CN104313584B - The electrolysis containing copper etchant solution obtains copper coin cyclic utilization method and system - Google Patents
The electrolysis containing copper etchant solution obtains copper coin cyclic utilization method and system Download PDFInfo
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- CN104313584B CN104313584B CN201410530489.3A CN201410530489A CN104313584B CN 104313584 B CN104313584 B CN 104313584B CN 201410530489 A CN201410530489 A CN 201410530489A CN 104313584 B CN104313584 B CN 104313584B
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- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 72
- 239000010949 copper Substances 0.000 title claims abstract description 43
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 33
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 7
- 238000005530 etching Methods 0.000 claims abstract description 98
- 239000007788 liquid Substances 0.000 claims abstract description 67
- 238000010521 absorption reaction Methods 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 230000008569 process Effects 0.000 claims abstract description 17
- 238000009826 distribution Methods 0.000 claims abstract description 14
- 230000003213 activating effect Effects 0.000 claims abstract description 8
- 230000007613 environmental effect Effects 0.000 claims abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 37
- 229910001431 copper ion Inorganic materials 0.000 claims description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 27
- 239000010936 titanium Substances 0.000 claims description 25
- 229910052719 titanium Inorganic materials 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 230000001502 supplementing effect Effects 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 8
- 230000007797 corrosion Effects 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 7
- -1 perfluorosulfonic acid ion Chemical class 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 238000000866 electrolytic etching Methods 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000003628 erosive effect Effects 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 description 67
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
Landscapes
- Electrolytic Production Of Metals (AREA)
- ing And Chemical Polishing (AREA)
Abstract
A kind of electrolysis containing copper etchant solution obtains copper coin cyclic utilization method and device, it is characterized in that described device includes: in etching solution overflow bucket (1), the anolyte circulation groove (4) of internal connection and catholyte circulating slot (3), anolyte circulation groove (4) and catholyte circulating slot (3) at least one be connected with the port of export of etching solution overflow bucket (1)；The electrolysis system being made up of anode electrolysis room (5) and catholyte chamber (6) array, anode electrolysis room GAS ABSORPTION gas distribution pipe (11) and catholyte chamber's GAS ABSORPTION gas distribution pipe (12)；The gas of entrance cathode chamber water electrolytic gas absorption cycle groove (8) forms saline solution after treatment and is discharged into synthesized environmental protection process pond process, and anode chamber's water electrolytic gas absorption cycle groove (7) and the cathode chamber water electrolytic gas untreated gas of absorption cycle groove (8) part discharge after entering activating QI tower (9) purified treatment.Injustice of the present invention can recycle etching liquid and can directly obtain copper coin.
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 processes skill
Art, specifically a kind of electrolysis containing copper etchant solution obtains copper coin cyclic utilization method and system.
Background technology
It is known that the circuit in printed circuit board is formed by the etching containing copper etchant solution.In order to ensure etching effect
Fruit needs to control oxidation-reduction potential (ORP), acidity and the proportion in etching solution, when these indexs are less than or exceed setting value
Arise that etching solution poor effect, it is necessary to add the oxidant such as copper chloride, hydrochloric acid in time and make etching solution recover power, oxidant
Etching solution overflow can be caused after interpolation, discharge or reprocess Posterior circle use, and reprocess recycling and can not only save production
Cost, and beneficially environmental protection, be etching solution treatment technology that is a kind of effective and that be widely adopted, but existing process skill
Art uses ionic membrane Direct Electrolysis technique mostly, and negative electrode output is low value-added copper powder, needs centrifugal separation equipment ability
Copper powder is taken out, and regenerated liquid ORP(oxidation-reduction potential) recover relatively low, it is impossible to reach recycling state, need extra benefit
Oxidizer；Due to process characteristic, the chlorine produced when equipment runs cannot effectively utilize, and needs the activating QI tower of a large amount of alkali liquor to combine
Conjunction processes；Need manually-operated program too much, consume a large amount of manpower.
Summary of the invention
It is an object of the invention to for etching solution treatment effect in existing printed circuit board etching production process the best, it is impossible to
Directly return production line to use, need to add using oxidant just can rejuvenate and recycle the copper poor of gained, it is impossible to
Directly utilizing, need to carry out the problem of after-treatment, the electrolysis containing copper etchant solution of invention one obtains copper coin recycling utilization
Method and system.
One of technical scheme is:
A kind of electrolysis containing copper etchant solution obtains copper coin cyclic utilization method, 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 passes through overfall
Enter in catholyte circulating slot 3；
Secondly, the spent etching solution in anolyte circulation groove 4 and catholyte circulating slot 3 is introduced anode electrolysis room
5 and the bottom of catholyte chamber 6 be electrolysed, use the isolation of modified ion film between anode electrolysis room 5 and catholyte chamber 6,
Use titanium plate as cathode electrode；Control the liquid level difference between anode electrolysis room 5 and catholyte chamber 6 less than 10 centimetres；
3rd, when the ORP of on-line checking etching solution is generally copper ion in 480mv, and etching solution less than controlling parameter
When concentration is 60-150 grams per liter, electrolysis with ion-exchange film system start-up, etching solution enters anode electrolysis room 5, by electrochemical action,
Univalent copper ion in etching solution loses electronics at anode and is oxidized to bivalent cupric ion, and bivalent cupric ion increases, univalent copper ion
It is reduced or eliminated, improves the oxidability of etching solution, return anolyte circulation groove 4 by anode electrolysis room 5 is high-order；With
This simultaneously, etching solution enters catholyte chamber 6, and under electrolysis, copper ion therein is reduced to copper simple substance also at negative electrode
At cathode surface formation of deposits fine copper plate, so that copper ion concentration reduces, reduce the etching solution after content of copper ion from the moon
Pole tank house 6 is high-order returns catholyte circulating slot 3, with the erosion after anode electrolysis returning anolyte circulation groove 4
Returning after carving liquid allotment in etching regenerated liquid interpolation storage barrel 2 and recycle for etching work procedure, the etching solution after supplementing enters loses
Carve and after liquid enters production line, make the index of etching solution recover normal, after supplementing etching solution ORP index and copper after production line
Ion concentration enters after again reducing and enters subsequent cycle in etching solution overflow bucket 1；
4th, anode electrolysis room and catholyte chamber are respectively mounted anodic gas absorption tube and cathode chamber GAS ABSORPTION
The gas absorbed also is introduced corresponding anode chamber's water electrolytic gas absorption cycle groove 7 and the absorption of cathode chamber water electrolytic gas by pipe respectively
Processing in treatment trough 8, wherein gas jet in anode chamber's water electrolytic gas absorption cycle groove 7 in anode chamber's absorbs, effectively profit
Promote the ORP of etching regenerated liquid further with anode chamber's gas, cathode chamber gas absorbs at treatment trough 8 through cathode chamber water electrolytic gas
After reason formed saline solution be emitted into synthesized environmental protection process pond carry out subsequent treatment, anode chamber's water electrolytic gas absorption cycle groove 7 and negative electrode
Room water electrolytic gas absorbs after the untreated gas of part in treatment trough 8 introduces activating QI tower 9 purification and discharges.
Described modified ion film is perfluorosulfonic acid ion film.
Described Faradaic current should meet following condition: when copper ion concentration is less than 60 grams per liter, Faradaic current anode and cathode
Electric current density is 0.1-1.0ASD, and when copper ion concentration is more than 130 grams per liter, Faradaic current anode and cathode electric current density is 1.2-
3.0ASD, when processing between the two, Faradaic current anode and cathode electric current density is 0.5-2.5ASD.
The two of technical scheme are:
A kind of electrolysis containing copper etchant solution obtains copper coin recycling utilization system, it is characterized in that it includes:
One etching solution overflow bucket 1, this etching solution overflow bucket is used for collecting on etching production line and producing because supplementing
Raw unnecessary etching solution the feed reservoir as electrolytic etching liquid；
The anolyte circulation groove 4 of one internal connection and catholyte circulating slot 3, anolyte circulation groove 4 He
In catholyte circulating slot 3 at least one be connected with the port of export of etching solution overflow bucket 1；
One electrolysis system being made up of anode electrolysis room 5 and catholyte chamber 6 array, the low level feed liquor of anode electrolysis room 5
Mouth is connected with the liquid outlet of anolyte circulation groove 4, the low level inlet of catholyte chamber 6 and catholyte circulating slot
The liquid outlet of 3 is connected, and the liquid level difference between anode electrolysis room 5 and catholyte chamber 6 is less than 5 centimetres；The height of anode electrolysis room 5
Position liquid outlet is connected with the inlet of anolyte circulation groove 4, the high-order liquid outlet of catholyte chamber 6 and catholyte
The inlet of circulating slot 3 is connected to realize circulation, the regenerated liquid liquid outlet of catholyte circulating slot 3 and anode chamber's water electrolytic gas
Absorption cycle groove 7 is connected；Activate yang and be separated by modified ion film 10 between pole tank house 5 and catholyte chamber 6；
One anode electrolysis room GAS ABSORPTION gas distribution pipe 11 and catholyte chamber's GAS ABSORPTION gas distribution pipe 12, anode electrolysis room
The inlet end of GAS ABSORPTION gas distribution pipe 11 and catholyte chamber's GAS ABSORPTION gas distribution pipe 12 respectively with corresponding each anode electrolysis
Room is connected with the gas outlet of each catholyte chamber, their gas outlet respectively with anode chamber's water electrolytic gas absorption cycle groove 7 and
Cathode chamber water electrolytic gas absorption cycle groove 8 is connected, and the gas entering anode chamber's water electrolytic gas absorption cycle groove 7 is electrolysed by the cathode
Etching after the ORP, ORP of lifting etching regenerated liquid promote further after the etching regenerated liquid absorption of backflow in liquid circulating slot 3 is again
Raw liquid is flowed into etching regenerated liquid to be added in storage barrel 2 and finally returns that etching line realizes automatic interpolation；Entrance cathode chamber is electrolysed
The gas of GAS ABSORPTION circulating slot 8 forms saline solution after treatment and is discharged into synthesized environmental protection process pond process, anode chamber's water electrolytic gas
Absorption cycle groove 7 and the cathode chamber water electrolytic gas absorption cycle groove 8 untreated gas of part enter activating QI tower 9 purified treatment heel row
Put.
Described modified ion film 10 is perfluorosulfonic acid ion film.
The minus plate installed in described catholyte chamber is titanium plate or corrosion resistant plate against corrosion, preferably thickness 0.5-
The high-quality titanium mesh (1 grade or 2 grades of titanium meshes must be used) of 2.5mm, the positive plate installed in described anode electrolysis room
For containing coated titanium plate (must use 1 grade or 2 grades of titanium meshes), coating mainly contains rare metal ruthenium and other trace
The rare metal such as iridium, tantalum.
Beneficial effects of the present invention:
1, the present invention uses modified ion film, the copper coin of negative electrode output high added value, it is not necessary to separation equipment can be by copper
The convenient taking-up of plate.
2, the present invention adjusts electric current automatically according to copper ion concentration in waste liquid, and regenerated liquid ORP(oxidoreduction can be substantially improved
Current potential) while, only trace chlorine produces, and this part chlorine is dissolved in regenerated liquid through special conveyance conduit circulation, is not required to
Want extra process, and can again promote regenerated liquid ORP(oxidation-reduction potential), make regenerated liquid need not additionally and add oxidant i.e.
Recycling requirement can be met.
3, the present invention is by controlling the ORP value of electrolytic etching liquid, and the effective generation controlling chlorine makes univalent copper ion become
For bivalent cupric ion, recover etch capabilities, completely return to produce, reduce and even cancel the oxidant used by producing, save raw
Product material, reduces production cost.
4, the present invention is by carrying out jet to the hydrochloric acid escaping gas of cathode chamber and the chlorine produced under emergency case
Absorb and the technique of ferrum reaction neutralization, it is to avoid waste gas is excessive, it is ensured that the safety of system.
5, the present invention makes copper by controlling anode titanium plate coating formula, membrane flux and three factors of cathode titanium plates material composition
Ion deposits in order in cathode titanium plates, obtains the copper coin of densification.
6, the present invention utilizes perfluorosulfonic acid ion membrane electrolysis, extracts copper purity and reaches more than 99.5%, and can output copper
Plate, staff labor intensity is little, and copper selling price is high.
7, automaticity of the present invention is high, and system operation maintenance is simple, does not affect production in installation and debugging.
Accompanying drawing explanation
Fig. 1 is the system principle diagram of the present invention；
Fig. 2 is the electrolysis system structure enlarged diagram of the present invention.
Detailed description of the invention
The present invention is further illustrated with embodiment below in conjunction with the accompanying drawings.
Embodiment one.
As shown in Figure 1.
A kind of electrolysis containing copper etchant solution obtains copper coin cyclic utilization method, and it comprises the following steps:
First, the etching solution in etching solution overflow bucket 1 fills in anolyte circulation groove 4, then passes through overfall
Enter in catholyte circulating slot 3；
Secondly, the spent etching solution in anolyte circulation groove 4 and catholyte circulating slot 3 is introduced anode electrolysis room
5 and the bottom of catholyte chamber 6 be electrolysed, use the isolation of modified ion film between anode electrolysis room 5 and catholyte chamber 6
(perfluorosulfonic acid ion film), minus plate is commercially available 1 grade of common titanium plate or corrosion resistant plate against corrosion, preferably thickness 0.5-2.5mm
Titanium plate or 2 grades of high-quality titanium plates, anode can be high-quality titanium mesh (commercially available 1 grade or 2 grades of titanium plates), it is desirable that be containing rare metal
The titanium plate of ruthenium coating (content of metal Ru, thickness etc. are same as the prior art), when being embodied as, except containing rare in coating
The rare metals such as the iridium of trace, tantalum also can be suitably increased outside metal Ru；Control between anode electrolysis room 5 and catholyte chamber 6
Liquid level difference is less than 10 centimetres to prevent liquid level difference from causing ionic membrane to rupture；
3rd, when the ORP of on-line checking etching solution is less than controlling the dense of copper ion in parameter 480-520mv and etching solution
When degree is for 60-150 grams per liter, electrolysis with ion-exchange film system start-up, etching solution enters anode electrolysis room 5, by electrochemical action, erosion
Carving the univalent copper ion in liquid to lose electronics at anode and be oxidized to bivalent cupric ion, bivalent cupric ion increases, and univalent copper ion subtracts
Less or eliminate, improve the oxidability of etching solution, return anolyte circulation groove 4 by anode electrolysis room 5 is high-order；With this
Meanwhile, etching solution enter catholyte chamber 6, under electrolysis, copper ion therein negative electrode be reduced to copper simple substance and
Cathode surface formation of deposits fine copper plate, so that copper ion concentration reduces, reduces the etching solution after content of copper ion from negative electrode
Tank house 6 is high-order returns catholyte circulating slot 3, with the etching after anode electrolysis returning anolyte circulation groove 4
Returning after liquid allotment in etching regenerated liquid interpolation storage barrel 2 and recycle for etching work procedure, the etching solution after supplementing enters and etches
Liquid enters and makes after production line the index of etching solution recover normal, the etching solution after supplementing after production line ORP index and copper from
Sub-concentration enters after again reducing and enters subsequent cycle in etching solution overflow bucket 1；For ensureing electrolysis effectiveness, should be according to etching
In liquid, the concentration of copper ion adjusts Faradaic current, and method of adjustment is: when copper ion concentration is less than 60 grams per liter, Faradaic current is cloudy
Anodic current density is 0.1-1.0ASD, and when copper ion concentration is more than 130 grams per liter, Faradaic current anode and cathode electric current density is
1.2-3.0ASD, when processing between the two, Faradaic current anode and cathode electric current density is 0.5-2.5ASD.
4th, anode electrolysis room and catholyte chamber are respectively mounted anodic gas absorption tube and cathode chamber GAS ABSORPTION
The gas absorbed also is introduced corresponding anode chamber's water electrolytic gas absorption cycle groove 7 and the absorption of cathode chamber water electrolytic gas by pipe respectively
Processing in treatment trough 8, wherein gas jet in anode chamber's water electrolytic gas absorption cycle groove 7 in anode chamber's absorbs, effectively profit
Promote the ORP of etching regenerated liquid further with anode chamber's gas, cathode chamber gas absorbs at treatment trough 8 through cathode chamber water electrolytic gas
After reason formed saline solution be emitted into synthesized environmental protection process pond carry out subsequent treatment, anode chamber's water electrolytic gas absorption cycle groove 7 and negative electrode
Room water electrolytic gas absorbs after the untreated gas of part in treatment trough 8 introduces activating QI tower 9 purification and discharges.
Embodiment two.
As shown in Figure 1.
A kind of electrolysis containing copper etchant solution obtains copper coin recycling utilization system, and it includes:
One etching solution overflow bucket 1, this etching solution overflow bucket is used for collecting on etching production line and producing because supplementing
Raw unnecessary etching solution the feed reservoir as electrolytic etching liquid；
The anolyte circulation groove 4 of one internal connection and catholyte circulating slot 3, anolyte circulation groove 4 He
In catholyte circulating slot 3 at least one be connected with the port of export of etching solution overflow bucket 1；
One electrolysis system (such as Fig. 2) being made up of anode electrolysis room 5 and catholyte chamber 6 array, anode electrolysis room 5 low
Position inlet is connected with the liquid outlet of anolyte circulation groove 4, the low level inlet of catholyte chamber 6 and catholyte
The liquid outlet of circulating slot 3 is connected, and the liquid level difference between anode electrolysis room 5 and catholyte chamber 6 is less than 5 centimetres；Anode electrolysis
The high-order liquid outlet of room 5 is connected with the inlet of anolyte circulation groove 4, and the high-order liquid outlet of catholyte chamber 6 is with cloudy
The inlet of pole electrolyte circulating slot 3 is connected to realize circulation, the regenerated liquid liquid outlet of catholyte circulating slot 3 and anode chamber
Water electrolytic gas absorption cycle groove 7 is connected；Activate yang between pole tank house 5 and catholyte chamber 6 by modified ion film 10(perfluor
Sulfonic acid ionic membrane) it is separated；
One anode electrolysis room GAS ABSORPTION gas distribution pipe 11 and catholyte chamber's GAS ABSORPTION gas distribution pipe 12, anode electrolysis room
The inlet end of GAS ABSORPTION gas distribution pipe 11 and catholyte chamber's GAS ABSORPTION gas distribution pipe 12 respectively with corresponding each anode electrolysis
Room is connected with the gas outlet of each catholyte chamber, their gas outlet respectively with anode chamber's water electrolytic gas absorption cycle groove 7 and
Cathode chamber water electrolytic gas absorption cycle groove 8 is connected, and the gas entering anode chamber's water electrolytic gas absorption cycle groove 7 is electrolysed by the cathode
Etching after the ORP, ORP of lifting etching regenerated liquid promote further after the etching regenerated liquid absorption of backflow in liquid circulating slot 3 is again
Raw liquid is flowed into etching regenerated liquid to be added in storage barrel 2 and finally returns that etching line realizes automatic interpolation；Entrance cathode chamber is electrolysed
The gas of GAS ABSORPTION circulating slot 8 forms saline solution after treatment and is discharged into synthesized environmental protection process pond process, anode chamber's water electrolytic gas
Absorption cycle groove 7 and the cathode chamber water electrolytic gas absorption cycle groove 8 untreated gas of part enter activating QI tower 9 purified treatment heel row
Put.
When being embodied as, the minus plate installed in catholyte chamber can use titanium plate or corrosion resistant plate against corrosion, preferably thickness
The degree commercially available titanium 1 grade of 0.5-2.5mm, 2 grades of metallic plates of titanium, be provided with positive plate for containing coated titanium plate in anode electrolysis room
(commercially available titanium 1,2 grades of titanium meshes of titanium), coating mainly contains rare metal ruthenium and a small amount of rare metal such as other iridium, tantalum etc..
Work process and the principle of the present invention be:
Anode electrolysis reaction mechanism: 2Cl-→Cl2+ 2e 2CuCl+Cl2→2CuCl2
When electrochemical regeneration, as long as there being Cu+Existence will preferentially carry out Cu+It is oxidized into Cu2+Reaction, but again
Cu during life+Concentration reduces or anodic current density increase all can cause Cl-Aoxidize and separate out chlorine.Native system controls Cu+
Concentration is not less than 10g/l, can effectively prevent chlorine from producing.
Negative electrode electrodeposit reaction mechanism: Cu2++ 2e=Cu
Electro-deposition controls predominantly according to etching solution specific gravity control, and in electro-deposition after etching liquid, Cu concentration is substantially 30-60
Grams per liter.
Part that the present invention does not relate to is the most same as the prior art maybe can use prior art to be realized.
Claims (8)
1. the electrolysis containing copper etchant solution obtains copper coin a cyclic utilization method, 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 passes through overfall
Enter in catholyte circulating slot (3)；
Secondly, the spent etching solution in anolyte circulation groove (4) and catholyte circulating slot (3) is introduced anode electrolysis room
(5) it is electrolysed with the bottom of catholyte chamber (6), between anode electrolysis room (5) and catholyte chamber (6), uses modified ion
Film is isolated, and uses titanium plate as cathode electrode；The liquid level difference controlled between anode electrolysis room (5) and catholyte chamber (6) does not surpasses
Cross 10 centimetres；
3rd, when the ORP of on-line checking etching solution less than controlling the concentration of copper ion in parameter 480-520mv and etching solution is
During 60-150 grams per liter, electrolysis with ion-exchange film system start-up, etching solution enters anode electrolysis room (5), by electrochemical action, etching
Univalent copper ion in liquid loses electronics at anode and is oxidized to bivalent cupric ion, and bivalent cupric ion increases, and univalent copper ion reduces
Or eliminate, improve the oxidability of etching solution, return anolyte circulation groove (4) by anode electrolysis room (5) are high-order；With
This simultaneously, etching solution enters catholyte chamber (6), and under electrolysis, copper ion therein is reduced to copper simple substance at negative electrode
And at cathode surface formation of deposits fine copper plate so that copper ion concentration reduces, reduce etching solution after content of copper ion from
Catholyte chamber (6) is high-order returns catholyte circulating slot (3), with return anolyte circulation groove (4) through anode electricity
Return in etching regenerated liquid interpolation storage barrel (2) after etching solution allotment after solution and recycle for etching work procedure, the erosion after supplementing
Carving after liquid enters etching solution entrance production line makes the index of etching solution recover normal, and the etching solution after supplementing is after production line
ORP index and copper ion concentration enter after again reducing and enter subsequent cycle in etching solution overflow bucket (1)；
4th, anode electrolysis room and catholyte chamber are respectively mounted anodic gas absorption tube and cathode chamber GAS ABSORPTION pipe also
The gas absorbed is introduced respectively at anode chamber's water electrolytic gas absorption cycle groove (7) and the cathode chamber water electrolytic gas absorption of correspondence
Processing in reason groove (8), wherein gas jet in anode chamber's water electrolytic gas absorption cycle groove (7) in anode chamber's absorbs, effectively
Utilizing anode chamber's gas to promote the ORP of etching regenerated liquid further, cathode chamber gas absorbs treatment trough through cathode chamber water electrolytic gas
(8) process after formed saline solution be emitted into synthesized environmental protection process pond carry out subsequent treatment, anode chamber's water electrolytic gas absorption cycle groove (7)
Absorb after the untreated gas of part in treatment trough (8) introduces activating QI tower (9) purification with cathode chamber water electrolytic gas and discharge.
Method the most according to claim 1, is characterized in that described modified ion film is perfluorosulfonic acid ion film.
Method the most according to claim 1, is characterized in that described Faradaic current should meet following condition: described electrolysis
Electric current should meet following condition: when copper ion concentration is less than 60 grams per liter, Faradaic current anode and cathode electric current density is 0.1-
1.0ASD, when copper ion concentration is more than 130 grams per liter, Faradaic current anode and cathode electric current density is 1.2-3.0ASD, when processing two
Time between person, Faradaic current anode and cathode electric current density is 0.5-2.5ASD.
4. the electrolysis containing copper etchant solution obtains copper coin a recycling utilization system, it is characterized in that it includes:
One etching solution overflow bucket (1), this etching solution overflow bucket is used for collecting on etching production line and producing because supplementing
Unnecessary etching solution and as the feed reservoir of electrolytic etching liquid；
The anolyte circulation groove (4) of one internal connection and catholyte circulating slot (3), anolyte circulation groove (4)
With in catholyte circulating slot (3) at least one be connected with the port of export of etching solution overflow bucket (1)；
One electrolysis system being made up of anode electrolysis room (5) and catholyte chamber (6) array, the low level of anode electrolysis room (5) enters
Liquid mouth is connected with the liquid outlet of anolyte circulation groove (4), the low level inlet of catholyte chamber (6) and catholyte
The liquid outlet of circulating slot (3) is connected, and the liquid level difference between anode electrolysis room (5) and catholyte chamber (6) is less than 5 centimetres；Sun
The high-order liquid outlet of pole tank house (5) is connected with the inlet of anolyte circulation groove (4), the height of catholyte chamber (6)
Position liquid outlet is connected with the inlet of catholyte circulating slot (3) to realize circulation, the regeneration of catholyte circulating slot (3)
Liquid liquid outlet is connected with anode chamber's water electrolytic gas absorption cycle groove (7)；Between anode electrolysis room (5) and catholyte chamber (6)
It is 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
The inlet end of GAS ABSORPTION gas distribution pipe (11) and catholyte chamber's GAS ABSORPTION gas distribution pipe (12) respectively with corresponding each anode
Tank house is connected with the gas outlet of each catholyte chamber, their gas outlet respectively with anode chamber's water electrolytic gas absorption cycle groove
(7) it is connected with cathode chamber water electrolytic gas absorption cycle groove (8), enters the gas of anode chamber's water electrolytic gas absorption cycle groove (7)
The ORP, ORP that promote etching regenerated liquid after being electrolysed by the cathode the etching regenerated liquid absorption of backflow in liquid circulating slot (3) further carry
Etching regenerated liquid after Shenging is flowed into etching regenerated liquid to be added in storage barrel (2) and finally returns that etching line realizes interpolation automatically；
The gas of entrance cathode chamber water electrolytic gas absorption cycle groove (8) forms saline solution after treatment and is discharged into synthesized environmental protection process Chi Chu
Reason, anode chamber's water electrolytic gas absorption cycle groove (7) and the cathode chamber water electrolytic gas untreated gas of absorption cycle groove (8) part enter
Discharge after entering activating QI tower (9) purified treatment.
System the most according to claim 4, is characterized in that described modified ion film (10) is perfluorosulfonic acid ion film.
System the most according to claim 4, it is characterized in that in described catholyte chamber install minus plate be titanium plate or
Corrosion resistant plate against corrosion, the positive plate installed in described anode electrolysis room is high-quality titanium plate.
System the most according to claim 6, is characterized in that the high-quality titanium that described minus plate is thickness 0.5-2.5mm
Plate.
System the most according to claim 6, is characterized in that described positive plate is that coating contains containing coated high-quality titanium plate
There are rare metal ruthenium and the iridium of trace thereof and tantalum.
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| CN106319577A (en) * | 2015-07-02 | 2017-01-11 | 阿克陶科邦锰业制造有限公司 | Energy-saving and environment-friendly anode plate |
| CN105177580B (en) * | 2015-08-25 | 2017-10-31 | 深圳市洁驰科技有限公司 | A kind of acidic etching liquid cupric electrolysis device |
| CN106480473B (en) * | 2015-08-31 | 2019-08-13 | 广东德同环保科技有限公司 | A kind of method of electrolytic acid copper chloride |
| CN106119852B (en) * | 2015-08-31 | 2019-09-03 | 叶旖婷 | A kind of electrolytic recovery and regeneration technology of acid copper chloride 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 |
| CN106007114A (en) * | 2016-07-29 | 2016-10-12 | 陈铭 | Electronic factory waste liquid treatment system |
| CN107059011A (en) * | 2017-04-01 | 2017-08-18 | 东莞市青玉环保设备科技有限公司 | The ferric trichloride etching solution regeneration device and method of cupric, nickel and chromium |
| CN106929857A (en) * | 2017-04-01 | 2017-07-07 | 东莞市青玉环保设备科技有限公司 | Cupric acidity etching liquid recycling equipment for reclaiming and method |
| CN107059012A (en) * | 2017-05-02 | 2017-08-18 | 广州合凯环保科技有限公司 | A kind of electrolytic reaction system, acidic etching liquid regeneration and copper-extracting process |
| CN108642518A (en) * | 2018-07-09 | 2018-10-12 | 南京舜业环保科技有限公司 | A kind of method and device of PCB acidic etching liquids extraction copper |
| CN108677192A (en) * | 2018-07-09 | 2018-10-19 | 南京舜业环保科技有限公司 | A kind of copper recovery system and method for alkaline etching waste liquid for producing |
| CN109881216B (en) * | 2019-04-12 | 2023-11-28 | 株洲稷维环境科技有限公司 | Acid electrolytic tank and electrolytic production line using same |
| CN110042425A (en) * | 2019-04-23 | 2019-07-23 | 博罗县华盈科技有限公司 | A kind of heavy process for copper of alkaline etching waste liquid for producing direct electrowinning |
| CN112095121B (en) * | 2019-06-17 | 2023-05-09 | 昆山卫司特环保设备有限公司 | Method and device for regenerating and recycling waste copper liquid of printed circuit board |
| CN110387561A (en) * | 2019-08-18 | 2019-10-29 | 深圳市世清环保科技有限公司 | The device of electro deposited copper is carried out to useless micro etching solution |
| CN113493915A (en) * | 2020-04-01 | 2021-10-12 | 健鼎（湖北）电子有限公司 | Regeneration method and system of acidic etching waste liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101988200A (en) * | 2009-08-04 | 2011-03-23 | 章晓冬 | Cyclic regeneration and metal reclamation equipment for acid chloride-containing etchant |
| CN102206835A (en) * | 2011-05-19 | 2011-10-05 | 广州鸿葳科技股份有限公司 | Acid etchant online electrolytic recycling device and etchant regenerating method |
| CN102851730A (en) * | 2011-07-01 | 2013-01-02 | 东莞市海力环保设备科技有限公司 | Method for recycling waste acid etching solution of printed circuit board and recovering copper |
| 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 |
| 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 |
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