CN103757664A - Electrolytic tank, etching liquid regeneration equipment using same and regeneration method - Google Patents
Electrolytic tank, etching liquid regeneration equipment using same and regeneration method Download PDFInfo
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- CN103757664A CN103757664A CN201410001343.XA CN201410001343A CN103757664A CN 103757664 A CN103757664 A CN 103757664A CN 201410001343 A CN201410001343 A CN 201410001343A CN 103757664 A CN103757664 A CN 103757664A
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Abstract
The invention discloses equipment and method capable of regenerating acid etching liquid and recycling copper. The equipment comprises a reactor and an electrolytic tank in mutual connection, wherein the reactor comprises a pre-overflow chamber, a first overflow chamber, a second overflow chamber and a third overflow chamber; the electrolytic tank comprises a compartment A and a compartment B; the compartment A comprises a first anode chamber for generating reaction gas O2, a first cathode chamber for recycling copper and a middle chamber arranged between the first anode chamber and the first cathode chamber; the compartment B comprises a second anode chamber for generating reaction gas O2 and an accelerator ClO<3-> and a second cathode chamber for recycling copper. The equipment and method disclosed by the invention have the outstanding effects that the electrolytic tank is simple and compact in structure and can perfectly provide the accelerator and reaction gas for the regeneration process; the whole regeneration process does not need any additive for regeneration; the stability and flexibility of the etching process are enhanced, and the etching process is greatly improved.
Description
Technical field
The present invention relates to a kind of electrolyzer and use the regeneration etching solution of this electrolyzer and the method and apparatus that reclaims copper, belong to resource reutilization and non-ferrous metal and reclaim field.
Background technology
In worldwide, electric appliance and electronic industry is one of fastest-rising industry, and printed circuit board (PCB) is as the important component part of electric appliance and electronic product, and output also increases day by day.It is that the etching solution that printed circuit board (PCB) is put into etching machine carries out etching reaction that conventional acid etching is processed.The removal limited time of copper on printing plate, and part may be because of some organic or other antacid antibody stoped with acidic etching liquid and set up conductor, thereby cause the time to be restricted.
Generally, the speed of 30 to 60 microns of copper of per minute removal can realize.But due to the saturated of copper and for maintaining an acceptable processing speed, the necessary regular replacing of etching solution, will cause a large amount of discarded etching solutions like this.
In prior art, the regeneration of etching solution need be added additive (as hydrogen peroxide H according to following etching reaction
2o
2, ozone O
3, sodium chlorate NaClO
3) could realize:
Cu+2HCl+H
2O
2→CuCl
2+2H
2O；
Cu+2HCl+1/3O
3→CuCl
2+H
2O；
Cu+2HCl+1/3NaClO
3→CuCl
2+1/3NaCl+H
2O；
In addition, there is chemical unmatched phenomenon between the amount of etch copper and the amount of reclaiming in traditional etch process, no matter is the supply of etching solution, and discharge or copper recovery system cause the regeneration of etching solution and the poor effect that copper reclaims.
Summary of the invention
In view of the defect that above-mentioned prior art exists, the object of the invention is to propose a kind of method and specific equipment of processing used etching solution and reclaiming copper, this etching solution is used for Etched Printed Circuit plate in etching machine.
Principle of the present invention is: in etching process, by electrochemical reaction mechanism [CuCl]
++ 3Cl
-+ Cu=>2[CuCl
2]
-, in spent etching solution, can produce a large amount of compound [CuCl
2]
-, regenerative process is by compound [CuCl
2]
-be oxidized to compound [CuCl]
+, because [CuCl]
+be one to the active chemical element of etching reaction.
Object of the present invention will be achieved by the following technical programs:
An electrolyzer, comprise be provided with electricity-electrodialysis system A compartment and in be provided with the B compartment of electrolytic system, described A compartment comprises for generation of reactant gases O
2first anode chamber; For reclaiming the first cathode compartment of copper, and be placed in described first anode chamber and and the first cathode compartment between intermediate chamber; Described B compartment comprises for generation of reactant gases O
2with accelerator ClO
3 -second anode chamber, and for reclaiming the second cathode compartment of copper.
Preferably, described B compartment comprises 2 second anode chambers and 2 the second cathode compartments, and described second anode chamber and the second cathode compartment interval arrange.
The present invention has also disclosed a kind of etching solution reclaim equiment that uses above-mentioned electrolyzer, comprising:
One reactor being connected with etching liquid pool in etching machine, described reactor comprises Yi Geyu overflow chamber and first, second, third overflow chamber, described etching solution Cong Yu overflow chamber enters San Ge overflow chamber after flowing out according to the order of sequence,
One electrolyzer being connected with described reactor, in described electrolyzer comprises, be provided with electricity-electrodialysis system A compartment and in be provided with the B compartment of electrolytic system, described A compartment comprises for generation of reactant gases O
2first anode chamber; For reclaiming the first cathode compartment of copper, and be placed in described first anode chamber and and the first cathode compartment between intermediate chamber; Described B compartment comprises for generation of reactant gases O
2with accelerator ClO
3 -second anode chamber, and for reclaiming the second cathode compartment of copper;
Described electrolyzer also comprises the first buffer memory groove and the second buffer memory groove, the entrance of described the first buffer memory groove is connected with described pre-overflow chamber, the outlet of described the first buffer memory groove is connected with described the first overflow chamber, described the first buffer memory groove is also communicated with the first cathode compartment and the second cathode compartment in described electrolyzer, described first anode chamber is communicated with the second buffer memory groove, described intermediate chamber is communicated with the second overflow chamber, described second anode chamber is communicated with the first overflow chamber, between described reactor and electrolyzer, be also provided with gas piping and both are coupled together, the outlet of described San overflow chamber is connected in etching liquid pool or the etching solution shower nozzle in described etching machine.
Preferably, between described first anode chamber and intermediate chamber, be provided with only for positively charged ion and enter into the cationic membrane in intermediate chamber from described first anode chamber, between described intermediate chamber and the first cathode compartment, be provided with only for negatively charged ion and enter into the anionic membrane in intermediate chamber from described the first cathode compartment.
Preferably, in described the first cathode compartment and the second cathode compartment, be provided with titanium plate electrode, current density is 1 to 10A/dm
2between.
Preferably, indoor sulphuric acid soln and the titanium plate electrode of comprising of the described first anode, the suitable concentration of sulfuric acid is between 10% to 20%, current density is 1 to 5A/dm
2.
Preferably, the gas piping being provided with between described reactor and electrolyzer specifically comprises: the pneumatic outlet of the first anode chamber of the first cathode compartment of described A compartment, the second cathode compartment of B compartment and A compartment is connected with the gas inlet of the first overflow chamber by gas piping, and the pneumatic outlet of the second anode chamber of described B compartment is connected with the gas inlet of the second overflow chamber.
Preferably, described inside reactor pipeline comprises: the excess air outlet of described the first overflow chamber is connected with the gas inlet of the second overflow chamber, and the excess air outlet of described the second overflow chamber is connected with the gas inlet of San overflow chamber.
The present invention has also disclosed a kind of etching solution regeneration method, by the reactor being interconnected and electrolyzer, completed, described reactor comprises first, second, third He Yigeyu overflow chamber, overflow chamber, and described electrolyzer is by electricity-electrodialysis system, electrolytic system, form with first, second buffer memory groove
Described regenerated acidic etching solution method comprises the steps,
Containing [CuCl
2]
-useless acidic etching liquid enter to the pre-overflow chamber in described reactor;
The useless acidic etching liquid Cong Yu of sub-fraction is injected in the first buffer memory groove of electrolyzer in overflow chamber, and remaining useless acidic etching liquid will flow to the first overflow chamber;
Enter to useless acidic etching liquid in the first buffer memory groove and be injected in the electrolytic system of described electrolyzer and the cathode compartment of electricity-electrodialysis system and separate out copper, and then become low copper containing amount acidic etching liquid and return in the first buffer memory groove,
Described low copper containing amount acidic etching liquid turns back in the first overflow chamber of described reactor;
Enter into after the useless acidic etching liquid and the mixing of low copper containing amount acidic etching liquid in the first overflow chamber, wherein a part is injected in the anolyte compartment of described electrolytic system, after reaction, returns; Another part will flow to the second overflow chamber;
Enter into the useless acidic etching liquid in the second overflow chamber, wherein a part is connected with the intermediate chamber of described electricity-electrodialysis system, after reaction, returns, and another part will continue to flow to San overflow chamber,
Acidic etching liquid after regeneration is finally got back to the nozzle of etching machine by pipeline.
Preferably, the solution of the middle storage of the second buffer memory groove is H
2sO
4, by the indoor H of the first anode in pumping and electricity-electrodialysis system
2sO
4solution circulates.
Preferably, the gas O producing in the anolyte compartment of described electricity-electrodialysis system
2be imported in the first overflow chamber the O that electrolytic system anolyte compartment produces
2with accelerator ClO
3 -be injected in the second overflow chamber.
Preferably, first, second, third overflow chamber is when being injected into gas, all through the injection pumping of a use magnetite parcel in described reactor.
Outstanding effect of the present invention is:
1, cell construction is simple, compact, can be well for regenerative process provides accelerator and the reactant gases needing;
2, whole regenerative process does not need to add the additive of any regeneration use;
3, improve stability and the handiness of etching process, will greatly improve etch process.
Below just accompanying drawing in conjunction with the embodiments, is described in further detail the specific embodiment of the present invention, so that technical solution of the present invention is easier to understand, grasp.
Accompanying drawing explanation
Fig. 1 is the structural representation of regenerated acidic etching solution of the present invention and recovery copper equipment.
Fig. 2 is regenerated acidic etching solution of the present invention and reclaims in copper equipment the Structure and Process schematic diagram in reactor when copper is reclaimed.
Fig. 3 is regenerated acidic etching solution of the present invention and reclaims in copper equipment the Structure and Process schematic diagram in electrolyzer when copper is reclaimed.
Fig. 4 is regenerated acidic etching solution of the present invention and reclaims in copper equipment when copper is reclaimed the Structure and Process schematic diagram in electrolyzer B compartment.
Fig. 5 is regenerated acidic etching solution of the present invention and reclaims in copper equipment when copper is reclaimed the Structure and Process schematic diagram in electrolyzer A compartment.
Embodiment
The present invention has disclosed a kind of equipment and method of can regenerated acidic etching solution and reclaiming copper.
As shown in Figures 1 to 5, printed circuit board (PCB) 3 is in the processing of the interior etching solution 2 spraying through nozzle 4 of etching machine 1.Then receive the rinsing of rinsing module 5.Through etching, etching solution 2 becomes acidic etching waste liquid, is sent to reactor 6, in waste liquid, may include following chemical substance: hydrochloric acid, cupric chloride, sodium-chlor, sodium perchlorate and water.Through processing, come the regenerated acidic etching solution 2 of autoreactor 6 to be sent in the shower nozzle 4 of etching machine 1.
Concrete, the described reactor being connected with etching machine 6 comprises the 6a of He Yigeyu overflow chamber of 3 overflow chambers, 3 overflow chambers are respectively the first 6b of overflow chamber, the second 6c of overflow chamber, the 6d of San overflow chamber.Simultaneous reactions device 6 is connected with electrolyzer 7 again, and described electrolyzer 7 is by electricity-electrodialysis system 7a, and electrolytic system 7b and the first buffer memory groove 7c, the second buffer memory groove 7d form.In reactor, the 6d of San overflow chamber of last overflow is connected with the nozzle 4 in etching machine.
The detailed process of regenerated acidic etching solution and recovery copper is:
Containing [CuCl
2]
-useless acidic etching liquid enter to the 6a place, pre-overflow chamber in described reactor;
The useless acidic etching liquid of sub-fraction is by being injected in pipeline 9 Cong Yu overflow chambers in the first buffer memory groove 7c of electrolyzer 7, and remaining useless acidic etching liquid will flow in the first 6b of overflow chamber;
The useless acidic etching liquid entering in the first buffer memory groove 7c is injected in the electrolytic system 7b of described electrolyzer 7 and the cathode compartment of electricity-electrodialysis system 7a and is separated out copper by pipeline 16, be used for reducing copper content, realize chemical regeneration, and then become low copper containing amount acidic etching liquid, 17 return in the first buffer memory groove 7c by the road.
Described low copper containing amount acidic etching liquid 19 turns back in the first 6b of overflow chamber of described reactor more by the road, with this, carrys out the concentration of copper in the useless acidic etching liquid 2 of balance;
Enter into useless acidic etching liquid 2 and low copper containing amount acidic etching liquid in the first 6b of overflow chamber, after mixing, wherein a part is injected in the anolyte compartment of described electrolytic system by pipeline 10, after reaction, by pipeline 12, returns; Another part will flow to the second 6c of overflow chamber;
Enter into the useless acidic etching liquid in the second 6c of overflow chamber, wherein a part is connected with the intermediate chamber of described electricity-electrodialysis system 7a by pipeline 11, reaction is returned by pipeline 13, and another part carries out regenerating oxidation reaction again by continuing to flow to the 6d of San overflow chamber.
Finally, the acidic etching liquid after regeneration is finally got back to the nozzle 4 of etching machine 1 by pipeline 20, starts the circulation of a new round.
Concrete,
Containing [CuCl
2]
-useless acidic etching liquid enter in a reactor, by electric chemical formula (1) (4) (5) oxidation, generate [CuCl
2]
+,
2CuCl
2-+2H
++1/2O
2→2CuCl
++2Cl
-+H
2O；（1），
2CuCl
2 -+1/3ClO
3 -+2H
+→2CuCl
++H
2O+7/3Cl
- （4）；
2CuCl
2-+Cl
2+4H
+→2CuCl
++HCl （5）。
One electrolyzer being connected with described reactor comprises one electricity-electrodialysis system and an electrolytic system, described electricity-electrodialysis system and electrolytic system by electric chemical formula (2) for required reactant gases is provided in described reactor:
H
2O→2H
++1/2O
2+2e
- （2），
Described electrolytic system by electric chemical formula (3) (7) (8) for accelerator is provided in described reactor:
Cl
-+3H
2O→ClO
3 -+6H
++6e
- （3），
2Cl
-→Cl
2+2e
- （7）；
Cl
2+6H
2O→2ClO
3 -+12H
++12e
- （8）。
[the CuCl obtaining in described reactor
2]
+being recycled to acidic etching liquid uses in station.
Further, in described electricity-electrodialysis system and electrolytic system, according to electric chemical formula (6), reclaim copper,
CuCl
++2e
-→Cu+Cl
- （6）。
Further, described electricity-electrodialysis system provides extra acidic solution by electric chemical formula (9) for acidic etching liquid,
2H
++2Cl
-→2HCl （9）。
In the present invention, reactor is mainly that the Cu (I) that etching material is produced is oxidized to Cu (II).In reactor, comprise three overflows and once pre-overflow, be used for reducing flow velocity and by once circulating to improve the reaction times to each overflow increase.Each overflow comprises the injection pumping with magnetite parcel, and benefit is when gas/liquid mixture is passed through magnetic field, can optionally pass through two kinds of copper complexs.In addition, consider that concentration is that 3% left and right diamagnetism Cu (I) complex compound is different concentration and the magnetic-field patterns of 97% left and right paramagnetism Cu (II) complex compound with concentration, the collision probability that it can increase copper complex Cu (I) and spray the gas sucking in pumping.Subsequently, Cu (I) complex compound is forced to flow through and sprays outside the solution of pumping, and solution is because spraying the gas layering in pumping, thereby has optimized the oxidizing reaction of Cu (I) to Cu (II).
Through the useless acidic etching liquid in etch processes after etching machine, contain Cu (I), by the pre-overflow chamber being all sent in reactor, wherein sub-fraction will be injected into the first buffer memory groove 7c, and the cathode compartment that the first buffer memory groove 7c is connected to electrolyzer is used for reclaiming etch copper.Remaining major part will continue to flow in reactor through overflow for the first time, the anolyte compartment of the B compartment of overflow for the first time and electrolyzer continues the circulation of solution, oxidizing reaction is relied on the existence of perchlorate, add by means of magnetic and spray pumping from the gas of the cathode compartment extraction of etching machine, AB compartment, and the oxygen extracting from A compartment anolyte compartment starts to carry out.In addition, the solution in electrolyzer buffer memory groove after copper removal will be added to overflow for the first time, with this, reduce the concentration of copper in useless acidic etching liquid.
Through overflow for the first time partial regeneration and by the useless acidic etching liquid of copper removal, by flowing to overflow for the second time, carry out Cu (I) to the chemical oxidation reaction of Cu (II), therefore, the intermediate chamber of the A compartment of overflow for the second time and electrolyzer starts circulate soln, passes through H
+ion and Cl
-the movement of ion, etching solution is because the generation of HCl becomes abundant.In addition, by being furnished with magnetic, spray the internal recycling of pumping, in electrolyzer A, oxygen that the anolyte compartment in B compartment produces by being drawn out of and being injected into, in etching solution, gone following oxidizing reaction: [CuCl
2]
-+ H
++ 1/4O
2→ [CuCl]
++ Cl
-+ 1/2H
2o.
The regeneration of useless acidic etching liquid will be through completing after overflow for the third time in reactor, and after solution is injected in overflow for the second time, the remaining excess air O2 from electrolyzer is refilled, Cu
++cupric ion changes into complex copper [CuCl]
+thereby the oxidizing reaction of completing, complex copper [CuCl]
+derive from the oxidation of Cu (I).
In the present invention, useless acidic etching liquid, in the residence time through overflow each time, is at least 1 minute especially for the second time and for the third time.In addition, the flow that sprays pumping per minute is the twice of its specific spillway discharge, and take this as chemical reaction and regenerating provides the complete time.
In the present invention, in electrolyzer, the capacity of B compartment is no more than 10% of whole electrolyzer capacity, with this, avoids Cl in system
2concentration excessive.
The present invention should meet copper and reclaim and to realize again etching solution regeneration, just need to use an electrolyzer of being furnished with buffer memory groove, and electrolysis and electricity-electrodialytic combination not only can be reclaimed copper, can also produce the acidic etching liquid that the gives up required oxygen of regenerating, acid H
+with etching accelerator perchloric acid.
For keeping the concentration of copper in reprocessing cycle etching machine to be in optimum level at reactor, from the lower etching solution of the content of electrolyzer buffer memory buried copper, by according to the demand of system copper control device, be injected into and in reactor, carry out overflow for the first time.The cathode compartment circulation etching solution of the first buffer memory groove itself and electrolyzer, in cathode compartment, copper is by electrolysis.Simultaneously, sub-fraction will be stored in the buffer memory groove of electrolyzer from the spent etching solution in the pre-overflow chamber of etching machine reactor, because the concentration of the copper that it comprises is rising, speed is 1.5% to 3%, consider that the required energy of electrolysis Cu (I) is 1/2 of electrolysis Cu (II), according to following formula, this specific character will make the speed of electrolysis improve 1.5% to 3%:[CuCl]
++ 2e
-→ Cu+Cl
-, [CuCl
2]
-+ e
-→ Cu+2Cl
-.
Concrete example:
One is equipped with a flow velocity is 18, the etching machine of the pumping of 000l/h, per hour can etching 30kg copper, in etching solution, the concentration of copper is approximately 145g/l< totally 2,610kg Cu (II) >, according to following reaction [CuCl]
++ 3Cl
-+ Cu → 2[CuCl
2]
-, etching 30kg copper per hour can produce the Cu (I) of 60kg.Therefore, in the pre-overflow chamber of reaction chamber, will obtain comprising the solution of the Cu (I) of 97,7% Cu (II) and 2,27%.
On the other hand, in the useless acidic etching liquid that contains Cu (I) copper, lack oxydant, have the advantage of the etching speed that can reduce negative electrode, thereby improve the efficiency that copper reclaims.
In the present invention, in electrolyzer, cathode compartment comprises a cathode titanium plates and an anionic membrane, and current density is 1 to 10A/m
2between.The liquid passing through need keep low speed, and the voltage between negative electrode and anode is no more than 10V, with the loss of avoiding causing because of heating.
According to following chemical reaction in cathode compartment: [CuCl]
++ 2e
-→ Cu+Cl
-, [CuCl
2]
-+ e
-→ Cu+2Cl
-, will obtain metallic copper and chlorion, they can move to the anolyte compartment of B compartment and the intermediate chamber of A compartment.
Form that it should be noted that gained copper depends on the content of copper in cathode solution: in cathode solution, the concentration of copper is less than 20g/l, and current density is greater than 5A/dm
2time, copper is by the form with copper powder by electrolysis, and when the concentration of copper is higher than 20g/l, current density is less than 5A/dm
2time, copper by the copper coin form with compact by electrolysis.
In order to produce by electrolyzer, realize useless acidic etching liquid regenerate required oxygen and acid H
+, the A compartment of electrolyzer has three cells, Yi Ge anolyte compartment, an intermediate chamber, a cathode compartment.Intermediate chamber and anolyte compartment are separated by a cationic membrane, and cathode compartment is separated by an anionic membrane.Anolyte compartment comprises sulfuric acid (H
2sO
4) solution and titanium plate electrode, the suitable concentration of sulfuric acid is between 10% to 20%, current density is 1 to 5A/dm
2.According to the chemical reaction of anolyte compartment: H
2o → 1/2O
2+ 2H
+, O will produce oxygen
2, this oxygen O
2by in the useless acidic etching liquid in the overflow for the first time that is extracted and is injected in reactor.Under the effect of electric field, H
+enter intermediate chamber and in solution, form acid HCl, in intermediate chamber solution and reactor, overflow for the second time circulates subsequently.
For producing the accelerator perchlorate that can accelerate electrolytic copper speed by means of electrodialytic membranes, the B compartment of electrolyzer comprises two boothes, Yi Ge anolyte compartment and a cathode compartment, and according to following chemical reaction, anode will produce perchlorate, acid and oxygen:
Cl
-+3H
2O→ClO
3 -+6H
++6e
-
H
2O→2H
++1/2O
2+2e
-
In a word, the acid etching liquid of holomorphosis will continuously offer the spray boom of etching machine, through etch process, gets back in reactor again as useless etching solution.Sub-fraction solution in reactor Nei Yu overflow chamber will directly import the cathode compartment of electrolyzer, reduces the concentration of copper in solution by electrolysis, and remaining major part is by the processing through two other continuous cell in reactor.These two cells are connected with electrolyzer anode chamber, and the oxygen of generation is oxidized to Cu (II) by Cu (I), produce HCl and are used for acidifying and produce solution, and etching accelerator perchlorate is also added in solution.The 3rd Room in reactor will offer etching machine spray boom and be rich in [CuCl
2]
-the etching acidic solution of holomorphosis, thereby repeat etching and the recovery in another cycle.
Secondly, the present invention has improved stability and the handiness of etching process, will greatly improve etch process.There is chemical unmatched phenomenon between the amount of etch copper and the amount of reclaiming in tradition etch process, no matter is the supply of etching solution, discharge or copper recovery system.For obtaining stable progress of etching, must keep the concentration of Cu (I) below 0,01%, thereby a good etching result just can be provided.Therefore,, in the present invention, etching machine and electrolyzer synchronous operation, continue with this regeneration etching solution that provides required, and be not subject to the impact of fluctuation.Therefore, the interruption of any regenerative process that etching process is had a negative impact will can not occur.
According to for example following, the metallic copper of etching 1kg:
(1) copper that 2kg exists with Cu (I) form produces according to following formula: [CuCl]
++ 3Cl
-+ Cu → 2[CuCl
2]
-.
(2), when reclaiming the etch copper of 1kg in etching machine, in tank room, the oxygen O of 251.8gr will be produced
2, the HCl of 574.44gr.
(3) will the regenerate Cu (I) of the 2kg that produces in etching machine, according to following formula, needs the oxygen O of 251.8gr
2with the HCl of 574.44gr, [CuCl
2]
-+ H
++ 1/4O
2→ [CuCl]
++ Cl-+1/2H
2o.
Therefore the gas, producing in electrolytic process and sour amount are equal to the required amount of regeneration.In above-mentioned illustration, regeneration 2kg Cu (I) required amount of reagent is equal to the amount that in electrolyzer, accelerator compartment (B compartment) anode produces, accelerator compartment must and etching machine synchronous operation with this, guarantee etching and reclaim between balance.In addition, electrolyzer need comprise two compartments, wherein accelerator compartment must be when etching material reduces work take that this provides enough reagent as continuous regenerative process.
A substantive distinguishing features of the present invention is that the acidic etching liquid in the water reservoir of the useless acidic etching liquid technique of processing, through reclaiming and processing respectively, is then sprayed at the nozzle of directly supplying with etching machine on printed circuit board (PCB).Meanwhile, used and/or useless acidic etching liquid will be collected, and process subsequently through useless acidic etching liquid treatment process/system, be re-used as afterwards the nozzle that high-quality etching solution offers etching machine.
The present invention is not limited to aforementioned embodiments, and those skilled in the art, under the enlightenment of the technology of the present invention marrow, also may make other changes, but as long as function and the present invention of its realization are same or similar, all should belong to protection scope of the present invention.
Claims (12)
1. an electrolyzer, is characterized in that: comprise be provided with electricity-electrodialysis system A compartment and in be provided with the B compartment of electrolytic system, described A compartment comprises for generation of reactant gases O
2first anode chamber; For reclaiming the first cathode compartment of copper, and be placed in described first anode chamber and and the first cathode compartment between intermediate chamber; Described B compartment comprises for generation of reactant gases O
2with accelerator ClO
3 -second anode chamber, and for reclaiming the second cathode compartment of copper.
2. electrolyzer according to claim 1, is characterized in that: described B compartment comprises 2 second anode chambers and 2 the second cathode compartments, and described second anode chamber and the second cathode compartment interval arrange.
3. right to use requires an etching solution reclaim equiment for the electrolyzer described in 1, it is characterized in that: comprise,
One reactor being connected with etching liquid pool in etching machine, described reactor comprises Yi Geyu overflow chamber and first, second, third overflow chamber, described etching solution Cong Yu overflow chamber enters San Ge overflow chamber after flowing out according to the order of sequence,
One electrolyzer being connected with described reactor, in described electrolyzer comprises, be provided with electricity-electrodialysis system A compartment and in be provided with the B compartment of electrolytic system, described A compartment comprises for generation of reactant gases O
2first anode chamber; For reclaiming the first cathode compartment of copper, and be placed in described first anode chamber and and the first cathode compartment between intermediate chamber; Described B compartment comprises for generation of reactant gases O
2with accelerator ClO
3 -second anode chamber, and for reclaiming the second cathode compartment of copper;
Described electrolyzer also comprises the first buffer memory groove and the second buffer memory groove, the entrance of described the first buffer memory groove is connected with described pre-overflow chamber, the outlet of described the first buffer memory groove is connected with described the first overflow chamber, described the first buffer memory groove is also communicated with the first cathode compartment and the second cathode compartment in described electrolyzer, described first anode chamber is communicated with the second buffer memory groove, described intermediate chamber is communicated with the second overflow chamber, described second anode chamber is communicated with the first overflow chamber, between described reactor and electrolyzer, be also provided with gas piping and both are coupled together, the outlet of described San overflow chamber is connected in etching liquid pool or the etching solution shower nozzle in described etching machine.
4. etching solution reclaim equiment according to claim 3, it is characterized in that: between described first anode chamber and intermediate chamber, be provided with only for positively charged ion and enter into the cationic membrane in intermediate chamber from described first anode chamber, between described intermediate chamber and the first cathode compartment, be provided with only for negatively charged ion and enter into the anionic membrane in intermediate chamber from described the first cathode compartment.
5. etching solution reclaim equiment according to claim 3, is characterized in that: in described the first cathode compartment and the second cathode compartment, be provided with titanium plate electrode, current density is 1 to 10A/dm
2between.
6. etching solution reclaim equiment according to claim 3, is characterized in that: indoor sulphuric acid soln and the titanium plate electrode of comprising of the described first anode, and the suitable concentration of sulfuric acid is between 10% to 20%, current density is 1 to 5A/dm
2.
7. etching solution reclaim equiment according to claim 3, it is characterized in that: the gas piping being provided with between described reactor and electrolyzer specifically comprises: the pneumatic outlet of the first anode chamber of the first cathode compartment of described A compartment, the second cathode compartment of B compartment and A compartment is connected with the gas inlet of the first overflow chamber by gas piping, and the pneumatic outlet of the second anode chamber of described B compartment is connected with the gas inlet of the second overflow chamber.
8. etching solution reclaim equiment according to claim 3, it is characterized in that: described inside reactor pipeline comprises: the excess air outlet of described the first overflow chamber is connected with the gas inlet of the second overflow chamber, the excess air outlet of described the second overflow chamber is connected with the gas inlet of San overflow chamber.
9. an etching solution regeneration method, it is characterized in that: by the reactor being interconnected and electrolyzer, completed, described reactor comprises first, second, third He Yigeyu overflow chamber, overflow chamber, described electrolyzer is by electricity-electrodialysis system, electrolytic system, form with the first buffer memory groove, the second buffer memory groove
Described regenerated acidic etching solution method comprises the steps,
Containing [CuCl
2]
-useless acidic etching liquid enter to the pre-overflow chamber in described reactor;
The useless acidic etching liquid Cong Yu of sub-fraction is injected in the first buffer memory groove of electrolyzer in overflow chamber, and remaining useless acidic etching liquid will flow to the first overflow chamber;
Enter to useless acidic etching liquid in the first buffer memory groove and be injected in the electrolytic system of described electrolyzer and the cathode compartment of electricity-electrodialysis system and separate out copper, and then become low copper containing amount acidic etching liquid and return in the first buffer memory groove,
Described low copper containing amount acidic etching liquid turns back in the first overflow chamber of described reactor;
Enter into after the useless acidic etching liquid and the mixing of low copper containing amount acidic etching liquid in the first overflow chamber, wherein a part is injected in the anolyte compartment of described electrolytic system, after reaction, returns; Another part will flow to the second overflow chamber;
Enter into the useless acidic etching liquid in the second overflow chamber, wherein a part is connected with the intermediate chamber of described electricity-electrodialysis system, after reaction, returns, and another part will continue to flow to San overflow chamber,
Acidic etching liquid after regeneration is finally got back to the nozzle of etching machine by pipeline.
10. etching solution regeneration method according to claim 9, is characterized in that: the solution of the middle storage of described the second buffer memory groove is H
2sO
4, by the indoor H of the first anode in pumping and electricity-electrodialysis system
2sO
4solution circulates.
11. etching solution regeneration methods according to claim 9, is characterized in that: the gas O producing in the anolyte compartment of described electricity-electrodialysis system
2be imported in the first overflow chamber the O that electrolytic system anolyte compartment produces
2with accelerator ClO
3 -be injected in the second overflow chamber.
12. etching solution regeneration methods according to claim 9, is characterized in that: first, second, third overflow chamber is when being injected into gas, all through the injection pumping of a use magnetite parcel in described reactor.
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| CN201410001343.XA CN103757664B (en) | 2013-12-13 | 2014-01-02 | Electrolysis bath, using etching solution generating apparatus and the renovation process again of the electrolysis bath |
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| CN201420001773.7U Withdrawn - After Issue CN203741422U (en) | 2013-12-13 | 2014-01-02 | Rinsing water circulation system |
| CN201410001343.XA Active CN103757664B (en) | 2013-12-13 | 2014-01-02 | Electrolysis bath, using etching solution generating apparatus and the renovation process again of the electrolysis bath |
| CN201410001129.4A Active CN103966608B (en) | 2013-12-13 | 2014-01-02 | Gas circulation method in a kind of gas-recycling plant and device |
| CN201410001530.8A Active CN103757635B (en) | 2013-12-13 | 2014-01-02 | Electrolysis bath and use regenerated acidic etching solution equipment and the renovation process of this electrolysis bath |
| CN201420001658.XU Expired - Lifetime CN203741421U (en) | 2013-12-13 | 2014-01-02 | Equipment capable of regenerating acidic etching solution |
| CN201420001975.1U Expired - Lifetime CN203741423U (en) | 2013-12-13 | 2014-01-02 | Electrolytic cell for regeneration of acidic etching solution |
| CN201420000816.XU Expired - Fee Related CN203743090U (en) | 2013-12-13 | 2014-01-02 | Magnetic jet pump |
| CN201410001324.7A Active CN103757634B (en) | 2013-12-13 | 2014-01-02 | A kind of rinse water recycle system and rinse water circulation means |
| CN201420001494.0U Expired - Lifetime CN203834017U (en) | 2013-12-13 | 2014-01-02 | Gas circulating device |
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| CN201410001530.8A Active CN103757635B (en) | 2013-12-13 | 2014-01-02 | Electrolysis bath and use regenerated acidic etching solution equipment and the renovation process of this electrolysis bath |
| CN201420001658.XU Expired - Lifetime CN203741421U (en) | 2013-12-13 | 2014-01-02 | Equipment capable of regenerating acidic etching solution |
| CN201420001975.1U Expired - Lifetime CN203741423U (en) | 2013-12-13 | 2014-01-02 | Electrolytic cell for regeneration of acidic etching solution |
| CN201420000816.XU Expired - Fee Related CN203743090U (en) | 2013-12-13 | 2014-01-02 | Magnetic jet pump |
| CN201410001324.7A Active CN103757634B (en) | 2013-12-13 | 2014-01-02 | A kind of rinse water recycle system and rinse water circulation means |
| CN201420001494.0U Expired - Lifetime CN203834017U (en) | 2013-12-13 | 2014-01-02 | Gas circulating device |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103757635B (en) | 2016-11-23 |
| CN103757634B (en) | 2016-04-20 |
| CN203741423U (en) | 2014-07-30 |
| CN203743090U (en) | 2014-07-30 |
| CN203741422U (en) | 2014-07-30 |
| CN203834017U (en) | 2014-09-17 |
| CN103757664B (en) | 2017-04-05 |
| CN103757634A (en) | 2014-04-30 |
| CN103966608A (en) | 2014-08-06 |
| CN103757635A (en) | 2014-04-30 |
| CN203741421U (en) | 2014-07-30 |
| CN103966608B (en) | 2018-05-22 |
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