CN100494500C - Method for simultaneous electrolysis and regeneration of acid etching solution and micro-etching solution - Google Patents
Method for simultaneous electrolysis and regeneration of acid etching solution and micro-etching solution Download PDFInfo
- Publication number
- CN100494500C CN100494500C CNB2006100620866A CN200610062086A CN100494500C CN 100494500 C CN100494500 C CN 100494500C CN B2006100620866 A CNB2006100620866 A CN B2006100620866A CN 200610062086 A CN200610062086 A CN 200610062086A CN 100494500 C CN100494500 C CN 100494500C
- Authority
- CN
- China
- Prior art keywords
- micro
- etching solution
- etching
- etching liquid
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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 invention relates to a method for electrolysis regenerating acid etching liquid and micro-etching liquid. The anode chamber (11) and the cathode chamber (12) are separated by the cation-exchange membrane. The reservoir of the acid etching liquid containing hydrochloric acid and chloratum culture-medium (17) is connected with the anode chamber (11). The reservoir of micr0-etching liquid containing ammonium persulfate and sulphuric acid is connected with the cathode chamber (12). During the electrolysis reaction, ammonium sulfate formed in the anode chamber (11) by micr0-etching reaction is oxidized to regenerate to ammonium persulfate, meanwhile, divalent copper ions pass through the cation-exchange membrane into the cathode chamber (12), univalent copper ions formed in the cathode chamber (12) through etching reaction is reduced to copper, and divalent copper ions return to acid etching liquid reservoir (17). The technological effects of the invention are: making full use of anode electric energy, copper resource, no creation of pollution and waste, and improving the quality of micro-etching and etching.
Description
Technical field the present invention relates to the chemical method etching technique of metallic substance, particularly relates to the regeneration techniques of the etch combination that etch copper uses.
The background technology electronic industry is used to cooperate components and parts to lay used printed circuit board (PCB), generally is to form specific wiring pattern by the Copper Foil that etching is overlying on the insulating material.Etching solution adopts the mixed solution of cupric chloride and hydrochloric acid usually, by the acid in the etching solution Copper Foil is corroded and copper ion releasing.Carry out along with etched, copper ion concentration rises, and acid reduces because of consumption concentration.Therefore, etching solution is through after a while, etch effect worse and worse, the etching solution that must more renew, and the depleted etching solution will cause environmental pollution.In the prior art, in order to prevent to produce the depleted etching solution, the acidic etching liquid electrolytic regeneration is one of solution preferably.For example publication number for the spy opens flat 10-18062, name be called " etching solution renovation process, etching solution regenerating unit and etching system " Japanese Patent Application Publication a kind of like this technical scheme: adopt perfluorocarbon resin cationic exchange membrane that electrolyzer is divided into anolyte compartment and cathode compartment, negative electrode adopts copper coin, and anode adopts titanium to be coated with the platinum family oxide coating.The liquid of cathode compartment is high density chlorination copper and trace salt acid solution, and the anolyte compartment is 5% sulphuric acid soln.By electrolysis, cupric ion is reduced into metallic copper at cathode compartment, oxidized generation oxygen of the Zhong Shui of anolyte compartment and hydrogen ion, and hydrogen ion enters cathode compartment by cationic exchange membrane and the chlorion reaction generates hydrochloric acid.Whole process has realized electrolytic regeneration.But this technical scheme has the following disadvantages: anodic reaction produces useless oxygen and enters in the air, has wasted the electric energy of this part.
The microetch operation is arranged in the production process of printed circuit board (PCB) one, is with micro-etching solution copper face to be carried out microetch to handle, and makes copper face form the micro-rough face and is beneficial to improve the bonding force of copper face between the coating of following electroplating work procedure.Described micro-etching solution contains 3% sulfuric acid, 10% ammonium persulphate.Carry out along with etched, copper ion concentration constantly rises, and ammonium persulphate concentration constantly descends.When the copper ion concentration in the micro-etching solution rose to 20g/l, ammonium persulphate had nearly all changed ammonium sulfate into.The way of prior art be with invalid micro-etching solution as wastewater treatment, so not only waste the copper resource, increase cost of water treatment, and ammonium sulfate makes the waste water eutrophication after entering waste water, favourable breeding bacterium makes water body smelly.
The summary of the invention the technical problem to be solved in the present invention is to avoid above-mentioned the deficiencies in the prior art part and the method that proposes a kind of while electrolytic regeneration acidic etching liquid and micro-etching solution, in the anolyte compartment, ammonium sulfate in the micro-etching solution is oxidized to ammonium persulphate, return the microetch liquid bath and use the cupric ion Cu in the micro-etching solution
2+Enter cathode compartment by cationic membrane, replenish, thereby realize anode regeneration micro-etching solution, the anode electric energy is made full use of as the effective constituent in the acidic etching liquid.At cathode compartment, the Cu in the acidic etching liquid
+Preferentially become copper to be reclaimed, Cu in cathodic reduction
2+Be not reduced, use but return the acid etching liquid bath.
The present invention solve the technical problem can be by realizing by the following technical solutions:
Propose the method for a kind of while electrolytic regeneration acidic etching liquid and micro-etching solution, be included in the electrolyzer that acid resisting material makes, anolyte compartment and cathode compartment are separated with cationic exchange membrane; Acidic etching liquid stationary tank and described cathode compartment are communicated with, and described acidic etching liquid comprises hydrochloric acid and cupric chloride; Micro-etching solution stationary tank and anolyte compartment are communicated with, and described micro-etching solution comprises ammonium persulphate and sulfuric acid; When carrying out electrolytic reaction, in the anolyte compartment, after the ammonium sulfate that reaction forms through microetch in the micro-etching solution is oxidized to ammonium persulphate, be back in the micro-etching solution stationary tank, bivalent cupric ion wherein passes through cationic exchange membrane and enters cathode compartment simultaneously; In cathode compartment, the univalent copper ion that forms through etching reaction in the acidic etching liquid preferentially becomes metallic copper in cathodic reduction, and bivalent cupric ion is back in the acidic etching liquid stationary tank simultaneously.
Compare with prior art, technique effect of the present invention is:
1. the ammonium sulfate in the micro-etching solution changes into useful ammonium persulphate in anodic oxygen, and the anode electric energy makes full use of;
2. the cupric ion Cu in the micro-etching solution
2+Pass through cationic exchange membrane and enter cathode compartment, carry out effectively additionally as the oxygenant of acid etching, make full use of the copper resource, do not produce and pollute and waste;
3. enter the invalid components Cu in the acidic etching liquid of cathode compartment
+Preferentially in cathodic reduction, the electric energy of its consumption only is traditional C u
2+Half of electrolytic reduction under the prerequisite that reclaims the copper resource, saved electric energy;
4. owing to adopt cationic exchange membrane, the chlorion of cathode compartment can't enter the anolyte compartment, has controlled the generation of chlorine, and whole electrolytic process does not pollute;
5. owing to adopt continuous electrolysis regeneration, make the effective concentration in micro-etching solution and the acidic etching liquid all constant, microetch and etched quality are all greatly improved in preferable states;
6. microetch and acid etching have been realized the spot patch adding medicine, zero release is polluted, and greatly reduces production cost, has improved productivity effect.
Description of drawings
Fig. 1 is the work synoptic diagram of the inventive method.
Embodiment is described in further detail below in conjunction with the most preferred embodiment shown in the accompanying drawing.
As shown in Figure 1, electrolyzer adopts the polyvinyl chloride plastic plate to make rectangular slot, with tetrafluoroethylene cationic exchange membrane 15 anolyte compartment 11 is separated with cathode compartment 12, and distance is 120mm between the anode and cathode, anode adopts boron-doped diamond film electrode, and it is electrode that negative electrode adopts the thick Copper Foil of 35 μ m.Acidic etching liquid stationary tank 17 and described cathode compartment 12 are communicated with, and described acidic etching liquid comprises hydrochloric acid and cupric chloride.Micro-etching solution stationary tank 16 and anolyte compartment 11 are communicated with, and described micro-etching solution comprises ammonium persulphate and sulfuric acid.Can also add a small amount of copper sulfate in the described micro-etching solution, when the microetch operation begins, in micro-etching solution, add a little copper sulfate, help accelerating microetch speed.Acidic etching liquid and micro-etching solution enter cathode compartment 12 respectively and carry out electrolytic regeneration with anolyte compartment 11.
1. useless micro-etching solution electrolytic regeneration principle in anolyte compartment and condition control
Anodic reaction: 2SO
4 2--2e → S
2O
8 2-
Anodic current density: 50-100A/dm
2, temperature: normal temperature
Because the concentration of ammonium sulfate is not high in the micro-etching solution, for improving current efficiency, the solution of anolyte compartment adopts circulation means to strengthen ammonium sulfate and anode touch opportunity.The Cu of anolyte compartment
2+Be subjected to the effect of negative electrode electrostatic attraction to pass cationic membrane and enter cathode compartment.
2. cathode compartment spent acid etching solution electrolytic regeneration principle and condition control
Contain a large amount of Cu in the acidic etching waste liquid
+And Cu
2+, total copper concentration generally maintains 120-150g/l, wherein Cu
2+Account for 55%, Cu
+Account for 45%.Utilize E ° of Cu
+/ Cu=+0.522V is greater than E ° of Cu
2+/ Cu=+0.34V, Cu
+Preferentially be reduced into metallic copper Cu
++ e → Cu, and make Cu with etch capabilities
2+Remain, add the Cu that the anolyte compartment comes
2+Converge and return etching bath together and go work.
Cathode current density is controlled at 6-15A/dm
2The employing thin copper foil is a negative electrode, and temperature is a normal temperature, and for making negative plate uniform quality up and down, catholyte adopts Recycle design to be evenly distributed on solution everywhere to guarantee cupric ion.
Reach the negative electrode regenerated acidic etching solution in order to be implemented in the electrolyzer, the purpose of anode regeneration micro-etching solution must adopt the cationic exchange membrane corrosion-resistant, anti-oxidant, that electric conductivity is high and membrane resistance is little as diaphragm material, so that cathode compartment and anolyte compartment are separated.Through the repetition test contrast, select the best results of tetrafluoroethylene cationic exchange membrane for use.Anode can adopt platinum anode, titanium to be coated with platinum group oxide anode and boron-doped diamond film electrode.But be coated with platinum group oxide anode and boron-doped diamond film electrode by comparison platinum anode, titanium, find that boron-doped diamond film electrode has remarkable advantages, it is a kind of anode material of long-life high oxygen separated overpotential.In 1 mol sulfuric acid medium, the oxygen evolution potential of boron-doped diamond film electrode is+2.4V that the platinum electrode oxygen evolution potential is+1.5V that titanium is coated with platinum group oxide electrode oxygen evolution potential and is+1.35V.From oxygen evolution potential as can be seen, boron-doped diamond film electrode is difficult for producing oxygen in anode oxidation process, and electric energy is used for sulfate radical is oxidized to persulfate fully, and rareer be, boron-doped diamond film sacrificial electrode material hardly in anode oxidation process, and one ton of ammonium persulphate of the every generation of platinum electrode will consume 3 gram platinum, and cost is too high, thus the embodiment of the invention to select boron-doped diamond film electrode for use be anode material.
Embodiment one:
Embodiment two:
Claims (6)
1. method of electrolytic regeneration acidic etching liquid and micro-etching solution simultaneously is included in the electrolyzer that acid resisting material makes, and with cationic exchange membrane anolyte compartment (11) and cathode compartment (12) is separated; Acidic etching liquid stationary tank (17) and described cathode compartment (12) are communicated with, and described acidic etching liquid comprises hydrochloric acid and cupric chloride, is used for etching and is overlying on Copper Foil on the insulating material; It is characterized in that:
Micro-etching solution stationary tank (16) and anolyte compartment (11) are communicated with, and described micro-etching solution comprises ammonium persulphate and sulfuric acid, is used for that the copper face on the printed circuit board (PCB) is carried out microetch and handles;
When carrying out electrolytic reaction, in anolyte compartment (11), after the ammonium sulfate that reaction forms through microetch is oxidized to ammonium persulphate, be back in the micro-etching solution stationary tank (16), bivalent cupric ion passes through cationic exchange membrane and enters cathode compartment (12) simultaneously; In cathode compartment (12), the univalent copper ion that forms through etching reaction preferentially is reduced into metallic copper at negative electrode (14), and bivalent cupric ion is back in the acidic etching liquid stationary tank (17) simultaneously.
2. the method for while electrolytic regeneration acidic etching liquid as claimed in claim 1 and micro-etching solution is characterized in that: described cationic exchange membrane adopts tetrafluoroethylene to make.
3. the method for while electrolytic regeneration acidic etching liquid as claimed in claim 1 and micro-etching solution is characterized in that: place the anode (13) of anolyte compartment (11) to adopt boron-doped diamond film electrode.
4. the method for while electrolytic regeneration acidic etching liquid as claimed in claim 1 and micro-etching solution is characterized in that: anodic current density is 50～100A/dm
2
5. the method for while electrolytic regeneration acidic etching liquid as claimed in claim 1 and micro-etching solution is characterized in that: cathode current density is 6～15A/dm
2
6. the method for while electrolytic regeneration acidic etching liquid as claimed in claim 1 and micro-etching solution, it is characterized in that: described micro-etching solution also comprises copper sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100620866A CN100494500C (en) | 2006-08-04 | 2006-08-04 | Method for simultaneous electrolysis and regeneration of acid etching solution and micro-etching solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100620866A CN100494500C (en) | 2006-08-04 | 2006-08-04 | Method for simultaneous electrolysis and regeneration of acid etching solution and micro-etching solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1966773A CN1966773A (en) | 2007-05-23 |
| CN100494500C true CN100494500C (en) | 2009-06-03 |
Family
ID=38075743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100620866A Active CN100494500C (en) | 2006-08-04 | 2006-08-04 | Method for simultaneous electrolysis and regeneration of acid etching solution and micro-etching solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100494500C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101988200A (en) * | 2009-08-04 | 2011-03-23 | 章晓冬 | Cyclic regeneration and metal reclamation equipment for acid chloride-containing etchant |
| CN102807294A (en) * | 2011-05-31 | 2012-12-05 | 无锡尚德太阳能电力有限公司 | Recirculation system for treating used etching liquid |
| CN102321908A (en) * | 2011-09-02 | 2012-01-18 | 广州市天承化工有限公司 | Recycling and regenerating process method and metal copper recovery system of acid chloride etching solution |
| CN102502925B (en) * | 2011-11-29 | 2013-11-13 | 浙江大学 | Device capable of generating electric energy and simultaneously removing metal ions and method of device |
| CN102732888A (en) * | 2012-07-19 | 2012-10-17 | 湖南万容科技股份有限公司 | Method and system for regenerating and recycling acidic etching waste liquor |
| CN104535636B (en) * | 2014-12-16 | 2017-10-10 | 宇宙电路板设备(深圳)有限公司 | A kind of oxidant inductor and oxidant addition control circuit and controller |
| 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 |
| 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 |
| CN107829111B (en) * | 2017-10-17 | 2019-05-14 | 天津大学 | A kind of regeneration of acid copper chloride etching liquid in-situ electrolysis and copper recovery method |
| CN108668452A (en) * | 2018-06-12 | 2018-10-16 | 江苏博敏电子有限公司 | A kind of PCB fine-lines electrolytic etching recycles correlation technology with copper |
| 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 |
| CN108950563A (en) * | 2018-07-16 | 2018-12-07 | 深圳市祺鑫天正环保科技有限公司 | Acid etching regenerates solution additive and acid etching regenerated liquid |
| CN110408936B (en) * | 2019-07-18 | 2021-09-03 | 惠州市臻鼎环保科技有限公司 | Method for electrolyzing acidic etching waste liquid of circuit board |
-
2006
- 2006-08-04 CN CNB2006100620866A patent/CN100494500C/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN1966773A (en) | 2007-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100494500C (en) | Method for simultaneous electrolysis and regeneration of acid etching solution and micro-etching solution | |
| CN101768742B (en) | Regenerated acidic etching solution, copper recycling method and special device thereof | |
| CN202945326U (en) | Acidic waste etching solution recycling system | |
| CN201834972U (en) | Regeneration system of acid etching liquid containing copper ions | |
| CN102732888A (en) | Method and system for regenerating and recycling acidic etching waste liquor | |
| CN106544703A (en) | Perforation Copper Foil foil machine and its production technology | |
| CN102912375B (en) | Method and the special purpose device thereof of copper is reclaimed from acidic etching liquid | |
| CN208279686U (en) | Acidity etching liquid recycling system | |
| CN202492580U (en) | Acid etching liquid recycling device of PCB (Printed Circuit Board) | |
| CN202492581U (en) | Acid etching solution cyclic regeneration unit for printed wiring board | |
| MXPA02010706A (en) | Cathode for electrochemical regeneration of permanganate etching solutions. | |
| CN102560499A (en) | Device for recycling printed circuit board acidic etching solution | |
| CN203976921U (en) | The circulation of acid copper chloride etching liquid electrolytic regeneration and copper coin retrieving arrangement | |
| CN203307434U (en) | Regeneration treatment system of acidic etching waste liquid | |
| CN206052186U (en) | Perforation Copper Foil foil machine | |
| CN205398736U (en) | Waste liquid regeneration utilizes and smart copper recovery device | |
| CN208087748U (en) | Two-component acidity etching liquid recycling device | |
| CN100585014C (en) | A kind of ceramic diaphragm electrolytic cells and its production and application | |
| CN212770968U (en) | Alkaline etching solution in-situ electrolysis copper extraction recycling device | |
| JPH07316863A (en) | Lead dioxide electrode for electrolysis and its production | |
| CN103590070B (en) | For the structure of copper bar of Electrode connection in electrolytically etching liquid | |
| JP3455705B2 (en) | Electro-copper plating apparatus and copper plating method using said apparatus | |
| CN203613055U (en) | Treatment device for wastewater with high salinity and chlorine | |
| CN205062184U (en) | Lose waste liquid recycle and regeneration system a little | |
| CN207659528U (en) | A kind of circuit board corrosion liquid regenerating unit |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Shenzhen Dongjiang Environmental Protection Co., Ltd. Assignor: Liu Jingliang Contract fulfillment period: 2009.5.20 to 2014.5.19 contract change Contract record no.: 2009440000513 Denomination of invention: Method for simultaneous electrolysis and regeneration of acid etching solution and micro-etching solution Granted publication date: 20090603 License type: Exclusive license Record date: 2009.6.18 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.5.20 TO 2014.5.19; CHANGE OF CONTRACT Name of requester: DONGJIANG ENVIRONMENTAL PROTECTION CO. LTD., SHENZ Effective date: 20090618 |
|
| ASS | Succession or assignment of patent right |
Owner name: YAN TAT PRINTED CIRCUIT (SHENZHEN) CO., LTD. Free format text: FORMER OWNER: LIU JINGLIANG Effective date: 20140925 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 518057 SHENZHEN, GUANGDONG PROVINCE TO: 518000 SHENZHEN, GUANGDONG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20140925 Address after: 518000 Guangdong province Shenzhen Pingshan New District Shenzhen Industrial Zone No. 8 Endalu Patentee after: Yan Tat Circuit (Shenzhen) Co., Ltd. Address before: 108 7H, 518057 village, Futian District, Shenzhen, Guangdong, Yitian Patentee before: Liu Jingliang |