CN202945326U - Acidic waste etching solution recycling system - Google Patents
Acidic waste etching solution recycling system Download PDFInfo
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- CN202945326U CN202945326U CN2012203518273U CN201220351827U CN202945326U CN 202945326 U CN202945326 U CN 202945326U CN 2012203518273 U CN2012203518273 U CN 2012203518273U CN 201220351827 U CN201220351827 U CN 201220351827U CN 202945326 U CN202945326 U CN 202945326U
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- liquid
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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
The utility model discloses an acidic waste etching solution recycling system. The system is used for recycling the waste etching solution to generate a recycled solution by using an electrochemical method. The system comprises an electrolytic cell divided into an anode chamber and a cathode chamber by a cation exchange membrane; the acidic waste etching solution is cyclically imported into the cathode chamber; the anode chamber is communicated with an anode solution circulating tank through a pipe; the cathode chamber is communicated with a cathode solution circulating tank through a pipe; and the cathode solution circulating tank is used for importing the acidic waste etching solution from a waste etching solution storage tank through a pipe and exporting the recycled solution from the cathode chamber into a recycled solution storage tank. By adopting the acidic waste etching solution recycling system, the acidic waste etching solution is ensured to be recycled, metal copper can be recycled simultaneously, no chlorine is separated out in an electrolytic recycling process, no waste solution is discharged, and economical purpose and environmental protection are achieved.
Description
Technical field
The utility model relates to the trade effluent environmental protection treatment and metallic copper reclaims the field, especially, relates to a kind of regeneration recovery system of acidic etching waste liquid.
Background technology
at printed electronic circuit, in the industry such as electronics and Metal Finishing, acid etching has a wide range of applications, it mainly contains the iron trichloride etching solution, sulfuric acid/hydrogen peroxide system etching solution, the acid copper chloride etching liquid three types, acidic copper chloride system etching solution is existing use etching solution the most widely, the outer etching of the internal layer of its applicable wiring board and positive method, increase along with height precise refinement circuit and high-layer printed board output, the waste liquid amount that the printed board acid etching produces will increase greatly, therefore increased the load to surrounding enviroment, serious harm operator's health, research and develop a kind of recovery method without any discharging of waste liquid recycling and device, have fabulous economic benefit and environmental benefit.
The regeneration of the old liquid of acid etching mainly changes it acidic solution of suitable proportion, transparent and high redox potential into by chemistry, electrochemical method, to keep printed electronic circuit stability of plates, etching fast.Wherein chemical regeneration is the main method of acid copper chloride etching liquid regeneration, its principle is by discharging the old liquid of a certain proportion of etching (high specific gravity), add a certain amount of sub-liquid (low-gravity), perhaps adding a certain amount of water, regulate the proportion of etching solution, the oxygenant in sub-liquid is with H simultaneously
2CuCl
3Be oxidized to H
2CuCl
4, perhaps add separately oxygenant, improve the etching solution redox potential, thereby recover original performance of etching solution.Common oxygenant has air, oxygen, chlorine, ozone, clorox, sodium chlorate, hydrogen peroxide etc.But total copper constantly increases, and the acidic etching liquid that finally needs externally to get rid of a part is to keep certain total copper concentration, and not only contaminate environment, also can cause the waste of a large amount of copper and acid; Electrochemical regeneration is a kind of online renovation process, not only makes etching solution recover original etching usefulness, and the metallic copper of output with commercial value simultaneously, is the main method that acidic etching liquid is reclaimed in regeneration at present.
At present, published acidic etching liquid electrolytic regeneration method mainly contains based on anodic oxidation Cu in etching solution
+Be oxidized to Cu
2+The electrolytic regeneration recovery method, perhaps analyse by anode the regeneration that oxygenant that chlorine produces promotes etching solution.
Publication number is copper recovery system and the etching solution regeneration method that the patent documentation of CN101748430A discloses a kind of acidic etching waste liquid, two chambers membrane electrolyser that the method adopts anolyte compartment and cathode compartment to consist of, take acidic etching waste liquid as anolyte, pass through anodic oxidation reactions, to enter the regenerating waste acidic etching liquid of anolyte compartment, deposit copper powder simultaneously in cathode compartment.This device needs the configuration equipment for separating liquid from solid, reclaims the copper operation easier large, in addition, and Cu in anolyte
+When quantity reduces, can separate out chlorine at anode, serious threat has increased the difficulty of vent gas treatment to personal security.
Publication number is the method and apparatus that the patent documentation of CN101768742A discloses a kind of regenerated acidic etching solution and recovery copper, electrolyzer in electrochemical treatment is divided into anolyte compartment, intermediate chamber and cathode compartment, for fear of producing chlorine at anode, hold dilute sulphuric acid in the anolyte compartment, hold copper-bath at cathode compartment, acidic etching waste liquid directly enters intermediate chamber, after energising, cupric ion at intermediate chamber enters into cathode compartment by cationic exchange membrane, precipitating metal on negative plate.Although fine the separating out of solving chlorine of this device, but between chamber and chamber in base exchange process, the preferential copper ion migration of hydrogen ion meeting, therefore can not guarantee the balance of cathode compartment cupric ion, this structure can cause interpole gap increase between anode and cathode simultaneously, increase the electrodeposition power consumption, the cost that complicated structure also can increasing device.
The utility model content
The utility model purpose be to provide a kind of simple in structure, reclaim when regenerating waste acidic etching liquid is reclaimed in metallic copper and electrolytic regeneration process and do not separate out chlorine, regeneration recovery system without the acidic etching waste liquid of discharging of waste liquid, separate out chlorine harm environment with the system's electrolytic regeneration process that solves acidity etching liquid recycling, thus the technical problem that perhaps the cathode compartment cupric ion is uneven, interpole gap increases power consumption and cost between anode and cathode.
For achieving the above object, the utility model provides a kind of regeneration recovery system of acidic etching waste liquid, be used for acidic etching waste liquid is regenerated as regenerated liquid by electrochemical method, comprise the electrolyzer that the anolyte compartment of being separated by cationic exchange membrane and cathode compartment form, the described cathode compartment of described acidic etching waste liquid circulation importing; Described anolyte compartment is communicated with the anolyte circulation groove by pipeline; Described cathode compartment is communicated with the catholyte circulation groove by pipeline, and described catholyte circulation groove imports described acidic etching waste liquid from the etching waste liquor storage tanks by pipeline, and the regenerated liquid that described cathode compartment is produced exports to the regenerated liquid storage tanks.
Further improvement as said system:
Regenerated liquid in described regenerated liquid storage tanks by the regenerated liquid auto-scheduling system be deployed into meet the sub-liquid of regeneration that etch process requires after, import in the sub-liquid storage tanks of regeneration, the sub-liquid of regeneration in the sub-liquid storage tanks of described regeneration adds in etching machine by the sub-liquid added automatically system of regenerating, and the sub-liquid added automatically system of described regenerated liquid auto-scheduling system and described regeneration is by automatic controlling system.
Described anolyte compartment comprises a plurality of anode seed cells of being separated by cationic exchange membrane.
Be provided with positive plate in described anolyte compartment, be provided with negative plate in described cathode compartment, described positive plate and negative plate respectively with the positive pole of direct supply and negative pole electrical connection, described positive plate is the insoluble anode plate.Described insoluble anode plate is coated anode plate or chloride plate, and described negative plate is the negative plate that the titanium material is made.
Described cationic exchange membrane is poly cationic exchange membrane or tetrafluoroethylene cationic exchange membrane.
The utlity model has following beneficial effect:
1, the regeneration recovery system of acidic etching waste liquid of the present utility model can realize that regenerating waste acidic etching liquid reclaims and the synchronous metallic copper that reclaims.Electrolyzer adopts cationic exchange membrane to separate anolyte compartment and cathode compartment, makes the chlorion in acidic etching liquid can't enter the anolyte compartment, has prevented the generation of chlorine in the electrolytic process, both for safety in production provides safeguard, can not produce topsoil again.The catholyte circulation groove is set and with itself and etching waste liquor storage tanks and regenerated liquid storage tanks unilaterally connected, makes native system not need and the etching machine synchronous production, coincidence system plate factory discontinuous production requirement more.
2, the regeneration recovery system of acidic etching waste liquid of the present utility model, by automatic controlling system regenerated liquid auto-scheduling system and the sub-liquid added automatically system work of described regeneration, make final formation: the automatic circulating system of etching machine → etching waste liquor storage tanks → catholyte circulation groove (electrochemical reaction the regeneration) → sub-liquid storage tanks of regenerated liquid storage tanks → regenerated liquid auto-scheduling system → regeneration → sub-liquid added automatically system → etching machine of regeneration, complete the automatic on-line regeneration of acidic etching waste liquid.
Except purpose described above, feature and advantage, the utility model also has other purpose, feature and advantage.The below is described in further detail the utility model with reference to figure.
Description of drawings
The accompanying drawing that consists of the application's a part is used to provide further understanding of the present utility model, and illustrative examples of the present utility model and explanation thereof are used for explaining the utility model, do not consist of improper restriction of the present utility model.In the accompanying drawings:
Fig. 1 is the principle of work schematic diagram of regeneration recovery system of the acidic etching waste liquid of the utility model preferred embodiment;
Fig. 2 is the structural representation of regeneration recovery system of the acidic etching waste liquid of the utility model preferred embodiment.
Marginal data:
1, electrolyzer; 2, cationic exchange membrane; 3, anolyte compartment; 4, cathode compartment; 5, positive plate; 6, negative plate.
Embodiment
Below in conjunction with accompanying drawing, embodiment of the present utility model is elaborated, but the multitude of different ways that the utility model can be defined by the claims and cover is implemented.
Referring to Fig. 1, Fig. 2, the regeneration recovery system of acidic etching waste liquid of the present utility model, be used for acidic etching waste liquid is regenerated as regenerated liquid by electrochemical method, comprise the electrolyzer 1 that the anolyte compartment 3 of being separated by cationic exchange membrane 2 and cathode compartment 4 form, acidic etching waste liquid circulation importing cathode compartment 4.
In the present embodiment, anolyte compartment 3 is communicated with the anolyte circulation groove by pipeline; Cathode compartment 4 is communicated with the catholyte circulation groove by pipeline, and the catholyte circulation groove imports acidic etching waste liquid by pipeline from the etching waste liquor storage tanks, and the regenerated liquid that cathode compartment 4 is produced exports to the regenerated liquid storage tanks.Regenerated liquid in the regenerated liquid storage tanks by the regenerated liquid auto-scheduling system be deployed into meet the sub-liquid of regeneration that etch process requires after, import in the sub-liquid storage tanks of regeneration, the sub-liquid of regeneration of regenerating in sub-liquid storage tanks adds in etching machine by the sub-liquid added automatically system of regenerating, regenerated liquid auto-scheduling system and the sub-liquid added automatically system of regeneration are controlled by the automatic control system (not shown), and automatic control system is realized by PLC.
In actual the use, anolyte compartment 3 can be comprised of a plurality of anode seed cells of being separated by cationic exchange membrane 2.Be provided with positive plate 5 in anolyte compartment 3, be provided with negative plate 6 in cathode compartment 4, positive plate 5 and negative plate 6 respectively with the positive pole of direct supply and negative pole electrical connection.The general insoluble anode plate that adopts of positive plate 5 can be coated anode plate or chloride plate.Negative plate 6 generally is adopted as the negative plate that the titanium material is made.
Adopt the regeneration recovery system of above-mentioned acidic etching waste liquid to carry out acidic etching liquid regeneration recovery, concrete steps are as follows:
1, adopt polyethylene cationic exchange membrane (the polyethylene cationic exchange membrane is existing material) that electrolyzer 1 is separated and be cathode compartment 4 and many groups anolyte compartment 3.
2, add the 2mol/L sulphuric acid soln in anolyte compartment 3 and anode circulation groove;
3, acidic etching waste liquid is imported to the cathode compartment 4 of negative electrode circulation groove and electrolyzer 1 from the etching waste liquor storage tanks;
4, add hydrochloric acid or water dilution catholyte and make the total concn of cupric ion and cuprous ion be controlled at 30g/L, pH concentration control is at 1mol/L.
5, electrolysis temperature is controlled at 30 ℃～35 ℃; Current density is controlled at 300A/m
2After electrolysis 10 hours, when in catholyte, hydrogen ion concentration rises to 4mol/L, the catholyte circulation groove is directed into the regenerated liquid storage tanks with the regenerated liquid that overflows, import in the sub-liquid circulation groove of regeneration after adding a small amount of additive by the regenerated liquid auto-scheduling system, the sub-liquid of regeneration in the sub-liquid storage tanks of regenerating adds to recycle in etching machine by the sub-liquid added automatically system of regenerating.Simultaneously, according to the timely anode of liquid level situation chamber 3 make up water of anolyte circulation groove to former liquid level height.
6, electrolysis after 48 hours, is taken out the copper-stripping that will be deposited on negative electrode with negative plate 6.
Get the copper of above-mentioned gained and test, the purity that can get copper is 99.5%.System power efficient is 85%, in whole regeneration removal process, has kept the material balance of whole etching solution system.
Referring to Fig. 1, the principle of above-mentioned electrochemical reaction is as follows:
Anode: 2OH
--2e → H
2O+1/2O
2↑; (1)
Negative electrode: Cu
++ 2e → Cu; (2)
Cu
2++e→Cu； （3）
2H
++2e→H
2↑。（4）
Above-mentioned electrochemical treatment need keep material balance, namely keeps the balance of copper, hydrogen ion, chlorion.Be specially: as shown in Figure 1, in electrochemical treatment process, anolyte in anolyte compartment 3 is sulfuric acid system, consume on the one hand hydroxide ion (referring to reaction formula (1)) by anodic reaction, the hydrogen ion that produces on the other hand enters into the catholyte of cathode compartment 4 by cationic exchange membrane 2, kept hydrionic balance in catholyte.In above-mentioned electrochemical treatment process, because the chlorion in catholyte can't enter into anolyte compartment 3 by cationic exchange membrane 2, therefore can not produce chlorine, chlorion (Cl
-) kept stable in catholyte.Catholyte constantly increases because of hydrionic constantly the moving in anolyte compartment 3, for the hydrogen ion that consumes in etching process provides the source, when being increased to a certain degree, can follow negative electrode side reaction releasing hydrogen gas (referring to reaction formula (4)) to reach a running balance.The cupric ion of cathode compartment 4 constantly becomes copper (referring to reaction formula (2), reaction formula (3)) at negative plate 6 surface depositions with cuprous ion, metallic copper and the etched balance of copper of etching machine that the balance of copper needs the electrolysis cathode deposition to reclaim, cuprous ion is preferentially separated out at negative electrode simultaneously, has guaranteed the recovery of regenerated liquid redox potential.
To sum up, the utility model can reclaim regenerating waste acidic etching liquid, and can synchronously reclaim metallic copper, and does not separate out chlorine in the electrolytic regeneration process, without discharging of waste liquid, and economic environmental protection; And the current efficiency of system is high, and the purity that reclaims copper is high.
The above is only preferred embodiment of the present utility model, is not limited to the utility model, and for a person skilled in the art, the utility model can have various modifications and variations.All within spirit of the present utility model and principle, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection domain of the present utility model.
Claims (6)
1. the regeneration recovery system of an acidic etching waste liquid, be used for acidic etching waste liquid is regenerated as regenerated liquid by electrochemical method, it is characterized in that, comprise the electrolyzer (1) that the anolyte compartment (3) of being separated by cationic exchange membrane (2) and cathode compartment (4) form, the described acidic etching waste liquid importing described cathode compartment (4) that circulates; Described anolyte compartment (3) is communicated with the anolyte circulation groove by pipeline; Described cathode compartment (4) is communicated with the catholyte circulation groove by pipeline, and described catholyte circulation groove imports described acidic etching waste liquid from the etching waste liquor storage tanks by pipeline, and the regenerated liquid that described cathode compartment (4) is produced exports to the regenerated liquid storage tanks.
2. regeneration recovery system according to claim 1, it is characterized in that, regenerated liquid in described regenerated liquid storage tanks by the regenerated liquid auto-scheduling system be deployed into meet the sub-liquid of regeneration that etch process requires after, import in the sub-liquid storage tanks of regeneration, the sub-liquid of regeneration in the sub-liquid storage tanks of described regeneration adds in etching machine by the sub-liquid added automatically system of regenerating, and the sub-liquid added automatically system of described regenerated liquid auto-scheduling system and described regeneration is by automatic controlling system.
3. regeneration recovery system according to claim 2, is characterized in that, described anolyte compartment (3) comprise a plurality of anode seed cells of being separated by cationic exchange membrane (2).
4. the described regeneration recovery system of any one according to claim 1 to 3, it is characterized in that, be provided with positive plate (5) in described anolyte compartment (3), be provided with negative plate (6) in described cathode compartment (4), described positive plate (5) and negative plate (6) respectively with the positive pole of direct supply and negative pole electrical connection, described positive plate (5) is the insoluble anode plate.
5. the regeneration recovery system described according to claim 4, is characterized in that, described insoluble anode plate is coated anode plate or chloride plate, the negative plate that described negative plate (6) is made for the titanium material.
6. regeneration recovery system according to claim 5, is characterized in that, described cationic exchange membrane (2) is polyethylene cationic exchange membrane or tetrafluoroethylene cationic exchange membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012203518273U CN202945326U (en) | 2012-07-19 | 2012-07-19 | Acidic waste etching solution recycling system |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012203518273U CN202945326U (en) | 2012-07-19 | 2012-07-19 | Acidic waste etching solution recycling system |
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| Publication Number | Publication Date |
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| CN202945326U true CN202945326U (en) | 2013-05-22 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104630825A (en) * | 2015-01-20 | 2015-05-20 | 昆山美源达环保科技有限公司 | Device and process for electrolytically extracting copper in acidic etching liquid |
| CN105177584A (en) * | 2015-09-09 | 2015-12-23 | 成都虹华环保科技股份有限公司 | Acidic waste etching solution cyclic regeneration system with regenerated liquid treatment function |
| CN106167915A (en) * | 2016-08-30 | 2016-11-30 | 广东成德电子科技股份有限公司 | A kind of regeneration recovery method of electrochemistry acidic etching liquid used for printed circuit board |
| CN104451770B (en) * | 2014-12-20 | 2017-01-11 | 井冈山大学 | Combined resource utilization method and device of brownification waste liquid and microetching waste liquid |
| CN108531914A (en) * | 2018-06-15 | 2018-09-14 | 哈尔滨工业大学深圳研究生院 | A kind of H2SO4/S2O82-The copper of microetch waste liquid recycles and synchronizing regeneration micro etching solution system and method |
| CN108796545A (en) * | 2017-05-05 | 2018-11-13 | 深圳市憬泰晖科技有限公司 | The method of circuit board acidic etching liquid electrolytic regeneration hydrochloric acid |
| CN108893742A (en) * | 2018-07-17 | 2018-11-27 | 深圳市祺鑫天正环保科技有限公司 | Acidic etching waste liquid processing and reclaiming system |
| CN111304657A (en) * | 2019-02-12 | 2020-06-19 | 叶旖婷 | Method for electrolyzing and recycling alkaline etching waste liquid |
| CN111394726A (en) * | 2019-09-10 | 2020-07-10 | 长沙利洁环保科技有限公司 | Acid etching solution recycling process |
| CN111809184A (en) * | 2020-07-15 | 2020-10-23 | 深圳市祺鑫环保科技有限公司 | Method for recycling regenerated seed liquid |
| CN113774430A (en) * | 2021-09-15 | 2021-12-10 | 广东德同环保科技有限公司 | Equipment and method for electrolyzing acidic etching solution without chlorine gas |
-
2012
- 2012-07-19 CN CN2012203518273U patent/CN202945326U/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104451770B (en) * | 2014-12-20 | 2017-01-11 | 井冈山大学 | Combined resource utilization method and device of brownification waste liquid and microetching waste liquid |
| CN104630825A (en) * | 2015-01-20 | 2015-05-20 | 昆山美源达环保科技有限公司 | Device and process for electrolytically extracting copper in acidic etching liquid |
| CN105177584A (en) * | 2015-09-09 | 2015-12-23 | 成都虹华环保科技股份有限公司 | Acidic waste etching solution cyclic regeneration system with regenerated liquid treatment function |
| CN106167915A (en) * | 2016-08-30 | 2016-11-30 | 广东成德电子科技股份有限公司 | A kind of regeneration recovery method of electrochemistry acidic etching liquid used for printed circuit board |
| CN108796545A (en) * | 2017-05-05 | 2018-11-13 | 深圳市憬泰晖科技有限公司 | The method of circuit board acidic etching liquid electrolytic regeneration hydrochloric acid |
| CN108531914A (en) * | 2018-06-15 | 2018-09-14 | 哈尔滨工业大学深圳研究生院 | A kind of H2SO4/S2O82-The copper of microetch waste liquid recycles and synchronizing regeneration micro etching solution system and method |
| CN108893742A (en) * | 2018-07-17 | 2018-11-27 | 深圳市祺鑫天正环保科技有限公司 | Acidic etching waste liquid processing and reclaiming system |
| CN111304657A (en) * | 2019-02-12 | 2020-06-19 | 叶旖婷 | Method for electrolyzing and recycling alkaline etching waste liquid |
| CN111304657B (en) * | 2019-02-12 | 2023-08-15 | 叶旖婷 | Method for electrolytic recycling of alkaline etching waste liquid |
| CN111394726A (en) * | 2019-09-10 | 2020-07-10 | 长沙利洁环保科技有限公司 | Acid etching solution recycling process |
| CN111394726B (en) * | 2019-09-10 | 2021-01-19 | 长沙利洁环保科技有限公司 | Acid etching solution recycling process |
| CN111809184A (en) * | 2020-07-15 | 2020-10-23 | 深圳市祺鑫环保科技有限公司 | Method for recycling regenerated seed liquid |
| CN113774430A (en) * | 2021-09-15 | 2021-12-10 | 广东德同环保科技有限公司 | Equipment and method for electrolyzing acidic etching solution without chlorine gas |
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| C14 | Grant of patent or utility model | ||
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Granted publication date: 20130522 Termination date: 20200719 |
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| CF01 | Termination of patent right due to non-payment of annual fee |