CN111977752A - Treatment process for copper-containing etching cleaning wastewater of printed circuit board - Google Patents
Treatment process for copper-containing etching cleaning wastewater of printed circuit board Download PDFInfo
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- CN111977752A CN111977752A CN202010797107.9A CN202010797107A CN111977752A CN 111977752 A CN111977752 A CN 111977752A CN 202010797107 A CN202010797107 A CN 202010797107A CN 111977752 A CN111977752 A CN 111977752A
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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
- 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
- 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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
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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
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
The invention provides a treatment process of copper-containing etching and cleaning wastewater of a printed circuit board, belongs to the technical field of copper-containing etching wastewater treatment, and particularly relates to a treatment process of copper-containing etching and cleaning wastewater of a printed circuit board. The process flow comprises the following steps: electrolytic ion membrane treatment, pure water recovery, pure water reuse, concentrated solution collection, electrolytic copper extraction and concentrated ammonia solution reuse. Compared with the prior art, the invention has the advantages and effects that: firstly, the process can realize the treatment cost close to zero cost, has considerable economic benefit and realizes high-level circular economy; secondly, the process does not add any chemical raw materials, does not generate any new chemical substances, realizes zero discharge of waste water and waste residue, has no pollution to the environment and has good social benefit; thirdly, the process can realize the recycling of the waste water and the etching solution and can recover copper ions in the etching solution by electrolysis; finally, the process is simple and convenient to popularize and use.
Description
Technical Field
The invention belongs to the technical field of copper-containing etching wastewater treatment, and particularly relates to a treatment process of copper-containing etching cleaning wastewater of a printed circuit board.
Background
The etching process in the etching process for manufacturing the printed circuit board comprises alkaline etching and acid etching, wherein the alkaline etching solution contains ammonia water, the content of the ammonia in the etched cleaning water is high, and the problems of high removal difficulty, high treatment cost, high standard-reaching difficulty and the like exist in the treatment of copper ammonia wastewater due to the complexing action of the ammonia and the copper.
The prior art discloses a wastewater treatment process for etching and cleaning wastewater with the patent number of CN201911069649.8, which comprises the following steps: flocculation precipitation, evaporation desalting and sludge treatment. The flocculation precipitation comprises the steps of collecting etching cleaning wastewater in a wastewater collection pool, conveying the etching cleaning wastewater to a reaction tank through a wastewater lifting pump, adding alkali into the reaction tank, adjusting the pH value to be neutral, adding a coagulant, and adding a flocculant finally; and the sediment in the reaction tank is sunk into a sludge hopper below in the sedimentation tank under the action of gravity, and the wastewater in the reaction tank flows to the clear water tank through an upper overflow weir. The wastewater treatment process for the etching cleaning wastewater disclosed by the invention is simple in process and convenient to operate, realizes zero discharge of sewage, does not generate toxic and harmful byproducts in treatment engineering, is pollution-free, and has extremely high economic benefit and environmental benefit, and the treated etching cleaning wastewater is clear in water quality, free of obvious suspended matters, less than or equal to 700us/cm in electric conductivity and wide in prospect. Although the process has the advantages of simple operation and no pollution in the production process, the process still has the defects of high treatment cost and incomplete recycling of waste water.
Disclosure of Invention
In order to solve the above problems, a primary object of the present invention is to provide a process for treating copper-containing etching and cleaning wastewater for printed circuit boards, which can achieve a treatment cost close to zero cost, has a very considerable economic benefit, and realizes a high level of recycling economy;
the invention also aims to provide a process for treating the copper-containing etching cleaning wastewater of the printed circuit board, which does not add any chemical raw material and generate any new chemical substance, realizes zero discharge of wastewater and waste residue, has no pollution to the environment and has good social benefit;
the invention also aims to provide a process for treating the copper-containing etching and cleaning wastewater of the printed circuit board, which can realize the recycling of the wastewater and the etching solution and can electrolyze and recover copper ions in the etching solution;
the final purpose of the invention is to provide a process for treating the copper-containing etching cleaning wastewater of the printed circuit board, which has simple process flow and is convenient for popularization and use.
In order to achieve the above object, the present invention has the following technical means.
The invention provides a process for treating copper-containing etching cleaning wastewater of a printed circuit board, which comprises the following steps:
the method comprises the following steps: electrolytic ion membrane treatment: the waste water containing copper ions from the etching and cleaning of the printed circuit board is led into an electrolytic ion membrane device by a water pump for concentration and separation to obtain pure water and concentrated etching solution containing copper ions, and the quality of the pure water can be further improved by processes such as anion-cation resin mixed bed and EDI after the pure water is produced by the electrolytic ion membrane.
Step two: and (3) pure water recovery: introducing water obtained by separation of electrolytic ion membrane equipment into a pure water recovery tank;
step three: and (3) recycling pure water: introducing the pure water in the pure water recovery tank into a workshop production line by a water pump for cyclic utilization;
step four: collecting concentrated solution: and collecting the etching solution obtained by the separation in the step into a concentrated solution collecting tank.
Step five: electrolytic copper extraction: and electrolyzing the etching solution in the concentrated solution collecting pool, and extracting copper ions in the concentrated solution to obtain the available etching solution.
Step six: and (3) recycling the etching solution: and (5) reusing the etching solution prepared in the fifth step in the production of etching tanks for reuse.
Further, the cleaning wastewater in the first step is acidic etching cleaning wastewater, and the wastewater contains ammonium chloride, hydrochloric acid, sodium chlorate, sodium chloride, urea and the like.
Further, the cleaning wastewater in the first step is alkaline etching cleaning wastewater, and the wastewater contains ammonium chloride, ammonia water and the like.
Further, the ionic membrane electrolysis device in the first step is provided with a direct current electric field.
Furthermore, the ionic membrane electrolysis device in the first step is provided with an ionic membrane, ions in the wastewater pass through the ionic membrane under the action of the direct current electric field, and only water molecules are left. Thereby achieving the purpose of concentrating the etching solution.
Further, the conductivity of the pure water in the second step is lower than 10 us/cm.
Furthermore, the etching solution in the fourth step can be sold to qualified recovery units for recovery processing, so that economic benefits are realized.
Further, in the fifth step, the etching solution is electrolyzed to extract copper, elemental copper can be prepared at the cathode of the electrolytic cell through reduction reaction, and the prepared elemental copper can be recycled.
Furthermore, a jet device is arranged in the fifth step, and the soluble gas generated by electrolysis can be dissolved into the etching solution through the jet device, so that the original etching solution can be recovered.
Further, a circulating pump is further arranged in the fifth step, and the circulating pump can guide the etching liquid into the ejector.
Furthermore, the etching solution in the sixth step can be recycled to the etching tank and can also be subjected to unit recycling treatment with recycling quality.
Furthermore, the process does not add chemical raw materials, does not generate new chemical substances, realizes zero emission of wastewater recycling, realizes that the etching solution in the wastewater is concentrated by about 100 times and sold to qualified units for recycling, can also electrolyze and separate out copper through electrolytic equipment, and dissolves soluble gas generated by electrolysis, such as chlorine and the like, into the etching solution through a jet device to realize the recycling of the original etching solution.
Furthermore, the process has low treatment cost, and the separated recycled water and the separated etching solution have recycling value, so that the treatment cost close to zero can be realized.
Furthermore, the process is mainly used for treating acidic etching cleaning wastewater and can also be used for treating alkaline etching cleaning wastewater.
Furthermore, the process can also be used for treating chemical copper plating wastewater.
Compared with the prior art, the invention has the advantages and effects that: firstly, the process can realize zero-cost treatment cost, has considerable economic benefit and realizes high-level circular economy; secondly, the process does not add any chemical raw materials, does not generate any new chemical substances, realizes zero discharge of waste water and waste residue, has no pollution to the environment and has good social benefit; thirdly, the process can realize the recycling of the waste water and the etching solution and can recover copper ions in the etching solution by electrolysis; finally, the process is simple and convenient to popularize and use.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In order to achieve the above object, the technical solution of the present invention is as follows.
Referring to fig. 1, the invention provides a process for treating copper-containing cleaning wastewater generated in etching of printed circuit boards, which comprises the following steps:
the method comprises the following steps: electrolytic ion membrane treatment: and (3) introducing the printed circuit board etching cleaning wastewater containing copper ions into an electrolytic ion membrane device by using a water pump, and concentrating and separating to obtain pure water and concentrated etching solution containing copper ions.
Step two: and (3) pure water recovery: introducing water obtained by separation of electrolytic ion membrane equipment into a pure water recovery tank;
step three: and (3) recycling pure water: introducing the pure water in the pure water recovery tank into a workshop production line by using a water pump for reuse;
step four: collecting concentrated solution: and collecting the etching solution obtained by the separation in the step into a concentrated solution collecting tank.
Step five: electrolytic copper removal: and electrolyzing the etching solution in the concentrated solution collecting pool to remove copper ions in the concentrated solution to obtain the available etching solution.
Step six: and (3) recycling the etching solution: and (5) reusing the etching solution prepared in the fifth step in the production of etching tanks for reuse.
In the example, after the ion membrane is electrolyzed to produce pure water, processes such as anion-cation resin mixed bed, EDI and the like can be added to further improve the quality of the pure water.
In this example, the cleaning wastewater in the first step is acidic etching cleaning wastewater, and the wastewater includes ammonium chloride, hydrochloric acid, sodium chlorate, sodium chloride, urea, and the like.
In this example, the cleaning wastewater in the first step is alkaline etching cleaning wastewater, and the wastewater includes ammonium chloride and ammonia water as components.
In this example, the electrolytic ion membrane device in the first step is provided with a direct current electric field.
In this example, the ionic membrane electrolysis device in the first step is provided with an ionic membrane, and anions and cations in the wastewater pass through the ionic membrane under the action of the direct current electric field, and only water molecules are left. Thereby achieving the purpose of concentrating the etching solution.
In the present example, the conductivity of the pure water in the second step is less than 10 us/cm.
In this example, the etching solution in the fourth step can be sold to qualified recycling units for recycling, so as to achieve economic benefits.
In this example, the etching solution in the fifth step is electrolyzed to extract copper, so that elemental copper can be prepared at the cathode of the electrolytic cell through a reduction reaction, and the prepared elemental copper can be recycled.
In this example, a gas-liquid mixing jet device is arranged in the fifth step, and the soluble gas generated by electrolysis can be dissolved into the etching solution through the jet device, so that the original etching solution recovery is realized.
In the present example, a circulating pump is also provided in the fifth step, and the circulating pump can push the etching liquid pressure into the ejector.
In this example, the etching solution in the sixth step can be recycled to the etching tank, and can be subjected to a unit recycling treatment with recycling qualification.
In the example, the process does not add chemical raw materials, does not generate new chemical substances, realizes zero discharge of the recycled wastewater, realizes high-multiple concentration of the etching solution in the wastewater for qualified unit recycling, can also electrolyze and separate out copper through electrolytic equipment, and dissolves soluble gas generated by electrolysis, such as chlorine and the like, into the etching solution through an ejector to realize recycling of the original etching solution.
In the embodiment, the treatment cost of the process is low, the separated recycled water and the separated etching solution have recycling values, and the treatment cost close to zero can be realized.
In the example, the process is mainly used for treating acid etching cleaning wastewater and can also be used for treating alkaline etching cleaning wastewater.
In the example, the process can also be used for treating the electroless copper plating wastewater.
The above embodiments are only for illustrating the present invention, and the scope of the present invention is not limited to the above embodiments. The objectives of the present invention can be achieved by the ordinary skilled person in the art according to the disclosure of the present invention and the ranges of the parameters.
Claims (10)
1. A process for treating copper-containing etching cleaning wastewater of a printed circuit board comprises the following steps:
the method comprises the following steps: electrolytic ion membrane treatment: and (3) introducing the printed circuit board etching cleaning wastewater containing copper ions into an electrolytic ion membrane device by using a water pump, and concentrating and separating to obtain pure water and concentrated etching solution containing copper ions.
Step two: and (3) pure water recovery: introducing water obtained by separation of electrolytic ion membrane equipment into a pure water recovery tank;
step three: and (3) recycling pure water: introducing the pure water in the pure water recovery tank into a workshop production line by a water pump for cyclic utilization;
step four: collecting concentrated solution: and collecting the etching solution obtained by the separation in the step into a concentrated solution collecting tank.
Step five: electrolytic copper extraction: and electrolyzing the etching solution in the concentrated solution collecting pool, and extracting copper ions in the concentrated solution to obtain the available etching solution.
Step six: and (3) recycling the etching solution: and (5) reusing the etching solution prepared in the fifth step in the production of etching tanks for reuse.
2. The process according to claim 1, wherein the wastewater from step one is acidic etching and cleaning wastewater, and the wastewater comprises ammonium chloride, hydrochloric acid, sodium chlorate, sodium chloride, and urea.
3. The process for treating the copper-containing etching and cleaning wastewater of the printed circuit board as claimed in claim 1, wherein the cleaning wastewater in the first step is alkaline etching and cleaning wastewater, and the wastewater comprises ammonium chloride and ammonia water.
4. The process for treating wastewater generated in the etching and cleaning process of copper-containing on printed circuit board according to claim 1, wherein the ionic membrane electrolysis device in the first step is provided with a DC electric field.
5. The process for treating the copper-containing etching and cleaning wastewater of the printed circuit board as claimed in claim 1, wherein the ionic membrane electrolysis device in the first step is provided with an ionic membrane, ions in the wastewater pass through the ionic membrane under the action of the direct current electric field, and only water molecules are left. Thereby achieving the purpose of concentrating the etching solution.
6. The process for treating wastewater from copper etching and cleaning of printed circuit boards according to claim 1, wherein the conductivity of pure water in the second step is less than 10 us/cm.
7. The process for treating copper-containing etching and cleaning wastewater for printed circuit boards according to claim 1, wherein the etching solution in the fourth step can be sold to qualified recovery units for recovery treatment, thereby realizing economic benefits.
8. The process for treating the copper-containing etching cleaning wastewater for the printed circuit board as claimed in claim 1, wherein in the fifth step, the etching solution is used for electrolyzing and extracting copper, elemental copper can be prepared by reduction reaction at the cathode of the electrolytic cell, and the prepared elemental copper can be recycled.
9. The process for treating the copper-containing etching and cleaning wastewater of the printed circuit board as claimed in claim 1, wherein an ejector is arranged in the step five, and the soluble gas generated by electrolysis can be dissolved into the etching solution through the ejector to realize the recovery of the etching solution as it is.
10. The process for treating the copper-containing etching and cleaning wastewater for the printed circuit board as claimed in claim 9, wherein a circulating pump is further provided in the fifth step, and the etching solution is introduced into the ejector by using the circulating pump.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010797107.9A CN111977752A (en) | 2020-08-10 | 2020-08-10 | Treatment process for copper-containing etching cleaning wastewater of printed circuit board |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010797107.9A CN111977752A (en) | 2020-08-10 | 2020-08-10 | Treatment process for copper-containing etching cleaning wastewater of printed circuit board |
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| CN111977752A true CN111977752A (en) | 2020-11-24 |
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| CN202010797107.9A Pending CN111977752A (en) | 2020-08-10 | 2020-08-10 | Treatment process for copper-containing etching cleaning wastewater of printed circuit board |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113213590A (en) * | 2021-05-27 | 2021-08-06 | 深圳市冠融辰环保科技有限公司 | Method for treating nickel electroplating cleaning wastewater |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4051001A (en) * | 1974-08-26 | 1977-09-27 | Hitachi, Ltd. | Process for regenerating etching solution |
| CN206916218U (en) * | 2017-05-15 | 2018-01-23 | 广州致优环境工程有限公司 | A kind of circuit board acidity etching liquid recycling equipment for reclaiming |
| CN109778193A (en) * | 2019-03-24 | 2019-05-21 | 宏俐（汕头）电子科技有限公司 | Equipment for reclaiming is electroplated in etching waste liquor and reuse method is electroplated in etching waste liquor |
| CN109868476A (en) * | 2019-01-28 | 2019-06-11 | 湖北永绍科技股份有限公司 | A kind of etching liquid recycling and reusing method of copper ions and nitrate anion |
-
2020
- 2020-08-10 CN CN202010797107.9A patent/CN111977752A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4051001A (en) * | 1974-08-26 | 1977-09-27 | Hitachi, Ltd. | Process for regenerating etching solution |
| CN206916218U (en) * | 2017-05-15 | 2018-01-23 | 广州致优环境工程有限公司 | A kind of circuit board acidity etching liquid recycling equipment for reclaiming |
| CN109868476A (en) * | 2019-01-28 | 2019-06-11 | 湖北永绍科技股份有限公司 | A kind of etching liquid recycling and reusing method of copper ions and nitrate anion |
| CN109778193A (en) * | 2019-03-24 | 2019-05-21 | 宏俐（汕头）电子科技有限公司 | Equipment for reclaiming is electroplated in etching waste liquor and reuse method is electroplated in etching waste liquor |
Non-Patent Citations (2)
| Title |
|---|
| 宋志伟等 主编: "《水污染控制工程》", 31 July 2013, 中国矿业大学出版社 * |
| 张招贤等 编著: "《钛电极反应工程学》", 30 April 2009, 冶金工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113213590A (en) * | 2021-05-27 | 2021-08-06 | 深圳市冠融辰环保科技有限公司 | Method for treating nickel electroplating cleaning wastewater |
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