CN112376049A - Method for recovering acidic etching solution - Google Patents
Method for recovering acidic etching solution Download PDFInfo
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- CN112376049A CN112376049A CN202011237058.XA CN202011237058A CN112376049A CN 112376049 A CN112376049 A CN 112376049A CN 202011237058 A CN202011237058 A CN 202011237058A CN 112376049 A CN112376049 A CN 112376049A
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- acidic etching
- solution
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- oil phase
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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
-
- 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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- 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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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrolytic Production Of Metals (AREA)
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Abstract
The invention discloses a method for recovering acidic etching solution, which comprises the following steps: pretreating the acidic etching waste liquid, and adjusting the pH value of the acidic etching waste liquid to be alkaline; extracting the acidic etching waste liquid by using a solvent to obtain a copper-loaded oil phase and a first water phase; carrying out secondary extraction on the copper-loaded oil phase to obtain a second oil phase and a second water phase; adding a copper extractant into the second oil phase to obtain a loaded copper extraction liquid; electrolyzing the second water phase, and depositing copper ions in the second water phase to obtain a solution after electrodeposition and deposited copper; and adjusting the pH value of the first water phase to be neutral, and then performing membrane treatment fine adjustment or adopting a reduced pressure distillation process to form an alkaline solution. The invention has the advantages that the process flow and the management program of a printed circuit board factory are not changed, only the waste liquid is discharged into the acid etching liquid treatment and recovery system, the whole process is continuously and automatically operated, the technological content of equipment is high, and zero emission of condensation utilization is realized.
Description
Technical Field
The invention relates to the technical field of etching solution regeneration and recovery, in particular to a method for recovering acidic etching solution.
Background
In 2008, the PCB circuit board output value of China reaches 1183 hundred million, which accounts for 32 percent of the world output value, the PCB output reaches 1.50 hundred million square meters, and the PCB enterprise is the first in the world, and the PCB enterprise in China is rapidly grown up, so that the large-scale and industrialized development trend is gradually formed. However, the production value is increased, and simultaneously, the environmental pollution is caused, especially, a large amount of chemical reagents are consumed in the PCB circuit board etching process, a large amount of waste liquid and waste water are generated, wherein the liquid medicine of half PCB manufacturers adopts the acidic etching liquid in the etching process section, most PCB environment-friendly enterprises mix the acidic etching liquid with the alkaline etching liquid to precipitate copper, and industrial copper sulfate is produced through separation, so that the high-quality metal copper cannot be recycled and produced. Therefore, the project is established, various reagents in each link are recycled by recycling the waste acidic etching solution, and the project has very important significance for realizing effective utilization of resources, maximizing economic benefits and breakthrough and innovation of the PCB environmental protection technology.
At present, a plurality of units for researching and developing the waste acidic etching solution at home and abroad are provided, including a plurality of scientific research institutions and higher colleges, after the researched and developed equipment is put into trial use, the whole resource recovery cannot be achieved, the problem of waste etching solution discharge exists, the environmental pollution is serious, and the waste acidic etching solution has no popularization and practical value in the aspects of condensation utilization economic benefits of enterprises, energy conservation, emission reduction and environmental protection.
1. Compared with direct electrolysis method, the conventional electrolysis method avoids Cu in cathode region+Migrate to the anode region and reoxidize to Cu2+The configuration of small cathode and large anode is adopted, but the operation is not very convenient, a large amount of chlorine is generated in the electrolysis process, the production safety risk of the collecting device is large, the labor intensity of peripheral equipment and staff is high, and the cost of electricity charge is high.
2. Compared with a method for recycling copper etching waste liquid by adopting ion membrane electrolysis, the method is often deteriorated along with the progress of the process due to the higher requirement of the ion membrane on the use environment, so that the membrane performance is unstable, and in addition, the ion membrane is expensive. The process voltage is high and is 5V-8V, and a large amount of joule heat is generated and needs to be cooled by cooling water. In addition, the current efficiency is only 84.3%, and the possibility of chlorine evolution and hydrogen evolution is relatively high.
3. Compared with a diaphragm electrolysis method, the manufacturing of equipment is complex, cuprous ions are very easy to oxidize, an electrolysis system needs to seal an electrolysis bath by nitrogen, the electrolysis bath cannot be checked in time, and the operation is very inconvenient.
Therefore, a convenient, efficient and low-cost method for recovering acidic etching solution is needed.
Disclosure of Invention
The invention discloses a method for recovering acidic etching solution to meet the actual requirement and overcome the defects of the prior art, which comprises the following steps:
s1, pretreating the acidic etching waste liquid, and adjusting the pH value of the acidic etching waste liquid to be alkaline;
s2, extracting the acidic etching waste liquid by using a solvent to obtain a copper-loaded oil phase and a first water phase;
s3, carrying out secondary extraction on the copper-loaded oil phase to obtain a second oil phase and a second water phase;
s4, adding a copper extractant into the second oil phase to obtain a loaded copper extraction liquid;
s5, electrolyzing the second water phase, and depositing copper ions in the second water phase to obtain an electrodeposited liquid and deposited copper;
and S6, adjusting the pH value of the first water phase to be neutral, and then performing membrane treatment fine adjustment or adopting a reduced pressure distillation process to form an alkaline solution.
As a further improvement of the embodiment of the present invention, the step S6 is followed by S7 of recovering the first aqueous phase by membrane treatment fine adjustment or by vacuum distillation.
As a further improvement of the embodiment of the present invention, the vacuum distillation process specifically includes vacuum concentrating the first aqueous phase to obtain distilled water containing hydrochloric acid and a concentrated solution, cooling and crystallizing the concentrated solution, and performing solid-liquid separation to obtain a chloride solid and an acidic solution.
As a further improvement of the embodiments of the present invention, the concentrating the first aqueous phase under reduced pressure comprises first concentrating the first aqueous phase and collecting distilled water to obtain first distilled water;
concentrating the first water phase for the second time to obtain a concentrated solution, and collecting distilled water again to obtain second distilled water;
concentrating the first water phase at a vacuum degree of 0.06mPa or more and a temperature of 50-90 ℃; after the first concentration, the volume of the first aqueous phase became 1/2 of the original volume; after the second concentration, the volume of the first aqueous phase is 1/5-2/5 of the original volume.
As a further improvement of the embodiment of the invention, the method also comprises the operation of carrying out S2-S4 again on the copper-loaded extract liquor in S4.
As a further improvement of the embodiment of the invention, the step S6 further comprises adding sulfuric acid to the post-electrodeposition solution for back extraction, and performing the operations S2-S4 again on the third oil phase obtained by back extraction.
As a further improvement of the embodiment of the present invention, the step S1 of pretreating the acidic waste etching solution includes adjusting the pH of the acidic waste etching solution to between 8.0 and 8.3, and precipitating the acidic waste etching solution until the solution is transparent; and diluting the concentration of the acidic etching waste liquid by one time.
As a further improvement of the embodiment of the invention, in the step S2, the acidic etching waste liquid is extracted by using a solvent, and the volume ratio of the copper-loaded oil phase to the first water phase is 2: 1.
As a further improvement of the embodiment of the invention, in the back extraction by adding sulfuric acid into the post-electrodeposition solution, the volume ratio of the third oil phase to the sulfuric acid is 1: 1.5.
As a further improvement of the embodiment of the present invention, the specific step of electrolyzing the second aqueous phase in step S5 includes:
d, electrifying direct current to electrolyze the acidic etching waste liquid;
and (3) anode reaction: 2Cl--2e-＝Cl2；
And (3) cathode reaction: cu2++e-＝Cu+，Cu++e-＝Cu；
And the content of copper ions in the electro-deposition solution obtained after electrolyzing the acidic etching waste solution is less than 20g/L, and the acidity of HCl is 1-3N.
The invention has the following beneficial effects:
1. the invention realizes the recovery of copper by converting the acidic etching waste liquid into a suitable extraction system, selecting a suitable extracting agent and utilizing the existing mature solvent extraction film treatment-electrodeposition copper process, the raffinate can be directly changed into an alkaline etching liquid product after the components are regulated, and simultaneously, the recovery of ammonium chloride, distilled water or hydrochloric acid and a pretreatment regulator is realized by utilizing reduced pressure distillation, the technology is reliable, and the operation is simple and easy;
2. the water phase is subjected to component adjustment or reduced pressure distillation to produce ammonium chloride, sodium chloride and distilled water which can be used for preparing the alkaline etching solution, no waste is generated, and harmless treatment and waste recycling of the etching waste liquid are realized;
3. the operation process related by the invention does not generate harmful gases such as chlorine and the like finally, the production is reliable, the high-purity standard cathode copper is recycled and prepared, the added value is high, and the relative cost is low;
4. the invention also has the advantages of high automation degree, obvious economic, environmental protection and social benefits, reduces the cost of enterprises, brings obvious economic benefits, improves the competitiveness of the enterprises and lightens the environmental protection pressure of the enterprises;
5. the invention can realize 100 percent recovery and use of the membrane treatment water phase waste liquid, the recovery rate of electrolytic copper reaches 99.9 percent, the purity of the electrolytic copper reaches 99.9 percent, the process flow and the management procedure of a printed circuit board factory are not changed, and only the waste liquid needs to be discharged into an acid etching liquid treatment and recovery system; the whole process is continuously and automatically operated, the equipment technology content is high, and zero emission of condensation utilization is really realized in the online treatment of the acidic etching solution in the printed circuit board industry.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a method for recovering acidic etching solution, which aims to meet the actual requirement and overcome the defects of the prior art and comprises the following steps:
s1, pretreating the acidic etching waste liquid, and adjusting the pH value of the acidic etching waste liquid to be alkaline;
s2, extracting the acidic etching waste liquid by using a solvent to obtain a copper-loaded oil phase and a first water phase;
s3, carrying out secondary extraction on the copper-loaded oil phase to obtain a second oil phase and a second water phase;
s4, adding a copper extractant into the second oil phase to obtain a loaded copper extraction liquid;
s5, electrolyzing the second water phase, and depositing copper ions in the second water phase to obtain an electrodeposited liquid and deposited copper;
and S6, adjusting the pH value of the first water phase to be neutral, and then performing membrane treatment fine adjustment or adopting a reduced pressure distillation process to form an alkaline solution.
S7, recovering the first water phase by adopting a reduced pressure distillation process; in other alternative embodiments, membrane treatment fine tuning may also be employed for the first aqueous phase recovery.
In the embodiment of the invention, the reduced pressure distillation process specifically comprises the steps of carrying out reduced pressure concentration on the first water phase to obtain distilled water containing hydrochloric acid and concentrated solution, cooling and crystallizing the concentrated solution, and carrying out solid-liquid separation to obtain chloride solid and acidic solution.
Specifically, the vacuum concentration of the first aqueous phase comprises first concentrating the first aqueous phase, and collecting distilled water to obtain first distilled water;
concentrating the first water phase for the second time to obtain a concentrated solution, and collecting distilled water again to obtain second distilled water;
concentrating the first water phase at a vacuum degree of 0.06mPa or higher and at a temperature of 50-90 ℃; after the first concentration, the volume of the first aqueous phase became 1/2; after the second concentration, the volume of the first aqueous phase was 1/5-2/5 of the original volume.
In the present example, the operations of S2-S4 were again performed on the copper-loaded extract in S4. And specifically comprises extracting the obtained copper-loaded extract again with solvent to obtain copper-loaded oil phase and first water phase;
re-extracting the loaded copper oil phase obtained in the second time to obtain a second oil phase and a second water phase again; and adding a copper extractant into the second oil phase to obtain a loaded copper extraction liquid.
In other alternative embodiments, step S6 is followed by adding sulfuric acid to the post-electrodeposition solution for back-extraction, and the third oil phase obtained by back-extraction is again subjected to operations S2-S4; and adding sulfuric acid into the solution after electrodeposition for back extraction, wherein the volume ratio of the third oil phase to the sulfuric acid is 1: 1.5.
In the embodiment of the present invention, the step S1 of pretreating the waste acidic etching solution includes adjusting the pH of the waste acidic etching solution to 8.0-8.3, and precipitating the waste acidic etching solution until the solution is transparent; and diluting the concentration of the acidic etching waste liquid by one time.
Wherein, in S2, the acidic etching waste liquid is extracted by a solvent, and the volume ratio of the loaded copper oil phase to the first water phase is 2: 1.
The specific step of electrolyzing the second aqueous phase in step S5 includes:
d, electrifying direct current to electrolyze the acidic etching waste liquid;
and (3) anode reaction: 2Cl--2e-＝Cl2；
And (3) cathode reaction: cu2++e-＝Cu+，Cu++e-＝Cu；
And the content of copper ions in the electro-deposition solution obtained after electrolyzing the acidic etching waste solution is less than 20g/L, and the acidity of HCl is 1-3N.
The invention has the following beneficial effects:
1. the invention realizes the recovery of copper by converting the acidic etching waste liquid into a suitable extraction system, selecting a suitable extracting agent and utilizing the existing mature solvent extraction film treatment-electrodeposition copper process, the raffinate can be directly changed into an alkaline etching liquid product after the components are regulated, and simultaneously, the recovery of ammonium chloride, distilled water or hydrochloric acid and a pretreatment regulator is realized by utilizing reduced pressure distillation, the technology is reliable, and the operation is simple and easy;
2. the water phase is subjected to component adjustment or reduced pressure distillation to produce ammonium chloride, sodium chloride and distilled water which can be used for preparing the alkaline etching solution, no waste is generated, and harmless treatment and waste recycling of the etching waste liquid are realized;
3. the operation process related by the invention does not generate harmful gases such as chlorine and the like finally, the production is reliable, the high-purity standard cathode copper is recycled and prepared, the added value is high, and the relative cost is low;
4. the invention also has the advantages of high automation degree, obvious economic, environmental protection and social benefits, reduces the cost of enterprises, brings obvious economic benefits, improves the competitiveness of the enterprises and lightens the environmental protection pressure of the enterprises;
5. the invention can realize 100 percent recovery and use of the membrane treatment water phase waste liquid, the recovery rate of electrolytic copper reaches 99.9 percent, the purity of the electrolytic copper reaches 99.9 percent, the process flow and the management procedure of a printed circuit board factory are not changed, and only the waste liquid needs to be discharged into an acid etching liquid treatment and recovery system; the whole process is continuously and automatically operated, the equipment technology content is high, and zero emission of condensation utilization is really realized in the online treatment of the acidic etching solution in the printed circuit board industry.
The above is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the inventive concept of the present invention, which falls into the protection scope of the present invention.
Claims (10)
1. The method for recovering the acidic etching solution is characterized by comprising the following steps of:
s1, pretreating the acidic etching waste liquid, and adjusting the pH value of the acidic etching waste liquid to be alkaline;
s2, extracting the acidic etching waste liquid by using a solvent to obtain a copper-loaded oil phase and a first water phase;
s3, carrying out secondary extraction on the copper-loaded oil phase to obtain a second oil phase and a second water phase;
s4, adding a copper extractant into the second oil phase to obtain a loaded copper extraction liquid;
s5, electrolyzing the second water phase, and depositing copper ions in the second water phase to obtain an electrodeposited liquid and deposited copper;
and S6, adjusting the pH value of the first water phase to be neutral, and then performing membrane treatment fine adjustment or adopting a reduced pressure distillation process to form an alkaline solution.
2. The method as claimed in claim 1, wherein the step S6 is followed by S7 of recovering the first aqueous phase, and the recovering of the first aqueous phase is performed by membrane fine adjustment or vacuum distillation.
3. The method for recovering acidic etching solution according to claim 2, wherein the vacuum distillation process specifically comprises the steps of carrying out vacuum concentration on the first aqueous phase to obtain distilled water containing hydrochloric acid and a concentrated solution, cooling and crystallizing the concentrated solution, and carrying out solid-liquid separation to obtain a chloride solid and an acidic solution.
4. The method according to claim 3, wherein the concentrating the first aqueous phase under reduced pressure comprises first concentrating the first aqueous phase and collecting distilled water to obtain first distilled water;
concentrating the first water phase for the second time to obtain a concentrated solution, and collecting distilled water again to obtain second distilled water;
concentrating the first water phase at a vacuum degree of 0.06mPa or more and a temperature of 50-90 ℃; after the first concentration, the volume of the first aqueous phase became 1/2 of the original volume; after the second concentration, the volume of the first aqueous phase is 1/5-2/5 of the original volume.
5. The method for recovering acidic etching solution according to claim 1, further comprising the step of performing operations S2-S4 again on the copper-loaded extract in S4.
6. The method for recycling acidic etching solution according to claim 1, further comprising, after the step S6, adding sulfuric acid into the post-electrodeposition solution for back-extraction, and performing the operations S2-S4 on the back-extracted third oil phase again.
7. The method for recycling acidic etching solution according to claim 1, wherein the step S1 of pretreating the acidic etching waste solution comprises adjusting the pH of the acidic etching waste solution to 8.0-8.3, and precipitating the acidic etching waste solution until the solution is transparent; and diluting the concentration of the acidic etching waste liquid by one time.
8. The method for recovering acidic etching solution according to claim 1, wherein the acidic etching waste solution is extracted with a solvent in S2 to obtain a copper-loaded oil phase and a first aqueous phase at a volume ratio of 2: 1.
9. The method for recovering acidic etching solution according to claim 6, wherein in the back extraction by adding sulfuric acid into the post-electrodeposition solution, the volume ratio of the third oil phase to sulfuric acid is 1: 1.5.
10. The method for recovering acidic etching solution according to claim 5, wherein the step S5 of electrolyzing the second aqueous phase comprises:
d, electrifying direct current to electrolyze the acidic etching waste liquid;
and (3) anode reaction: 2Cl--2e-＝Cl2；
And (3) cathode reaction: cu2++e-＝Cu+，Cu++e-＝Cu；
And the content of copper ions in the electro-deposition solution obtained after electrolyzing the acidic etching waste solution is less than 20g/L, and the acidity of HCl is 1-3N.
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| CN202011237058.XA CN112376049A (en) | 2020-11-09 | 2020-11-09 | Method for recovering acidic etching solution |
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| CN202011237058.XA CN112376049A (en) | 2020-11-09 | 2020-11-09 | Method for recovering acidic etching solution |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115193076A (en) * | 2021-04-14 | 2022-10-18 | 中国科学院过程工程研究所 | Method for separating and recovering oil and copper from oil-containing copper material |
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| CN108624885A (en) * | 2017-08-07 | 2018-10-09 | 鲁铭 | A kind of spent acid and the method for alkaline etching liquid processing |
| CN108914129A (en) * | 2018-08-24 | 2018-11-30 | 德雅（深圳）环境科技有限公司 | A kind of alkaline etching liquid indirect regeneration and its method |
| CN111635994A (en) * | 2020-06-15 | 2020-09-08 | 四川大学 | Method for recovering copper from acidic copper-containing etching solution and preparing cuprous oxide |
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2020
- 2020-11-09 CN CN202011237058.XA patent/CN112376049A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101693997A (en) * | 2009-09-30 | 2010-04-14 | 深圳市洁驰科技有限公司 | Method for processing acidic etching waste solution of printed circuit board |
| CN102251244A (en) * | 2011-07-13 | 2011-11-23 | 重庆浩康医药化工集团有限公司 | Cyclic regeneration and copper extraction process for printed circuit board etching waste solution |
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| CN111635994A (en) * | 2020-06-15 | 2020-09-08 | 四川大学 | Method for recovering copper from acidic copper-containing etching solution and preparing cuprous oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115193076A (en) * | 2021-04-14 | 2022-10-18 | 中国科学院过程工程研究所 | Method for separating and recovering oil and copper from oil-containing copper material |
| CN115193076B (en) * | 2021-04-14 | 2024-01-30 | 中国科学院过程工程研究所 | Method for separating and recycling oil and copper from oil-containing copper material |
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