CN203741422U - Rinsing water circulation system - Google Patents
Rinsing water circulation system Download PDFInfo
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- CN203741422U CN203741422U CN201420001773.7U CN201420001773U CN203741422U CN 203741422 U CN203741422 U CN 203741422U CN 201420001773 U CN201420001773 U CN 201420001773U CN 203741422 U CN203741422 U CN 203741422U
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- compartment
- cathode compartment
- intermediate chamber
- rinse water
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Water Treatment By Electricity Or Magnetism (AREA)
- Jet Pumps And Other Pumps (AREA)
Abstract
The utility model provides a rinsing water circulation system of an etching solution regeneration system. The rinsing water circulation system comprises an electro-electro dialyzer, an electordialyzer and a permeator. The regulation of salinity in the rinsing water and purification of the rinsing water are carried out by the electro-electro dialyzer, the electordialyzer and the permeator. The rinsing water circulation system is connected with the etching solution regeneration system so that the rinsing water can be recycled and regenerated continuously. The rinsing water circulation system disclosed by the utility model has prominent benefits that the electrolytic cell has a simple and compact structure and can provide an accelerator and reaction gas required for the regeneration process very well; the rinsing water can be circulated continuously and no any additive for the regeneration is added into the entire regeneration process.
Description
Technical field
The present invention relates to a kind of and the rinse water recycle system and rinse water circulation means etching solution equipment connection, 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.Meanwhile, the processing of rinse water is also a hang-up.
Summary of the invention
In view of the defect that above-mentioned prior art exists, the object of the invention is to propose the recycle system and the rinse water circulation means of rinse water in a kind of etching solution equipment.
Object of the present invention will be achieved by the following technical programs:
A rinse water recycle system, the described rinse water recycle system is connected with the rinsing chamber in etching solution equipment;
Described rinsing indoor separation has first, second, third cleaning shop, is provided with for scavenging solution being sprayed to the cleaning shower nozzle of product in three described cleaning shops;
The described rinse water recycle system comprises one electricity-electrodialyzer, an electrodialyzer and a permeator;
Described electricity-electrodialyzer comprises the 3rd cathode compartment, third anode chamber, and be placed in the 3rd intermediate chamber between the 3rd cathode compartment and third anode chamber, described electrodialyzer comprises Si anolyte compartment, the 4th cathode compartment, and is placed in the 4th intermediate chamber between the 4th cathode compartment and Si anolyte compartment;
Described the 3rd intermediate chamber entrance is connected by pipeline with the first cleaning shop outlet, and the outlet of the 3rd intermediate chamber is connected with the entrance of the first cleaning shop, and described third anode chamber is connected by pipeline with etching solution regeneration system rapidly with the 3rd cathode compartment;
The Si anolyte compartment of described electrodialyzer, the 4th intermediate chamber and the 4th cathode compartment entrance are all connected by pipeline with the outlet of the first cleaning shop, Si anolyte compartment, the 4th intermediate chamber and the 4th cathode compartment outlet are connected with the import of the first cleaning shop, the 4th intermediate chamber entrance of described electrodialyzer is connected with the first outlet of the second cleaning shop, and intermediate chamber outlet is connected with the first entrance of the second cleaning shop;
The entrance of described permeator is connected with the second outlet of the second cleaning shop, and the concentrated solution outlet of permeator is connected with the second entrance of the second cleaning shop, and the clear water output of permeator is connected with the entrance of the 3rd cleaning shop.
Preferably, in described the 4th intermediate chamber, be provided with concentrated solution, described concentrated solution refers to the solution in the first cleaning shop.
Preferably, in described electricity-electrodialyzer and electrodialyzer, the width of cathode compartment is more than or equal to 7cm.
Preferably, described etching solution regeneration system rapidly comprises reactor and the electrolyzer being connected with described reactor;
Described reactor comprises Yi Geyu overflow chamber and first, second, third overflow chamber, and described etching solution Cong Yu overflow chamber enters San Ge overflow chamber after flowing out according to the order of sequence;
In described electrolyzer, be provided with A compartment and B compartment, described A compartment comprises first anode chamber, intermediate chamber, the first cathode compartment; Between described first anode chamber and intermediate chamber, be provided with cationic membrane, between described intermediate chamber and the first cathode compartment, be provided with anionic membrane; Described B compartment comprises second anode chamber and the second cathode compartment;
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, and 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;
Described third anode chamber is connected by pipeline with the outlet of the first buffer memory groove with the entrance of the 3rd cathode compartment, and third anode chamber is connected with the entrance of the first buffer memory groove with the outlet of the 3rd cathode compartment.
Preferably, between described third anode chamber and the 3rd intermediate chamber, be provided with only for negatively charged ion and enter into the indoor cationic membrane of third anode from described the 3rd intermediate chamber, between described the 3rd intermediate chamber and the 3rd cathode compartment, be provided with only for positively charged ion and enter into the anionic membrane in the 3rd cathode compartment from described the 3rd intermediate chamber.
Preferably, between described Si anolyte compartment and the 4th intermediate chamber, be provided with only for positively charged ion and enter into the anionic membrane in the 4th intermediate chamber from described Si anolyte compartment, between described the 4th intermediate chamber and the 4th cathode compartment, be provided with only for negatively charged ion and enter into the cationic membrane in the 4th intermediate chamber from described the 4th cathode compartment.
Preferably, in described the 4th intermediate chamber, be provided with the zwitterion film that at least two group spaces arrange.
A rinse water circulation means for the rinse water recycle system, comprises following process,
The regulate process of rinse water self salts contg in the first cleaning shop: the rinse water of described the first cleaning shop enter into the 3rd intermediate chamber of electricity-electrodialyzer by pipeline, simultaneously, solution in maintenance electricity-electrodialyzer third anode chamber and the 3rd cathode compartment and the solution in the first buffer memory groove circulate, and reduce the salts contg of rinse water;
The supplementary process of rinse water salts contg in the first cleaning shop: the rinse water of the second cleaning shop enter into the 4th intermediate chamber of electrodialyzer by pipeline, and enter into the first cleaning shop by pipeline, make the first cleaning shop obtain salts contg in the second cleaning shop;
The scavenging process of rinse water: the rinse water of the second cleaning shop enter into permeator by pipeline, by the purification of permeator, the rinse water after purification enter into the 3rd cleaning shop, and the rinse water of permeator concentrating part return and enter into the second cleaning shop.
Preferably, the salts contg of described the first cleaning shop rinse water is the content that comprises the salt of perchlorate and hydrochloride.
Preferably, the solution circulating in the solution in described electricity-electrodialyzer third anode chamber and the 3rd cathode compartment and the first buffer memory groove is etching solution.
Preferably, the concrete steps of the regulate process of rinse water self salts contg are in described the first cleaning shop, and the reaction formula of the third anode chamber by electricity-electrodialyzer produces acid: H
2o → 2H+1/2O
2+ 2e
-, 2Cl
-+ 6H
2o → 2ClO
3 -+ 12H
++ 12e
-, by the following reaction formula of the 3rd cathode compartment, reclaim copper: Cu
2++ 2e
-→ Cu, 2H
++ 2e
-→ H
2.
Preferably, the supplementary process concrete steps of rinse water salts contg are in described the first cleaning shop: the following reaction formula of the Si anolyte compartment by electrodialyzer produces acid: H
2o → 2H+1/2O
2+ 2e
-, Cl
-+ 3H
2o → ClO
3 -+ 6H
++ 6e
-; Following reaction formula by the 4th cathode compartment reclaims copper: Cu
2++ 2e
-→ Cu, 2H
++ 2e
-→ H
2.
Preferably, the third anode chamber of described electricity-electrodialyzer comprises hydrochloric acid and perchloric acid, the Si anolyte compartment of electrodialyzer produces acid.
Certainly, in the anolyte compartment of above A compartment and B compartment, also can produce the volatile component of the solution such as some water vapour and acid, copper.
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, rinse water are constantly circulated, whole regenerative process does not need to add the additive of any regeneration use.
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 rinse water recycle system of the present invention, comprises etching solution regeneration system rapidly structural representation.
Fig. 2 is in the rinse water recycle system of the present invention, and the ionic current of rinse water in electricity-electrodialyzer is to schematic diagram.
Fig. 3 is in the rinse water recycle system of the present invention, and the ionic current of rinse water in electrodialyzer is to schematic diagram.
Embodiment
The present invention has disclosed a kind of equipment of can regenerated acidic etching solution and reclaiming copper.
As shown in Figure 1, 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.
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
-.
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 this 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.
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.This treatment process comprises two steps: one is etching solution regeneration and copper recovery, and another is the processing of the wash-down water that partly produces of waste gas and etching machine rinsing.
The recycling of excess air and washing water is divided into two independently treatment systems.
Below in conjunction with Fig. 2, Fig. 3, describe the recycle system to rinse water in etching machine in lower the present invention, the recycle system comprises electricity-electrodialyzer 23, electrodialyzer 22 and permeator 21;
In described rinsing chamber 5, divide and be separated with the first cleaning shop 5a, the second cleaning shop 5b, the 3rd cleaning shop 5c, in three cleaning shops, be provided with for scavenging solution being sprayed to the cleaning shower nozzle of product.
In rinsing chamber 5, the highly polluted rinse water in the first cleaning shop 5a place flow to the intermediate chamber of electricity-electrodialyzer 23 by minute pipeline 24a of pipeline 24, and the 25b that is in charge of by pipeline 25 turns back to the first cleaning shop 5a place subsequently.The anolyte compartment of electricity-electrodialyzer 23 and cathode compartment are by minute pipeline 31a of pipeline 31, and 31b is connected with the first buffer memory groove 7c of electrolyzer 7, and by minute pipeline 32a of pipeline 32,32b realizes the circulation of useless acidic etching liquid.By the electric field of 23 li of foundation of electricity-electrodialyzer, negatively charged ion will be through cationic membrane trip anode chamber, simultaneously, positively charged ion is through cationic membrane trip to cathode compartment, and subsequently, anolyte compartment produces acid, cathode compartment reclaims copper, thereby reduces the pollution level of the first cleaning shop 5a place rinse water in rinsing chamber 5.
By the 24b that is in charge of of pipeline 24, the first contaminated rinse water in cleaning shop 5a place are sent to the anolyte compartment of electrodialyzer 22, cathode compartment and the intermediate chamber that has concentrated solution, and 25 the 25b that is in charge of returns by the road subsequently.On the one hand, this,, by purifying the rinse water at the second cleaning shop 5b place, on the other hand the salts contg in solution is transferred to the first cleaning shop 5a place, and the first cleaning shop 5a itself reduces saliferous rate by electricity-electrodialyzer 23.
More than can complete the intermediate chamber of rinse water and electricity-electrodialyzer 23 for the first time and circulate, effects of ion trip anode chamber and cathode compartment, anolyte compartment and cathode compartment all carry out the circulation of solution with the first buffer memory groove 7c, thereby have reduced the saliferous rate in rinse water.Meanwhile, the intermediate chamber of the power and water dialyzer 22 of rinse stage circulates for the first time, and from obtaining salinity rinse water for the second time, between electrodialyzer 22 anodes and negative electrode, such water cycle makes ion trip to intermediate chamber.
The third anode chamber of the above electricity-electrodialyzer produces acid: H by reaction formula
2o → 2H+1/2O
2+ 2e
-, 2Cl
-+ 6H
2o → 2ClO
3 -+ 12H
++ 12e
-, the 3rd cathode compartment reclaims copper: Cu by following reaction formula
2++ 2e
-→ Cu, 2H
++ 2e
-→ H
2.
The Si anolyte compartment of described electrodialyzer produces acid: H by following reaction formula
2o → 2H+1/2O
2+ 2e
-, Cl
-+ 3H
2o → ClO
3 -+ 6H
++ 6e
-; The 4th cathode compartment reclaims copper: Cu by following reaction formula
2++ 2e
-→ Cu, 2H
++ 2e
-→ H
2.
Above reaction formula is all only with ionic species, to embody, and the reaction in solution between material is not all listed at this.
Finally, the solution that in this circulation, saliferous rate reduces will be imported into permeator 21, from permeator 21, produce be cleaned water will offer last rinse stage, concentrated solution will be restored to rinse stage for the second time.Described permeator 21 is conventional permeator in prior art, and concrete principle and process are not described in detail in this.
According to the design of unit for treating water, in electricity-electrodialyzer and electrodialyzer, the width of cathode compartment minimum is 7cm, thereby can from these chambers, reclaim like a cork electrolytic copper.
In this invention, a permeator 21 is connected with electrodialyzer 22.In rinsing chamber 5, the second contaminated rinse water in cleaning shop 5b place import permeator 21 by pipeline 28.Wherein, the water after purification imports the 3rd cleaning shop 5c place of rinsing chamber 5 through pipeline 30.Concentrating part will 29 import the second cleaning shop 5b place by the road.Finally, the second cleaning shop 5b place provides rinse water, the rinse water after therefrom being diluted by pipeline 27 again to the dilution chamber of electrodialyzer 22 by pipeline 26.
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 (8)
1. a rinse water recycle system, is characterized in that: the described rinse water recycle system is connected with the rinsing chamber in etching solution equipment;
Described rinsing indoor separation has first, second, third cleaning shop, is provided with for scavenging solution being sprayed to the cleaning shower nozzle of product in three described cleaning shops;
The described rinse water recycle system comprises one electricity-electrodialyzer, an electrodialyzer and a permeator;
Described electricity-electrodialyzer comprises the 3rd cathode compartment, third anode chamber, and be placed in the 3rd intermediate chamber between the 3rd cathode compartment and third anode chamber, described electrodialyzer comprises Si anolyte compartment, the 4th cathode compartment, and is placed in the 4th intermediate chamber between the 4th cathode compartment and Si anolyte compartment;
Described the 3rd intermediate chamber entrance is connected by pipeline with the first cleaning shop outlet, and the outlet of the 3rd intermediate chamber is connected with the entrance of the first cleaning shop, and described third anode chamber is connected by pipeline with etching solution regeneration system rapidly with the 3rd cathode compartment;
The Si anolyte compartment of described electrodialyzer, the 4th intermediate chamber and the 4th cathode compartment entrance are all connected by pipeline with the outlet of the first cleaning shop, Si anolyte compartment, the 4th intermediate chamber and the 4th cathode compartment outlet are connected with the import of the first cleaning shop, the 4th intermediate chamber entrance of described electrodialyzer is connected with the first outlet of the second cleaning shop, and intermediate chamber outlet is connected with the first entrance of the second cleaning shop;
The entrance of described permeator is connected with the second outlet of the second cleaning shop, and the concentrated solution outlet of permeator is connected with the second entrance of the second cleaning shop, and the clear water output of permeator is connected with the entrance of the 3rd cleaning shop.
2. a kind of rinse water recycle system as claimed in claim 1, is characterized in that: in described the 4th intermediate chamber, be provided with concentrated solution, described concentrated solution refers to the solution in the first cleaning shop.
3. a kind of rinse water recycle system as claimed in claim 1, is characterized in that: in described electricity-electrodialyzer and electrodialyzer, the width of cathode compartment is more than or equal to 7cm.
4. a kind of rinse water recycle system as claimed in claim 1, is characterized in that: described etching solution regeneration system rapidly comprises reactor and the electrolyzer being connected with described reactor;
Described reactor comprises Yi Geyu overflow chamber and first, second, third overflow chamber, and described etching solution Cong Yu overflow chamber enters San Ge overflow chamber after flowing out according to the order of sequence;
In described electrolyzer, be provided with A compartment and B compartment, described A compartment comprises first anode chamber, intermediate chamber, the first cathode compartment; Between described first anode chamber and intermediate chamber, be provided with cationic membrane, between described intermediate chamber and the first cathode compartment, be provided with anionic membrane; Described B compartment comprises second anode chamber and the second cathode compartment;
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, and 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;
Described third anode chamber is connected by pipeline with the outlet of the first buffer memory groove with the entrance of the 3rd cathode compartment, and third anode chamber is connected with the entrance of the first buffer memory groove with the outlet of the 3rd cathode compartment.
5. a kind of rinse water recycle system as claimed in claim 1, it is characterized in that: between described third anode chamber and the 3rd intermediate chamber, be provided with only for negatively charged ion and enter into the indoor cationic membrane of third anode from described the 3rd intermediate chamber, between described the 3rd intermediate chamber and the 3rd cathode compartment, be provided with only for positively charged ion and enter into the anionic membrane in the 3rd cathode compartment from described the 3rd intermediate chamber.
6. a kind of rinse water recycle system as claimed in claim 1, it is characterized in that: between described Si anolyte compartment and the 4th intermediate chamber, be provided with only for positively charged ion and enter into the anionic membrane in the 4th intermediate chamber from described Si anolyte compartment, between described the 4th intermediate chamber and the 4th cathode compartment, be provided with only for negatively charged ion and enter into the cationic membrane in the 4th intermediate chamber from described the 4th cathode compartment.
7. a kind of rinse water recycle system as claimed in claim 6, is characterized in that: in described the 4th intermediate chamber, be provided with the zwitterion film that at least two group spaces arrange.
8. a kind of rinse water recycle system as claimed in claim 4, is characterized in that: the solution circulating in the solution in described electricity-electrodialyzer third anode chamber and the 3rd cathode compartment and the first buffer memory groove is etching solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201420001773.7U CN203741422U (en) | 2013-12-13 | 2014-01-02 | Rinsing water circulation system |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310681244 | 2013-12-13 | ||
| CN201310681244.6 | 2013-12-13 | ||
| CN201420001773.7U CN203741422U (en) | 2013-12-13 | 2014-01-02 | Rinsing water circulation system |
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| CN203741422U true CN203741422U (en) | 2014-07-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201420001658.XU Expired - Lifetime CN203741421U (en) | 2013-12-13 | 2014-01-02 | Equipment capable of regenerating acidic etching solution |
| CN201420000816.XU Expired - Fee Related CN203743090U (en) | 2013-12-13 | 2014-01-02 | Magnetic jet pump |
| CN201420001975.1U Expired - Lifetime CN203741423U (en) | 2013-12-13 | 2014-01-02 | Electrolytic cell for regeneration of acidic etching solution |
| 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 |
| CN201410001324.7A Active CN103757634B (en) | 2013-12-13 | 2014-01-02 | A kind of rinse water recycle system and rinse water circulation means |
| 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 |
| CN201420001494.0U Expired - Lifetime CN203834017U (en) | 2013-12-13 | 2014-01-02 | Gas circulating device |
| CN201420001773.7U Withdrawn - After Issue CN203741422U (en) | 2013-12-13 | 2014-01-02 | Rinsing water circulation system |
| CN201410001129.4A Active CN103966608B (en) | 2013-12-13 | 2014-01-02 | Gas circulation method in a kind of gas-recycling plant and device |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201420001658.XU Expired - Lifetime CN203741421U (en) | 2013-12-13 | 2014-01-02 | Equipment capable of regenerating acidic etching solution |
| CN201420000816.XU Expired - Fee Related CN203743090U (en) | 2013-12-13 | 2014-01-02 | Magnetic jet pump |
| CN201420001975.1U Expired - Lifetime CN203741423U (en) | 2013-12-13 | 2014-01-02 | Electrolytic cell for regeneration of acidic etching solution |
| 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 |
| CN201410001324.7A Active CN103757634B (en) | 2013-12-13 | 2014-01-02 | A kind of rinse water recycle system and rinse water circulation means |
| 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 |
| CN201420001494.0U Expired - Lifetime CN203834017U (en) | 2013-12-13 | 2014-01-02 | Gas circulating device |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201410001129.4A Active CN103966608B (en) | 2013-12-13 | 2014-01-02 | Gas circulation method in a kind of gas-recycling plant and device |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103757634A (en) * | 2013-12-13 | 2014-04-30 | 陶克（苏州）机械设备有限公司 | Rinsing water circulating system and rinsing water circulating method |
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| CN105506728B (en) * | 2014-09-29 | 2019-10-15 | 盛美半导体设备（上海）有限公司 | The device of precipitating metal ion from electrochemical polish liquid |
| CN104914626B (en) * | 2015-06-04 | 2018-12-18 | 深圳市华星光电技术有限公司 | LCD alignment method |
| CN108348857A (en) * | 2015-09-18 | 2018-07-31 | 巴斯夫欧洲公司 | System and method for chemical rinses filtration system |
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| 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 |
| CN109487098B (en) * | 2018-12-20 | 2020-12-25 | 昆明理工大学 | Method and device for preparing Al-Ti-B refiner based on circulating gas reaction |
| CN109852996B (en) * | 2019-04-12 | 2024-02-23 | 株洲稷维环保有限公司 | Electrodeposition copper recovery device and copper recovery production line using same |
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- 2014-01-02 CN CN201420001658.XU patent/CN203741421U/en not_active Expired - Lifetime
- 2014-01-02 CN CN201420000816.XU patent/CN203743090U/en not_active Expired - Fee Related
- 2014-01-02 CN CN201420001975.1U patent/CN203741423U/en not_active Expired - Lifetime
- 2014-01-02 CN CN201410001530.8A patent/CN103757635B/en active Active
- 2014-01-02 CN CN201410001324.7A patent/CN103757634B/en active Active
- 2014-01-02 CN CN201410001343.XA patent/CN103757664B/en active Active
- 2014-01-02 CN CN201420001494.0U patent/CN203834017U/en not_active Expired - Lifetime
- 2014-01-02 CN CN201420001773.7U patent/CN203741422U/en not_active Withdrawn - After Issue
- 2014-01-02 CN CN201410001129.4A patent/CN103966608B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103757634A (en) * | 2013-12-13 | 2014-04-30 | 陶克（苏州）机械设备有限公司 | Rinsing water circulating system and rinsing water circulating method |
| CN103757634B (en) * | 2013-12-13 | 2016-04-20 | 陶克（苏州）机械设备有限公司 | A kind of rinse water recycle system and rinse water circulation means |
Also Published As
| Publication number | Publication date |
|---|---|
| CN203743090U (en) | 2014-07-30 |
| CN103757635A (en) | 2014-04-30 |
| CN203741421U (en) | 2014-07-30 |
| CN203741423U (en) | 2014-07-30 |
| CN103757634A (en) | 2014-04-30 |
| CN103757664B (en) | 2017-04-05 |
| CN103757664A (en) | 2014-04-30 |
| CN103966608A (en) | 2014-08-06 |
| CN103966608B (en) | 2018-05-22 |
| CN103757635B (en) | 2016-11-23 |
| CN203834017U (en) | 2014-09-17 |
| CN103757634B (en) | 2016-04-20 |
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