CN104313584A - Method and system for electrolyzing copper-containing etching liquid to obtain copper plate and regenerating and recycling etching liquid - Google Patents
Method and system for electrolyzing copper-containing etching liquid to obtain copper plate and regenerating and recycling etching liquid Download PDFInfo
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- CN104313584A CN104313584A CN201410530489.3A CN201410530489A CN104313584A CN 104313584 A CN104313584 A CN 104313584A CN 201410530489 A CN201410530489 A CN 201410530489A CN 104313584 A CN104313584 A CN 104313584A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to method and device for electrolyzing a copper-containing etching liquid to obtain a copper plate and regenerating and recycling the etching liquid. The device is characterized by comprising an etching liquid overflow storage barrel (1) as well as an anolyte circulating groove (4) and a catholyte circulating groove (3) which are internally communicated, wherein at least one of the anolyte circulating groove (4) and the catholyte circulating groove (3) is communicated with the outlet end of the etching liquid overflow storage barrel (1); an electrolytic system consists of an anode electrolytic room (5) and a cathode electrolytic room (6), and a gas absorption distributing pipe (11) of the anode electrolytic room and a gas absorption distributing pipe (12) of the cathode electrolytic room are arranged; gas which enters into an electrolytic gas adsorption circulating groove (8) of the cathode room is treated to form a salt liquid which is discharged to a comprehensive environment-friendly treatment pond, and part of untreated gas in the electrolytic gas adsorption circulating groove (7) of the anode room and the electrolytic gas adsorption circulating groove (8) of the cathode room enters into a gasifying tower (9) so as to be purified and discharged. According to the method and device provided by the invention, not only can the etching liquid be recycled, but also the copper plate can be directly obtained.
Description
Technical field
The present invention relates to a kind of printed circuit board technology, especially a kind of printed circuit board etching solution reclaiming treatment technology, specifically one obtains copper coin and cyclic utilization method and system containing copper etchant solution electrolysis.
Background technology
As everyone knows, the circuit in printed circuit board is by being formed containing copper etchant solution etching.In order to ensure that etch effect needs to control the redox potential (ORP) in etching solution, acidity and proportion, when these indexs lower than or just there will be etching solution poor effect when exceeding set(ting)value, cupric chloride must be added in time, the oxygenants such as hydrochloric acid make etching solution recover power, oxygenant can cause etching solution overflow after adding, discharge or reprocessing Posterior circle use, and reprocessing recycles and can not only save production cost, and be conducive to environmental protection, it is a kind of effective etching solution treatment technology with being widely adopted, but existing treatment technology adopts ionic membrane Direct Electrolysis technique mostly, negative electrode output be low value-added copper powder, need centrifugal separation equipment copper powder could be taken out, and regenerated liquid ORP(redox potential) recover lower, the state of recycling cannot be reached, need additionally to add oxygenant, due to process characteristic, the chlorine produced when equipment runs cannot effectively utilize, and needs the change gas tower comprehensive treating process of a large amount of alkali lye, need manually-operated program too much, consume a large amount of manpower.
Summary of the invention
The object of the invention is for etching solution treatment effect in existing printed circuit board etching production process not good, directly can not return production line to use, need to add and use oxygenant just can rejuvenate and recycle the copper poor of gained, can not directly utilize, need the problem of carrying out secondary treatment, invention is a kind of obtains copper coin and cyclic utilization method and system containing copper etchant solution electrolysis.
One of technical scheme of the present invention is:
One obtains copper coin and cyclic utilization method containing copper etchant solution electrolysis, it is characterized in that it comprises the following steps:
First, the etching solution in etching solution overflow bucket 1 fills in anolyte circulation groove 4, then enters in catholyte circulation groove 3 by overflow port;
Secondly, electrolysis is carried out in the bottom that spent etching solution in anolyte circulation groove 4 and catholyte circulation groove 3 introduces anode electrolysis room 5 and catholyte chamber 6, adopt modified ion film to isolate between anode electrolysis room 5 and catholyte chamber 6, adopt titanium plate as cathode electrode; The liquid level difference controlled between anode electrolysis room 5 and catholyte chamber 6 is no more than 10 centimetres;
3rd, when the ORP of on-line checkingi etching solution is generally 480mv lower than controling parameters, and when in etching solution, the concentration of cupric ion is 60-150 grams per liter, electrolysis with ion-exchange film system starts, and etching solution enters anode electrolysis room 5, pass through electrochemical action, univalent copper ion in etching solution loses electrons oxidizes at anode and becomes bivalent cupric ion, and bivalent cupric ion increases, and univalent copper ion reduces or eliminates, improve the oxidation capacity of etching solution, return anolyte circulation groove 4 by anode electrolysis room 5 high position, meanwhile, etching solution enters catholyte chamber 6, under electrolytic action, cupric ion is wherein reduced to copper simple substance and at cathode surface formation of deposits fine copper plate at negative electrode, thus copper ion concentration is reduced, the etching solution reduced after content of copper ion returns catholyte circulation groove 3 from catholyte chamber 6 high position, return after allocating with the etching solution after anode electrolysis returning anolyte circulation groove 4 and etch regenerated liquid and add in storage barrel 2 and recycle for etching work procedure, etching solution after supplementing enters and makes the index of etching solution recover normal after etching solution enters production line, etching solution ORP index and copper ion concentration after production line after supplementing enter after again reducing in etching solution overflow bucket 1 and enter next circulation,
4th, anode electrolysis room and catholyte chamber are installed anodic gas absorption tube and cathode compartment gas absorption pipe respectively and absorbed gas is introduced respectively corresponding anolyte compartment's water electrolytic gas absorption cycle groove 7 and cathode compartment water electrolytic gas and absorb in treatment trough 8 and process, wherein gas jet in anolyte compartment's water electrolytic gas absorption cycle groove 7 in anolyte compartment's absorbs, anolyte compartment's gas is effectively utilized to promote the ORP of etching regenerated liquid further, cathode compartment gas absorbs through cathode compartment water electrolytic gas and forms saline solution after treatment trough 8 processes and be disposed to synthesized environmental protection treating pond and carry out subsequent disposal, anolyte compartment's water electrolytic gas absorption cycle groove 7 and cathode compartment water electrolytic gas absorb in treatment trough 8 and discharge after the purification of part untreated gas introducingization gas tower 9.
Described modified ion film is perfluorosulfonic acid ion film.
Described Faradaic current should meet the following conditions: when copper ion concentration is less than 60 grams per liter, Faradaic current anode and cathode current density is 0.1-1.0ASD, when copper ion concentration is greater than 130 grams per liter, Faradaic current anode and cathode current density is 1.2-3.0ASD, when processing between the two, Faradaic current anode and cathode current density is 0.5-2.5ASD.
Two of technical scheme of the present invention is:
One obtains copper coin and recycling utilization system containing copper etchant solution electrolysis, it is characterized in that it comprises:
One etching solution overflow bucket 1, this etching solution overflow bucket is for collecting on etching production line the unnecessary etching solution that produces because supplementing and as the feed reservoir of electrolytically etching liquid;
The one inner anolyte circulation groove 4 that is communicated with and catholyte circulation groove 3, anolyte circulation groove 4 with have one in catholyte circulation groove 3 at least and be connected with the exit end of etching solution overflow bucket 1;
One electrolytic system be made up of anode electrolysis room 5 and catholyte chamber 6 array, the low level fluid inlet of anode electrolysis room 5 is connected with the liquid outlet of anolyte circulation groove 4, the low level fluid inlet of catholyte chamber 6 is connected with the liquid outlet of catholyte circulation groove 3, and the liquid level difference between anode electrolysis room 5 and catholyte chamber 6 is less than 5 centimetres; The high-order liquid outlet of anode electrolysis room 5 is connected with the fluid inlet of anolyte circulation groove 4, the high-order liquid outlet of catholyte chamber 6 is connected to realize circulating with the fluid inlet of catholyte circulation groove 3, the regenerated liquid liquid outlet of catholyte circulation groove 3 is connected with anolyte compartment's water electrolytic gas absorption cycle groove 7; Activate yang between pole tank room 5 and catholyte chamber 6 and be separated by modified ion film 10;
One anode electrolysis room gas absorption gas distribution pipe 11 and catholyte chamber's gas absorption gas distribution pipe 12, anode electrolysis room gas absorption gas distribution pipe 11 is connected with the air outlet of each catholyte chamber with corresponding each anode electrolysis room respectively with the inlet end of catholyte chamber's gas absorption gas distribution pipe 12, their air outlet is connected with cathode compartment water electrolytic gas absorption cycle groove 8 with anolyte compartment's water electrolytic gas absorption cycle groove 7 respectively, the gas entering anolyte compartment's water electrolytic gas absorption cycle groove 7 is electrolysed by the cathode the rear ORP promoting etching regenerated liquid further of etching regenerated liquid absorption of backflow in liquid circulation groove 3, etching regenerated liquid after ORP promotes flow into etch in regenerated liquid interpolation storage barrel 2 and finally return etching line and realizes interpolation automatically, the gas entering cathode compartment water electrolytic gas absorption cycle groove 8 forms saline solution after treatment and is discharged into the process of synthesized environmental protection treating pond, discharges after anolyte compartment's water electrolytic gas absorption cycle groove 7 and entering of the untreated gas of cathode compartment water electrolytic gas absorption cycle groove 8 part gas tower 9 purifying treatment.
Described modified ion film 10 is perfluorosulfonic acid ion film.
The negative plate installed in described catholyte chamber is titanium plate or stainless steel plate against corrosion, be preferably the high-quality titanium mesh (1 grade or 2 grades of titanium meshes must be adopted) of thickness 0.5-2.5mm, the positive plate installed in described anode electrolysis room is for containing coated titanium plate (must adopt 1 grade or 2 grades of titanium meshes), and coating mainly contains the rare metal such as iridium, tantalum of rare metal ruthenium and other trace.
Beneficial effect of the present invention:
1, the present invention adopts modified ion film, the copper coin of negative electrode output high added value, does not need separating device can by convenient for copper coin taking-up.
2, the present invention adjusts electric current automatically according to copper ion concentration in waste liquid, significantly can promote regenerated liquid ORP(redox potential) while, only micro-chlorine produces, this part chlorine is dissolved in regenerated liquid through the circulation of special transport pipe, do not need extra process, and again can promote regenerated liquid ORP(redox potential), make regenerated liquid not need additionally to add oxygenant and can meet and recycle requirement.
3, the present invention is by controlling the ORP value of electrolytically etching liquid, and the effective generation controlling chlorine, makes univalent copper ion become bivalent cupric ion, recover etch capabilities, return production completely, reduce or even cancel and produce oxygenant used, save production material, reduce production cost.
4, the present invention to be undertaken in jet absorption and iron reaction by the hydrochloric acid volatile gases of anticathode room and the chlorine that produces under emergency case and technique, avoid waste gas excessive, ensure the security of system.
5, the present invention makes cupric ion deposit in order in cathode titanium plates by controlling anode titanium plate coating formula, membrane flux and cathode titanium plates material composition three factors, obtains fine and close copper coin.
6, the present invention utilizes perfluorosulfonic acid ion membrane electrolysis, extracts copper purity and reaches more than 99.5%, and energy output copper coin, staff labor intensity is little, and copper selling price is high.
7, level of automation of the present invention is high, and system operation maintenance is simple, in installation and debugging, do not affect production.
Accompanying drawing explanation
Fig. 1 is system principle diagram of the present invention;
Fig. 2 is electrolytic system structure enlarged diagram of the present invention.
embodiment
Below in conjunction with drawings and Examples, the present invention is further illustrated.
Embodiment one.
As shown in Figure 1.
One obtains copper coin and cyclic utilization method containing copper etchant solution electrolysis, and it comprises the following steps:
First, the etching solution in etching solution overflow bucket 1 fills in anolyte circulation groove 4, then enters in catholyte circulation groove 3 by overflow port;
Secondly, electrolysis is carried out in the bottom that spent etching solution in anolyte circulation groove 4 and catholyte circulation groove 3 introduces anode electrolysis room 5 and catholyte chamber 6, modified ion film is adopted to isolate (perfluorosulfonic acid ion film) between anode electrolysis room 5 and catholyte chamber 6, negative plate is common titanium plate or stainless steel plate against corrosion, be preferably commercially available 1 grade of titanium plate or 2 grades of high-quality titanium plates of thickness 0.5-2.5mm, anode can be high-quality titanium mesh (commercially available 1 grade or 2 grades of titanium plates), but be preferably containing the rare metal ruthenium coating (content of metal Ru, thickness etc. are same as the prior art) titanium plate, during concrete enforcement, in coating except containing also can suitably increase except rare metal ruthenium trace iridium, the rare metals such as tantalum, the liquid level difference controlled between anode electrolysis room 5 and catholyte chamber 6 is no more than 10 centimetres and causes ionic membrane to break to prevent liquid level difference,
3rd, when the ORP of on-line checkingi etching solution lower than controling parameters 480-520mv and in etching solution, the concentration of cupric ion is 60-150 grams per liter time, electrolysis with ion-exchange film system starts, etching solution enters anode electrolysis room 5, and by electrochemical action, the univalent copper ion in etching solution loses electrons oxidizes at anode and becomes bivalent cupric ion, bivalent cupric ion increases, univalent copper ion reduces or eliminates, and improves the oxidation capacity of etching solution, returns anolyte circulation groove 4 by anode electrolysis room 5 high position, meanwhile, etching solution enters catholyte chamber 6, under electrolytic action, cupric ion is wherein reduced to copper simple substance and at cathode surface formation of deposits fine copper plate at negative electrode, thus copper ion concentration is reduced, the etching solution reduced after content of copper ion returns catholyte circulation groove 3 from catholyte chamber 6 high position, return after allocating with the etching solution after anode electrolysis returning anolyte circulation groove 4 and etch regenerated liquid and add in storage barrel 2 and recycle for etching work procedure, etching solution after supplementing enters and makes the index of etching solution recover normal after etching solution enters production line, etching solution ORP index and copper ion concentration after production line after supplementing enter after again reducing in etching solution overflow bucket 1 and enter next circulation, for ensureing electrolysis effectiveness, should according to the concentration adjustment Faradaic current of cupric ion in etching solution, inflation method is: when copper ion concentration is less than 60 grams per liter, Faradaic current anode and cathode current density is 0.1-1.0ASD, when copper ion concentration is greater than 130 grams per liter, Faradaic current anode and cathode current density is 1.2-3.0ASD, and when processing between the two, Faradaic current anode and cathode current density is 0.5-2.5ASD.
4th, anode electrolysis room and catholyte chamber are installed anodic gas absorption tube and cathode compartment gas absorption pipe respectively and absorbed gas is introduced respectively corresponding anolyte compartment's water electrolytic gas absorption cycle groove 7 and cathode compartment water electrolytic gas and absorb in treatment trough 8 and process, wherein gas jet in anolyte compartment's water electrolytic gas absorption cycle groove 7 in anolyte compartment's absorbs, anolyte compartment's gas is effectively utilized to promote the ORP of etching regenerated liquid further, cathode compartment gas absorbs through cathode compartment water electrolytic gas and forms saline solution after treatment trough 8 processes and be disposed to synthesized environmental protection treating pond and carry out subsequent disposal, anolyte compartment's water electrolytic gas absorption cycle groove 7 and cathode compartment water electrolytic gas absorb in treatment trough 8 and discharge after the purification of part untreated gas introducingization gas tower 9.
Embodiment two.
As shown in Figure 1.
One obtains copper coin and recycling utilization system containing copper etchant solution electrolysis, and it comprises:
One etching solution overflow bucket 1, this etching solution overflow bucket is for collecting on etching production line the unnecessary etching solution that produces because supplementing and as the feed reservoir of electrolytically etching liquid;
The one inner anolyte circulation groove 4 that is communicated with and catholyte circulation groove 3, anolyte circulation groove 4 with have one in catholyte circulation groove 3 at least and be connected with the exit end of etching solution overflow bucket 1;
One electrolytic system be made up of anode electrolysis room 5 and catholyte chamber 6 array, the low level fluid inlet of anode electrolysis room 5 is connected with the liquid outlet of anolyte circulation groove 4, the low level fluid inlet of catholyte chamber 6 is connected with the liquid outlet of catholyte circulation groove 3, and the liquid level difference between anode electrolysis room 5 and catholyte chamber 6 is less than 5 centimetres; The high-order liquid outlet of anode electrolysis room 5 is connected with the fluid inlet of anolyte circulation groove 4, the high-order liquid outlet of catholyte chamber 6 is connected to realize circulating with the fluid inlet of catholyte circulation groove 3, the regenerated liquid liquid outlet of catholyte circulation groove 3 is connected with anolyte compartment's water electrolytic gas absorption cycle groove 7; Activate yang between pole tank room 5 and catholyte chamber 6 by modified ion film 10(perfluorosulfonic acid ion film) be separated;
One anode electrolysis room gas absorption gas distribution pipe 11 and catholyte chamber's gas absorption gas distribution pipe 12, anode electrolysis room gas absorption gas distribution pipe 11 is connected with the air outlet of each catholyte chamber with corresponding each anode electrolysis room respectively with the inlet end of catholyte chamber's gas absorption gas distribution pipe 12, their air outlet is connected with cathode compartment water electrolytic gas absorption cycle groove 8 with anolyte compartment's water electrolytic gas absorption cycle groove 7 respectively, the gas entering anolyte compartment's water electrolytic gas absorption cycle groove 7 is electrolysed by the cathode the rear ORP promoting etching regenerated liquid further of etching regenerated liquid absorption of backflow in liquid circulation groove 3, etching regenerated liquid after ORP promotes flow into etch in regenerated liquid interpolation storage barrel 2 and finally return etching line and realizes interpolation automatically, the gas entering cathode compartment water electrolytic gas absorption cycle groove 8 forms saline solution after treatment and is discharged into the process of synthesized environmental protection treating pond, discharges after anolyte compartment's water electrolytic gas absorption cycle groove 7 and entering of the untreated gas of cathode compartment water electrolytic gas absorption cycle groove 8 part gas tower 9 purifying treatment.
During concrete enforcement, the negative plate installed in catholyte chamber can adopt titanium plate or stainless steel plate against corrosion, be preferably the commercially available titanium 1 grade of thickness 0.5-2.5mm, titanium 2 grades of metal sheets, be provided with positive plate in anode electrolysis room for containing coated titanium plate (commercially available titanium 1, titanium 2 grades of titanium meshes), coating is mainly containing rare metal ruthenium and a small amount of rare metal such as other iridium, tantalum etc.
Working process of the present invention and principle are:
Anode electrolysis reaction mechanism: 2Cl
-→ Cl
2+ 2e 2CuCl+Cl
2→ 2CuCl
2
When electrochemical regeneration, as long as there is Cu
+existence preferentially will carry out Cu
+be oxidized into Cu
2+reaction, but Cu in regenerative process
+concentration reduces or anodic current density increase all can cause Cl
-be oxidized and separate out chlorine.Native system control Cu
+concentration is not less than 10g/l, can effectively prevent chlorine from producing.
Cathode electrodeposition reaction mechanism: Cu
2++ 2e=Cu
Galvanic deposit controls to be mainly according to etching solution specific gravity control, and in galvanic deposit after etching liquid, Cu concentration is roughly at 30-60 grams per liters.
The part that the present invention does not relate to prior art that maybe can adopt all same as the prior art is realized.
Claims (6)
1. obtain copper coin and a cyclic utilization method containing copper etchant solution electrolysis, it is characterized in that it comprises the following steps:
First, the etching solution in etching solution overflow bucket (1) fills in anolyte circulation groove (4), then enters in catholyte circulation groove (3) by overflow port;
Secondly, electrolysis is carried out in the bottom that spent etching solution in anolyte circulation groove (4) and catholyte circulation groove (3) introduces anode electrolysis room (5) and catholyte chamber (6), adopt modified ion film to isolate between anode electrolysis room (5) and catholyte chamber (6), adopt titanium plate as cathode electrode; The liquid level difference controlled between anode electrolysis room (5) and catholyte chamber (6) is no more than 10 centimetres;
3rd, when the ORP of on-line checkingi etching solution lower than controling parameters 480-520mv and in etching solution, the concentration of cupric ion is 60-150 grams per liter time, electrolysis with ion-exchange film system starts, etching solution enters anode electrolysis room (5), pass through electrochemical action, univalent copper ion in etching solution loses electrons oxidizes at anode and becomes bivalent cupric ion, bivalent cupric ion increases, univalent copper ion reduces or eliminates, improve the oxidation capacity of etching solution, return anolyte circulation groove (4) by anode electrolysis room (5) high position, meanwhile, etching solution enters catholyte chamber (6), under electrolytic action, cupric ion is wherein reduced to copper simple substance and at cathode surface formation of deposits fine copper plate at negative electrode, thus copper ion concentration is reduced, the etching solution reduced after content of copper ion returns catholyte circulation groove (3) from catholyte chamber (6) high position, return after allocating with the etching solution after anode electrolysis returning anolyte circulation groove (4) and etch regenerated liquid and add in storage barrel (2) and recycle for etching work procedure, etching solution after supplementing enters and makes the index of etching solution recover normal after etching solution enters production line, etching solution ORP index and copper ion concentration after production line after supplementing enter after again reducing in etching solution overflow bucket (1) and enter next circulation,
4th, anode electrolysis room and catholyte chamber are installed anodic gas absorption tube and cathode compartment gas absorption pipe respectively and absorbed gas is introduced respectively in corresponding anolyte compartment's water electrolytic gas absorption cycle groove (7) and cathode compartment water electrolytic gas absorption treatment trough (8) and process, wherein in anolyte compartment's water electrolytic gas absorption cycle groove (7), middle jet absorbs anolyte compartment's gas, anolyte compartment's gas is effectively utilized to promote the ORP of etching regenerated liquid further, cathode compartment gas formation saline solution after cathode compartment water electrolytic gas absorption treatment trough (8) process is disposed to synthesized environmental protection treating pond and carries out subsequent disposal, anolyte compartment's water electrolytic gas absorption cycle groove (7) and cathode compartment water electrolytic gas absorb in treatment trough (8) and discharge after part untreated gas introducingization gas tower (9) purification.
2. method according to claim 1, is characterized in that described modified ion film is perfluorosulfonic acid ion film.
3. method according to claim 1, it is characterized in that described Faradaic current should meet the following conditions: described Faradaic current should meet the following conditions: when copper ion concentration is less than 60 grams per liter, Faradaic current anode and cathode current density is 0.1-1.0ASD, when copper ion concentration is greater than 130 grams per liter, Faradaic current anode and cathode current density is 1.2-3.0ASD, when processing between the two, Faradaic current anode and cathode current density is 0.5-2.5ASD.
4. obtain copper coin and a recycling utilization system containing copper etchant solution electrolysis, it is characterized in that it comprises:
One etching solution overflow bucket (1), this etching solution overflow bucket is for collecting on etching production line the unnecessary etching solution that produces because supplementing and as the feed reservoir of electrolytically etching liquid;
The one inner anolyte circulation groove (4) that is communicated with and catholyte circulation groove (3), anolyte circulation groove (4) with have one in catholyte circulation groove (3) at least and be connected with the exit end of etching solution overflow bucket (1);
One electrolytic system be made up of anode electrolysis room (5) and catholyte chamber (6) array, the low level fluid inlet of anode electrolysis room (5) is connected with the liquid outlet of anolyte circulation groove (4), the low level fluid inlet of catholyte chamber (6) is connected with the liquid outlet of catholyte circulation groove (3), and the liquid level difference between anode electrolysis room (5) and catholyte chamber (6) is less than 5 centimetres; The high-order liquid outlet of anode electrolysis room (5) is connected with the fluid inlet of anolyte circulation groove (4), the high-order liquid outlet of catholyte chamber (6) is connected to realize circulating with the fluid inlet of catholyte circulation groove (3), and the regenerated liquid liquid outlet of catholyte circulation groove (3) is connected with anolyte compartment's water electrolytic gas absorption cycle groove (7); Activate yang between pole tank room (5) and catholyte chamber (6) and be separated by modified ion film (10);
One anode electrolysis room gas absorption gas distribution pipe (11) and catholyte chamber's gas absorption gas distribution pipe (12), anode electrolysis room gas absorption gas distribution pipe (11) is connected with the air outlet of each catholyte chamber with corresponding each anode electrolysis room respectively with the inlet end of catholyte chamber's gas absorption gas distribution pipe (12), their air outlet is connected with cathode compartment water electrolytic gas absorption cycle groove (8) with anolyte compartment's water electrolytic gas absorption cycle groove (7) respectively, the gas entering anolyte compartment's water electrolytic gas absorption cycle groove (7) is electrolysed by the cathode the rear ORP promoting etching regenerated liquid further of etching regenerated liquid absorption of backflow in liquid circulation groove (3), etching regenerated liquid after ORP promotes flow into etch in regenerated liquid interpolation storage barrel (2) and finally return etching line and realizes interpolation automatically, the gas entering cathode compartment water electrolytic gas absorption cycle groove (8) forms saline solution after treatment and is discharged into the process of synthesized environmental protection treating pond, discharges after anolyte compartment's water electrolytic gas absorption cycle groove (7) and entering of the untreated gas of cathode compartment water electrolytic gas absorption cycle groove (8) part gas tower (9) purifying treatment.
5. system according to claim 3, is characterized in that described modified ion film (10) is perfluorosulfonic acid ion film.
6. system according to claim 3, it is characterized in that the negative plate installed in described catholyte chamber is titanium plate or stainless steel plate against corrosion, be preferably the high-quality titanium mesh of thickness 0.5-2.5mm, the positive plate installed in described anode electrolysis room is high-quality titanium plate, be preferably containing coated high-quality titanium plate, coating contains iridium and the tantalum of rare metal ruthenium and trace thereof.
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