
The browning liquid performs a micro-etching effect on the surface of the copper foil through sulfuric acid and hydrogen peroxide in the browning liquid, and a film layer for increasing the interlayer pressing performance and protecting the copper surface is formed under the participation of an organic additive.
The brown oxidation waste liquid contains a plurality of toxic organic matters including a large amount of triazole, polyglycol and other macromolecules with lone pair electrons such as N, S, P, one part of the toxic organic matters and copper ions form a complex, and the other part of the toxic organic matters are in a free solution. At present, some data exist for processing the copper-containing alloy, wherein the chemical precipitation method has the problems of high reagent consumption, poor copper precipitation quality, low economic benefit, secondary pollution and the like, so that the copper-containing alloy is not popular in the market. The brownification waste liquid treatment also tends to meet the requirements of more economical treatment, higher quality of recovered copper and tighter environmental protection.
Because a large amount of macromolecular organic matters and micromolecular organic matters which are complexed with copper exist in the browning waste liquid, the treatment cost of the browning waste liquid is high, and the content of effectively extracted copper is low. At present, the treatment methods aiming at the browning waste liquid comprise the following steps:
1. adding a cationic polymer, and then carrying out copper extraction treatment in an electrolytic manner;
2. performing electro-Fenton treatment to break complexation and oxidize organic matters;
3. treating by using a mixed treatment mode of microetching liquid and browning waste liquid;
4. a complex for treating brownification waste liquid by using an ultrahigh oxygen evolution electrode and variable valence metal cations and an electrolytic copper extraction method;
5. removing macromolecular organic complex by flocculation precipitation, and adding oxidizing medium to electrolyze and extract copper.
But the defects of the prior mode are as follows:
1. the cationic complex is added to form an electrolytic complex effectively, but the problems that the anode efficiency is influenced by the aggregation of organic matters of a prototype due to macromolecular organic matters in the solution and the electroplating efficiency is low and the plating is not formed due to the fact that the macromolecular organic matters can be complexed with copper ions again and the cathode is coated with copper-plated organic matters are not solved substantially;
2. the electro-Fenton can effectively treat small molecular organic matters, but has poor treatment effect on large molecular organic matters;
3. the mixing treatment only dilutes the concentration of the copper complex compound, and has poor electroplating forming effect;
4. the extraction and recovery treatment cost of the variable valence metal cations is high, and the operation and maintenance cost is high due to the failure of an extracting agent;
5. the flocculation precipitation can reduce the concentration of copper ions to a great extent, and the oxidative medium is added to slow down the degradation speed of organic matters, so that the copper adding effect is not greatly improved.
Disclosure of Invention
Aiming at the defects, the invention provides a method for recovering brown oxide waste liquid of a printed circuit board, which can effectively solve the problems that electro-coppering is not shaped and can not be electroplated, and provides a process method for solving the problems, wherein the content of the invention is as follows:
the invention aims to provide a method for recovering brownification waste liquid of a printed circuit board, which is technically characterized by comprising the following steps of: the method for recovering the brown oxidation waste liquid of the printed circuit board comprises the following steps:
the method comprises the following steps: adding 0.1-1 wt% of oxidant into the brown oxidation waste liquid of the printed circuit board, adding 0.1-1 wt% of digesting agent, stirring for 1-3h at the temperature of 18-35 ℃, and then carrying out oxidation decomplexation reaction for 10-14h to obtain a mixture A;
step two: filtering the mixture A obtained in the second step by a filter to obtain an organic matter A and a filtered solution A, adding chloride salt into the filtered solution A, then carrying out pre-electrolysis reaction for 1-2h, wherein the current density of the pre-electrolysis is 1-3asd, and carrying out circulating filtration on the filtered solution A in the electrolysis process until the filtered solution A does not generate visible organic floating matters any more, thus obtaining a filtered solution B;
step three: and (3) adding 0.2-0.3 wt% of electroplating additive into the filtered clear liquid B obtained in the step (II) to perform electroplating copper extraction, maintaining the concentration of chloride ions in the clear liquid B to be 4-6gL, and the electroplating current density to be 0.3-1.5asd to obtain treated liquid C and metal copper, wherein the treated liquid C is discharged after reaching the standard in detection.
In some embodiments of the present invention, in the first step of the method for recovering brown oxidation waste liquid of a printed circuit board, the oxidizing agent is one of potassium permanganate and sodium chlorate, and the digesting agent is at least one of hydrogen peroxide and sodium tungstate.
In some embodiments of the present invention, in the first step of the method for recovering brown oxidation waste liquid of a printed circuit board, the COD content of the brown oxidation waste liquid of the printed circuit board is 10000-.
In some embodiments of the present invention, the chlorine salt in the second step of the method for recovering brown waste liquid of a printed circuit board is at least one of sodium chloride and potassium chloride.
In some embodiments of the present invention, the COD content in the filtrate a in the second step of the method for recovering brownification waste liquid of a printed circuit board is 4000-.
6. The method for recovering the brownification waste liquid of the printed wiring board as claimed in claim 1, characterized in that: the COD content in the clear filtrate B in the second step is 500-1000, and the copper ion content is 20-25 g/L.
In some embodiments of the present invention, the electroplating additive in the third step of the method for recovering brown waste liquid of printed circuit board is at least one of polyether, thiourea, gelatin and sodium dodecyl benzene sulfonate.
In some embodiments of the invention, when the content of copper ions in the liquid C in the third step of the method for recovering brown oxidation waste liquid of a printed circuit board is 12 to 25g/L, the current density of electroplating is 1 to 1.5 asd.
In some embodiments of the invention, when the content of copper ions in the liquid C in the third step of the method for recovering brown oxidation waste liquid of a printed circuit board is 5 to 12g/L, the current density of electroplating is 0.5 to 0.8 asd.
In some embodiments of the invention, when the content of copper ions in the liquid C in the third step of the method for recovering brown oxidation waste liquid of a printed circuit board is 0 to 5g/L, the current density of electroplating is 0 to 0.3 asd.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the oxidant is adopted for pretreatment, so that part of organic matters which are difficult to degrade can be decomposed into micromolecular organic matters, the treatment difficulty of pre-electrolysis is reduced, and the addition amount of the oxidant is small, and the effect is good; the method adds chloride salt by pre-electrolysis before electroplating, the anode generates the effect of oxidizing organic matters by chlorine, and the problem of low anode efficiency caused by the attachment of the organic matters on the anode can be solved; after the organic matter is degraded through decomplexation and the organic matter is oxidized through pre-electrolysis twice, the influence of the organic matter on copper deposition during cathode copper deposition is basically solved, and an electrolysis additive is added, so that the copper plating effect in the electrolysis process is better, the electroplated copper can be effectively crystallized into blocks and is easy to strip, the copper yield is increased, the copper yield is improved, the copper yield is simpler and easier to relax, the COD (chemical oxygen demand) of the solution after electric cleaning is low, the heavy metal content is low, and the treatment difficulty and the treatment cost of brown waste liquid treatment in a comprehensive wastewater station are reduced.
Drawings
FIG. 1 is a flow chart of the method for recovering brownification waste liquid of a printed circuit board of the present invention.
Detailed Description
The invention relates to a method for recovering brownification waste liquid of a printed circuit board, which comprises the following steps:
the method comprises the following steps: adding 0.1-1 wt% of oxidant (at least one of potassium permanganate and sodium chlorate) into the brown waste liquid of the printed circuit board, adding 0.1-1 wt% of digesting agent (at least one of hydrogen peroxide and sodium tungstate) into the brown waste liquid of the printed circuit board, stirring the mixture at the temperature of 18-35 ℃ for 1-3h, and then carrying out oxidation complex breaking reaction for 10-14h to obtain a mixture A, wherein the oxidant is used for breaking main organic matters and polymer complexes in the brown waste liquid of the printed circuit board.
Wherein, the COD content of the brown oxidation waste liquid of the printed circuit board is 10000-20000, and the copper ion content is 25-30 g/L.
Step two: and filtering the mixture A obtained in the second step by a filter to obtain an organic matter A and a filtered solution A, adding chloride salt (at least one of sodium chloride or potassium chloride) into the filtered solution A, then carrying out pre-electrolysis reaction for 1-2h, wherein the current density of the pre-electrolysis is 1-3asd, and carrying out circulating filtration on the filtered solution A in the electrolysis process until the filtered solution A does not generate visible organic floating matters any more, thus obtaining a filtered solution B.
Wherein, the COD content in the clear filtrate A is 4000-6000, and the copper ion content is 20-30 g/L.
Wherein the COD content in the clear filtrate B is 500-1000, and the copper ion content is 20-25 g/L.
Step three: and (2) adding 0.2-0.3 wt% of electroplating additive (at least one of polyether, thiourea, gelatin and sodium dodecyl benzene sulfonate) into the filtered clear liquid B obtained in the second step for electroplating to extract copper, adding chloride to improve the anode efficiency and the organic matter treatment rate, maintaining the concentration of chloride ions in the clear liquid B to be 4-6gL, and the electroplating current density to be 0.3-1.5asd to obtain treated liquid C and metal copper, wherein the treated liquid C is discharged after reaching the standard in detection.
Wherein, when the copper ion content of the liquid C is 12-25g/L, the current density of the electroplating is 1-1.5 asd.
When the copper ion content of the liquid C is 5-12g/L, the current density of the electroplating is 0.5-0.8 asd.
When the copper ion content of the liquid C is 0-5g/L, the current density of the electroplating is 0-0.3 asd.
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.
Example 1
A method for recovering brownification waste liquid of a printed circuit board comprises the following steps:
the method comprises the following steps: adding 0.55 wt% of oxidant into the brown oxide waste liquid of the printed circuit board, adding 0.55 wt% of digesting agent, stirring for 2h at the temperature of 25 ℃, and then carrying out oxidation complex breaking reaction for 12h to obtain a mixture A.
Wherein the oxidant is potassium permanganate, and the digesting agent is hydrogen peroxide.
Wherein, the COD content of the brown oxidation waste liquid of the printed circuit board is 15000, and the copper ion content is 25 g/L.
Step two: and filtering the mixture A obtained in the second step by a filter to obtain an organic matter A and a filtered solution A, adding chloride salt into the filtered solution A, carrying out pre-electrolysis reaction for 1.5h, wherein the current density of the pre-electrolysis is 2asd, and carrying out circulating filtration on the filtered solution A in the electrolysis process until the filtered solution A does not generate visible organic floating matters any more, thus obtaining a filtered solution B.
Wherein the chloride salt is sodium chloride.
Wherein, the COD content in the filtrate A is 5000, and the copper ion content is 30 g/L.
Wherein the COD content in the clear filtrate B is 500-1000, and the copper ion content is 23 g/L.
Step three: and (3) adding 0.25 wt% of electroplating additive into the filtered clear liquid B obtained in the step two for electroplating to extract copper, maintaining the concentration of chloride ions in the clear liquid B to be 5gL, thus obtaining treated liquid C and metal copper, and discharging the treated liquid C after the detection reaches the standard.
Wherein the electroplating additive is polyether.
Wherein when the copper ion content of the liquid C is 12-23g/L, the current density of the electroplating is 1-1.5 asd.
When the copper ion content of the liquid C is 5-12g/L, the current density of the electroplating is 0.5-0.8 asd.
When the copper ion content of the liquid C is 0-5g/L, the current density of the electroplating is 0-0.3 asd.
Example 2
A method for recovering brownification waste liquid of a printed circuit board comprises the following steps:
the method comprises the following steps: adding 0.1 wt% of oxidant into the brown oxide waste liquid of the printed circuit board, adding 0.1 wt% of digesting agent, stirring for 1h at the temperature of 18 ℃, and then carrying out oxidation complex breaking reaction for 14h to obtain a mixture A.
Wherein the oxidant is sodium chlorate, and the digesting agent is sodium tungstate.
Wherein, the COD content of the brown oxidation waste liquid of the printed circuit board is 10000, and the copper ion content is 25 g/L.
Step two: and filtering the mixture A obtained in the second step by a filter to obtain an organic matter A and a filtrate A, adding chloride salt into the filtrate A, carrying out pre-electrolysis reaction for 1h, wherein the current density of the pre-electrolysis is 1asd, and carrying out circulating filtration on the filtrate A in the electrolysis process until the filtrate A does not generate visible organic floating matters any more, thus obtaining a filtrate B.
Wherein the chloride salt is potassium chloride.
Wherein, the COD content in the clear filtrate A is 4000-6000, and the copper ion content is 20 g/L.
Wherein the COD content in the clear filtrate B is 500-1000, and the copper ion content is 18 g/L.
Step three: and (3) adding 0.2 wt% of electroplating additive into the filtered clear liquid B obtained in the step two for electroplating to extract copper, maintaining the concentration of chloride ions in the clear liquid B to be 4gL, thus obtaining treated liquid C and metal copper, and discharging the treated liquid C after the detection reaches the standard.
Wherein the plating additive is thiourea.
Wherein when the copper ion content of the liquid C is 12-20g/L, the current density of the electroplating is 1-1.5 asd.
When the copper ion content of the liquid C is 5-12g/L, the current density of the electroplating is 0.5-0.8 asd.
When the copper ion content of the liquid C is 0-5g/L, the current density of the electroplating is 0-0.3 asd.
Example 3
A method for recovering brownification waste liquid of a printed circuit board comprises the following steps:
the method comprises the following steps: adding 1 wt% of oxidant into the brown oxide waste liquid of the printed circuit board, adding 1 wt% of digesting agent, stirring for 3h at the temperature of 18-35 ℃, and then carrying out oxidation decomplexation reaction for 10h to obtain a mixture A.
Wherein the oxidant is potassium permanganate, and the digesting agent is hydrogen peroxide.
Wherein, the COD content of the brown oxidation waste liquid of the printed circuit board is 20000, and the copper ion content is 30 g/L.
Step two: and filtering the mixture A obtained in the second step by a filter to obtain an organic matter A and a filtrate A, adding chloride salt into the filtrate A, carrying out pre-electrolysis reaction for 2 hours, wherein the current density of the pre-electrolysis is 3asd, and carrying out circulating filtration on the filtrate A in the electrolysis process until the filtrate A does not generate visible organic floating matters any more, thus obtaining a filtrate B.
Wherein the chloride salt is potassium chloride.
Wherein, the COD content in the filtrate A is 6000, and the copper ion content is 30 g/L.
Wherein, the COD content in the filtrate B is 1000, and the copper ion content is 25 g/L.
Step three: and (3) adding 0.3 wt% of electroplating additive into the filtered clear liquid B obtained in the step (II) for electroplating to extract copper, maintaining the concentration of chloride ions in the clear liquid B to be 6gL, thus obtaining treated liquid C and metal copper, and discharging the treated liquid C after the detection reaches the standard.
Wherein the electroplating additive is gelatin.
Wherein, when the copper ion content of the liquid C is 12-25g/L, the current density of the electroplating is 1-1.5 asd.
When the copper ion content of the liquid C is 5-12g/L, the current density of the electroplating is 0.5-0.8 asd.
When the copper ion content of the liquid C is 0-5g/L, the current density of the electroplating is 0-0.3 asd.
Example 4
A method for recovering brownification waste liquid of a printed circuit board comprises the following steps:
the method comprises the following steps: adding 0.8 wt% of oxidant into the brown oxide waste liquid of the printed circuit board, adding 0.8 wt% of digesting agent, stirring for 2h at the temperature of 20 ℃, and then carrying out oxidation complex breaking reaction for 12h to obtain a mixture A.
Wherein the oxidant is sodium chlorate, and the digesting agent is sodium tungstate.
Wherein, the COD content of the brown oxidation waste liquid of the printed circuit board is 18000, and the copper ion content is 28 g/L.
Step two: and filtering the mixture A obtained in the second step by a filter to obtain an organic matter A and a filtrate A, adding chloride salt into the filtrate A, carrying out pre-electrolysis reaction for 1h, wherein the current density of the pre-electrolysis is 2asd, and carrying out circulating filtration on the filtrate A in the electrolysis process until the filtrate A does not generate visible organic floating matters any more, thus obtaining a filtrate B.
Wherein the chloride salt is at least one of sodium chloride or potassium chloride.
Wherein, the COD content in the filtrate A is 4500, and the copper ion content is 25 g/L.
Wherein, the COD content in the filtrate B is 750, and the copper ion content is 23 g/L.
Step three: and (3) adding 0.22 wt% of electroplating additive into the filtered clear liquid B obtained in the step two for electroplating to extract copper, maintaining the concentration of chloride ions in the clear liquid B to be 4.5gL, thus obtaining treated liquid C and metal copper, and discharging the treated liquid C after the detection reaches the standard.
Wherein the electroplating additive is sodium dodecyl benzene sulfonate.
Wherein when the copper ion content of the liquid C is 12-23g/L, the current density of the electroplating is 1-1.5 asd.
When the copper ion content of the liquid C is 5-12g/L, the current density of the electroplating is 0.5-0.8 asd.
When the copper ion content of the liquid C is 0-5g/L, the current density of the electroplating is 0-0.3 asd.
The current efficiency of the electrolysis of the embodiments 1 to 4 reaches 90 to 96 percent, the cathode copper is not brittle and easy to strip after being formed, and the surface of the cathode copper cannot be powdered after the current is adjusted according to different copper ions.
Comparative example 1
In comparative example 1, the oxidation decomplexation reaction in step one is not performed, the pre-electrolysis reaction is performed after chloride is directly added into the brown oxidation waste liquid of the printed circuit board, and the rest of the operation is the same as that in example 1. The comparative example has a large amount of organic matters during pre-electrolysis treatment, has large load on filtration, is easy to block a filter pump, has small organic matter treatment capacity, and causes that the copper surface on the cathode surface is blackened or has a brown film during electroplating, and the electroplated copper is not lumpy and uneven and is powdery.
Comparative example 2
In this comparative example, the filtrate A obtained by the oxidative complexation breaking reaction was directly subjected to an electroplating reaction, and a pre-electrolysis reaction was carried out without adding a chloride salt, and the rest of the operation was the same as in example 1. In the comparative example, some organic matters are adhered to the surface of the anode during electroplating, so that the current efficiency is influenced, and the final current efficiency of electrolysis is 70-85%. And the surface of the cathode is also adhered, so that copper is brittle and cannot form a complete copper block.
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 (10)
1. A method for recovering brownification waste liquid of a printed circuit board is characterized by comprising the following steps: the method for recovering the brown oxidation waste liquid of the printed circuit board comprises the following steps:
the method comprises the following steps: adding 0.1-1 wt% of oxidant into the brown oxidation waste liquid of the printed circuit board, adding 0.1-1 wt% of digesting agent, stirring for 1-3h at the temperature of 18-35 ℃, and then carrying out oxidation decomplexation reaction for 10-14h to obtain a mixture A;
step two: filtering the mixture A obtained in the second step by a filter to obtain an organic matter A and a filtered solution A, adding chloride salt into the filtered solution A, then carrying out pre-electrolysis reaction for 1-2h, wherein the current density of the pre-electrolysis is 1-3asd, and carrying out circulating filtration on the filtered solution A in the electrolysis process until the filtered solution A does not generate visible organic floating matters any more, thus obtaining a filtered solution B;
step three: and (3) adding 0.2-0.3 wt% of electroplating additive into the filtered clear liquid B obtained in the step (II) to perform electroplating copper extraction, maintaining the concentration of chloride ions in the clear liquid B to be 4-6gL, and the electroplating current density to be 0.3-1.5asd to obtain treated liquid C and metal copper, wherein the treated liquid C is discharged after reaching the standard in detection.
2. The method for recovering the brownification waste liquid of the printed wiring board as claimed in claim 1, characterized in that: the oxidant in the step one is one of potassium permanganate and sodium chlorate, and the digesting agent is at least one of hydrogen peroxide and sodium tungstate.
3. The method for recovering the brownification waste liquid of the printed wiring board as claimed in claim 1, characterized in that: the COD content of the brown oxidation waste liquid of the printed circuit board in the first step is 10000-20000, and the copper ion content is 25-30 g/L.
4. The method for recovering the brownification waste liquid of the printed wiring board as claimed in claim 1, characterized in that: and the chloride salt in the second step is at least one of sodium chloride or potassium chloride.
5. The method for recovering the brownification waste liquid of the printed wiring board as claimed in claim 1, characterized in that: the COD content in the clear filtrate A in the second step is 4000-6000, and the copper ion content is 20-30 g/L.
6. The method for recovering the brownification waste liquid of the printed wiring board as claimed in claim 1, characterized in that: the COD content in the clear filtrate B in the second step is 500-1000, and the copper ion content is 20-25 g/L.
7. The method for recovering the brownification waste liquid of the printed wiring board as claimed in claim 1, characterized in that: and the electroplating additive in the third step is at least one of polyether, thiourea, gelatin and sodium dodecyl benzene sulfonate.
8. The method for recovering the brownification waste liquid of the printed wiring board as claimed in claim 1, characterized in that: and when the content of copper ions in the liquid C in the third step is 12-25g/L, the current density of electroplating is 1-1.5 asd.
9. The method for recovering the brownification waste liquid of the printed wiring board as claimed in claim 1, characterized in that: and when the content of copper ions in the liquid C in the third step is 5-12g/L, the current density of electroplating is 0.5-0.8 asd.
10. The method for recovering the brownification waste liquid of the printed wiring board as claimed in claim 1, characterized in that: and when the content of copper ions in the liquid C in the third step is 0-5g/L, the current density of electroplating is 0-0.3 asd.
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| CN202011451395.9A CN112695345A (en) | 2020-12-10 | 2020-12-10 | Method for recovering brownification waste liquid of printed circuit board |
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| CN202011451395.9A CN112695345A (en) | 2020-12-10 | 2020-12-10 | Method for recovering brownification waste liquid of printed circuit board |
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| CN202011451395.9A Pending CN112695345A (en) | 2020-12-10 | 2020-12-10 | Method for recovering brownification waste liquid of printed circuit board |
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