CN103966608A - Gas circulating device and method of gas circulation in device - Google Patents
Gas circulating device and method of gas circulation in device Download PDFInfo
- Publication number
- CN103966608A CN103966608A CN201410001129.4A CN201410001129A CN103966608A CN 103966608 A CN103966608 A CN 103966608A CN 201410001129 A CN201410001129 A CN 201410001129A CN 103966608 A CN103966608 A CN 103966608A
- Authority
- CN
- China
- Prior art keywords
- gas
- compartment
- chamber
- overflow chamber
- outlet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- ing And Chemical Polishing (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Jet Pumps And Other Pumps (AREA)
Abstract
The invention provides a gas circulating system connected with an etching liquid device as well as a method of gas circulation in the device. Harmful gas generated in an etching liquid regeneration process can be treated effectively through a condensing stage, a washing stage and an electrodialytic stage. The gas circulating system and the gas circulating method have the prominent effects as follows: an electrolytic cell for regeneration of the etching liquid is simple and compact in structure and can well provide a required accelerator and reaction gas for the regeneration process; any regeneration additive is not required to be added in the whole regeneration process; the stability and flexibility of an etching process are improved, and the etching technology can be greatly improved; and no harmful gas is exhausted eventually, and environmental protection is achieved.
Description
Technical field
The present invention relates to a kind of and gas-recycling plant and gas circulation method etching liquid equipment connection, belong to resource reutilization 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 waste gas is also a large problem.
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 and gas-recycling plant and gas circulation method etching liquid equipment connection.
Object of the present invention will be achieved by the following technical programs:
A kind of gas-recycling plant, described exhaust gas circulating device and etching solution equipment connection, described exhaust gas circulating device comprises the first electricity-electrodialyzer, a washer and a condenser, described etching solution equipment connection one 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;
The waste gas outlet of described San overflow chamber is connected with the entrance of described condenser, with so that the waste gas of San overflow chamber flows to condenser by pipeline, the pneumatic outlet of described condenser is connected with the gas inlet of washer, and the condensation product outlet of described condenser is connected with the first overflow chamber by pipeline;
Washings outlet in described washer is connected with the intermediate chamber import of the first electricity-electrodialyzer, and the intermediate chamber outlet of described the first electricity-electrodialyzer is connected by pipeline with cathode compartment entrance, and described cathode compartment outlet is connected with another inlet end of washer;
The outlet of described the first buffer memory groove is connected with anolyte compartment's entrance of the first electricity-electrodialyzer in gas-recycling plant, the outlet of anolyte compartment is connected with the entrance of the first buffer memory groove, uses so that the interior etching solution of the first buffer memory groove is back in the first buffer memory groove after obtaining the ion in washing soln;
Described washer is also provided with whole pneumatic outlet, for discharging the gas of final generation.
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 excessive outlet of gas 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.
Preferably, in described reactor, first, second, third overflow chamber, when being injected into gas, all needs the injection pumping through a use magnetite parcel.
Preferably, the gas O producing in the anolyte compartment of described A compartment
2.
Preferably, the gas producing in described B compartment anolyte compartment is O
2, HClO
3, HCl.
Preferably, described waste gas comprises O
2, HClO
3, HCl.
A gas circulation method in gas-recycling plant, comprises following condensation phase, washing stage and electrodialysis stage:
Condensation phase: the gas by San overflow chamber enters condenser by pipeline and carries out condensation, enters into the first overflow chamber through condensed material by pipeline;
Washing stage: the excess air producing after condenser being processed by the sodium hydroxide solution in washer is cleaned;
The electrodialysis stage: the sodium hydroxide solution after rinsing is first through the intermediate chamber in the first electricity-electrodialyzer, then enter into after cathode compartment is regenerated and get back to washer, wherein, negatively charged ion will move by cationic membrane anode chamber, positively charged ion moves to cathode compartment by anionic membrane, solution in solution in anolyte compartment and the first buffer memory groove circulates, and the negatively charged ion in described electrodialysis stage comprises Cl
-, ClO
-, ClO
3 -, positively charged ion comprises Na
+.
Preferably, the gas of described condensation phase comprises water vapor, hydrochloric acid, perchloric acid and complex copper.
Preferably, the anolyte compartment in described electrodialysis stage occurs to react so that the acid in system, H to be provided as follows
2o+2 (xCl
-, xOCl
-, xClO
3 -) → 2 (xHCl, xHOCl, xHClO
3)+1/2O
2+ 2e
-, described cathode compartment produces the sodium hydroxide solution in washer: 2H by following reaction
2o+2Na
++ 2e
-→ H
2+ 2N
a ++ 2OH
-.
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, whole regenerative process does not need to add the additive of any regeneration use; Finally without obnoxious flavour, discharge environmental protection.
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 the gas-recycling plant that is connected with etching solution regeneration system rapidly of the present invention, comprising the rinse water recycle system.
Fig. 2 is the reaction structure schematic diagram of etching solution of the present invention in reactor.
Embodiment
The present invention disclosed a kind of can regenerated acidic etching solution and the device for gas is circulated.
As shown in Figure 1 and Figure 2, 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
-.
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 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.
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.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.
The gas that etching machine and recovery system produce comprises water vapour, hydrochloric acid, perchloric acid and the complex copper of being hauled out substantially.Before entering and rinsing unit, these gases are first imported into condenser, and by water and the material condensation of being deviate from, these materials are by the first overflow chamber being sent in reactor.Condenser is one and by droplet separator, is divided into the right cylinder of four sections, comprising 5 coolships.The gas that in reactor, overflow for the third time produces sucks the blower fan of the device that is condensed, and is imported into right cylinder bottom.After 3 droplet separators and 5 coolships, make the temperature of gas above right cylinder lower than 10 ℃, thereby reach good condensation effect.In You Liangge air outlet, cylindrical top, the larger gas of temperature higher density of discharging from higher outlet, the blower fan being attached thereto is sucked to the condensation of carrying out a new round, the lower gas of density of discharging from lower outlet will enter washer first cylinder for washing.
Washing is divided into two steps.The first step, i.e. first right cylinder for washing, gas enters eminence from lower, the direction of solution rinsing in contrast, from high to low.Rinsing is via a special nozzle, and solution sprays with the form of spraying, with this, improves intermolecular contact.In addition, this right cylinder for washing, first paragraph comprises a separating layer being comprised of baton round, and this one deck is also for optimizing the contact of gas/liquid body.On plastic layer, having a nozzle, is a droplet separator on nozzle.The second step of washing need be by means of spraying pumping and nozzle, and gas will pass through the processing of four separating layers in this right cylinder: the first layer, baton round, second layer droplet separator, the 3rd layer, baton round, the 4th layer, droplet separator.Two are sprayed pumping suction from the gas in first washing right cylinder, inject second cylindrical bottom, then at right cylinder middle part and top, are subject to respectively the flushing from nozzles spray liquid.
Finally be washed rear completely clean gas and will be released to outside.
The solution using during cleaning is sodium hydroxide solution, its concentration 1,5%～8%, and temperature is between 5 ℃～20 ℃, and pH value is 7～8, with this, reaches neutralizing effect completely.
In rinse stage, will there is following chemical reaction:
HCl+NaOH → NaCl+H
2o principal reaction
Cl
2+ 2NaOH → NaCl+NaOCl almost can ignore
3Cl
2+ 6NaOH → 5NaCL+NaClO
3+ 3H
2o almost can ignore
In rinse stage, sodium hydroxide solution will progressively reach the pH value boundary of solution, must realize regeneration by electricity-electrodialytic three chambers.
Then used sodium hydroxide solution is imported into the intermediate chamber through electricity-electrodialyzer the cathode compartment of dialyzer, through holomorphosis, is again sent to washer, and the buffer memory groove of the anolyte compartment of this electricity-electrodialyzer and electrolyzer carries out the circulation of solution.
In the intermediate chamber of electricity-electrodialyzer, the negatively charged ion in sodium hydroxide cleaning solution will be swum anode chamber and positively charged ion (Na by cationic membrane
+) will swim to cathode compartment by anionic membrane.
At the intermediate chamber of electricity-electrodialyzer, the negatively charged ion (Cl-in sodium hydroxide solution ...) will swim anode chamber by cationic membrane.And positively charged ion (Na
+) will swim to cathode compartment by anionic membrane.In anolyte compartment, basis is reacted to the acid of losing in formation system as follows, as (HCl, HOCl, HClO
3..).
H
2O+2(xCl
-,xOCl
-,xClO
3 -)→2(xHCl,xHOCl,xHClO
3)+1/2O
2+2e
-。
The useless sodium hydroxide solution that flows to cathode compartment from intermediate chamber, by the sodium ion being endowed in cathode compartment from intermediate chamber, according to following reaction, will form the sodium hydroxide solution using in washer in cathode compartment:
2H
2O+2Na
++2e
-→H
2+2Na
++2OH
-
Below in conjunction with Fig. 2, 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 saltiness 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.
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.
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.Described permeator is product of the prior art, and concrete principle does not describe in detail at this.
Below introduce in detail gas treating system.
In the excess air of extracting etching machine 1 and producing, the gas of electrolyzer A compartment 7a and B compartment 7b cathode compartment, and by pipeline 36 by the first 6b place, overflow chamber in gas inject reactor 6, it is particularly advantageous in this respect that this invention is proved to be.In addition, the gas that the anolyte compartment of A compartment 7a extracts from electrolyzer 7, by pipeline 38, is equally also injected in the first 6b of overflow chamber of reactor 6, and this will provide support to the regeneration of useless acidic etching liquid.The injection of these mixed gass, especially chloride composition can increase redox couple Cu
++/ Cu
+and Cu
+partial potential between/Cu, thus etched speed and quality improved.
The excess air that the pre-6a of overflow chamber and the first 6b place, overflow chamber produce, the mixed gas that in electrolyzer 7, B compartment 7b place cathode compartment produces is all imported into the second 6c place, overflow chamber in reactor by the gas of pipeline 39 and B compartment 7bChu anolyte compartment via pipeline 37, thereby has supported the regeneration of useless acidic etching liquid 2.
The first treated useless acidic etching liquid in 6b place, overflow chamber in reactor 6, be injected into the gas of extraction, the first volatile gas in 6b place, overflow chamber will be inhaled into and refill the second 6c place, overflow chamber by pipeline 39, thereby assist again the regeneration of useless acidic etching liquid.
The excessive gas in 6c place, San overflow chamber is by 40 6d places, San overflow chamber that are injected into reactor 6 by the road, and final gas will be imported into condenser 33 via pipeline 41.
Condensation product 2c after condenser 33 is processed 43 is injected in the first 6b of overflow chamber of reactor 6 by the road, with this, makes up system because hauled out and evaporate the solution loss causing.
Through condensation process, excessive gas 42 is imported into washer 34 by the road, and through the cleaning of washings 2b, composition is sodium hydroxide solution and clear water substantially, and completely clean gas will be discharged via pipeline 46 afterwards.
For regeneration washing soln 2b, solution, by 44 intermediate chambers that are imported into the electricity-electrodialyzer 35 in gas-circulating system by the road, enters the cathode compartment of electrodialyzer 35 subsequently via pipeline 47.Finally, the cleaning solution 2b of regeneration turns back in washer 34 via pipeline 45, thereby starts a new circulation.Meanwhile, the acidic etching liquid 2a that in the first buffer memory groove 7c of electrolyzer 7, copper content is lower enters 31c by the road the anolyte compartment of electrodialyzer 35, obtains the ion in washing soln 2b, and then 32c turns back in the first buffer memory groove 7c by the road.
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 (10)
1. a gas-recycling plant, it is characterized in that: described exhaust gas circulating device and etching solution equipment connection, described exhaust gas circulating device comprises the first electricity-electrodialyzer, a washer and a condenser, described etching solution equipment connection one 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;
The waste gas outlet of described San overflow chamber is connected with the entrance of described condenser, with so that the waste gas of San overflow chamber flows to condenser by pipeline, the pneumatic outlet of described condenser is connected with the gas inlet of washer, and the condensation product outlet of described condenser is connected with the first overflow chamber by pipeline;
Washings outlet in described washer is connected with the intermediate chamber import of the first electricity-electrodialyzer, and the intermediate chamber outlet of described the first electricity-electrodialyzer is connected by pipeline with cathode compartment entrance, and described cathode compartment outlet is connected with another inlet end of washer;
The outlet of described the first buffer memory groove is connected with anolyte compartment's entrance of the first electricity-electrodialyzer in gas-recycling plant, the outlet of anolyte compartment is connected with the entrance of the first buffer memory groove, uses so that the interior etching solution of the first buffer memory groove is back in the first buffer memory groove after obtaining the ion in washing soln;
Described washer is also provided with whole pneumatic outlet, for discharging the gas of final generation.
2. a kind of gas-recycling plant as claimed in claim 1, 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.
3. a kind of gas-recycling plant as claimed in claim 1, it is characterized in that: described inside reactor pipeline comprises: the excessive outlet of gas 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.
4. a kind of gas-recycling plant as claimed in claim 3, is characterized in that: in described reactor, first, second, third overflow chamber, when being injected into gas, all needs the injection pumping through a use magnetite parcel.
5. a kind of gas-recycling plant as claimed in claim 1, is characterized in that: the gas O producing in the anolyte compartment of described A compartment
2.
6. a kind of gas-recycling plant as claimed in claim 1, is characterized in that: the gas producing in described B compartment anolyte compartment is O
2, HClO
3, HCl.
7. a kind of gas-recycling plant as claimed in claim 1, is characterized in that: described waste gas comprises O
2, HClO
3, HCl.
8. a gas circulation method in gas-recycling plant, is characterized in that: comprise following condensation phase, washing stage and electrodialysis stage:
Condensation phase: the gas by San overflow chamber enters condenser by pipeline and carries out condensation, enters into the first overflow chamber through condensed material by pipeline;
Washing stage: the excess air producing after condenser being processed by the sodium hydroxide solution in washer is cleaned;
The electrodialysis stage: the sodium hydroxide solution after rinsing is first through the intermediate chamber in the first electricity-electrodialyzer, then enter into after cathode compartment is regenerated and get back to washer, wherein, negatively charged ion will move by cationic membrane anode chamber, positively charged ion moves to cathode compartment by anionic membrane, solution in solution in anolyte compartment and the first buffer memory groove circulates, and the negatively charged ion in described electrodialysis stage comprises Cl
-, ClO
-, ClO
3 -, positively charged ion comprises Na
+.
9. gas circulation method in a kind of gas-recycling plant as claimed in claim 8, is characterized in that: the gas of described condensation phase comprises water vapor, hydrochloric acid, perchloric acid and complex copper.
10. gas circulation method in a kind of gas-recycling plant as claimed in claim 8, is characterized in that: the anolyte compartment in described electrodialysis stage occurs to react so that the acid in system, H to be provided as follows
2o+2 (xCl
-, xOCl
-, xClO
3 -) → 2 (xHCl, xHOCl, xHClO
3)+1/2O
2+ 2e
-, described cathode compartment produces the sodium hydroxide solution in washer: 2H by following reaction
2o+2Na
++ 2e
-→ H
2+ 2Na
++ 2OH
-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410001129.4A CN103966608B (en) | 2013-12-13 | 2014-01-02 | Gas circulation method in a kind of gas-recycling plant and device |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310681244.6 | 2013-12-13 | ||
| CN2013106812446 | 2013-12-13 | ||
| CN201310681244 | 2013-12-13 | ||
| CN201410001129.4A CN103966608B (en) | 2013-12-13 | 2014-01-02 | Gas circulation method in a kind of gas-recycling plant and device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103966608A true CN103966608A (en) | 2014-08-06 |
| CN103966608B CN103966608B (en) | 2018-05-22 |
Family
ID=50524948
Family Applications (9)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 |
Family Applications After (6)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 |
Country Status (1)
| Country | Link |
|---|---|
| CN (9) | CN203741422U (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104914626A (en) * | 2015-06-04 | 2015-09-16 | 深圳市华星光电技术有限公司 | Liquid crystal alignment method |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203741422U (en) * | 2013-12-13 | 2014-07-30 | 陶克（苏州）机械设备有限公司 | Rinsing water circulation system |
| CN104087938A (en) * | 2014-06-18 | 2014-10-08 | 京东方科技集团股份有限公司 | Etching-liquid storing apparatus and wet-method etching equipment |
| 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 |
| EP3349883B1 (en) * | 2015-09-18 | 2019-07-03 | Basf Se | System and method for chemical rinsing of a filtration system |
| CN106676527B (en) * | 2015-11-06 | 2019-03-08 | 库特勒环保科技（苏州）有限公司 | A kind of chloric acid sodium form acidic etching liquid regenerated offline system |
| 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 |
| CN118019232B (en) * | 2024-04-09 | 2024-06-21 | 广州市巨龙印制板设备有限公司 | Circuit board two-fluid spraying device with recycling and atomizing functions |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050258134A1 (en) * | 2002-05-20 | 2005-11-24 | Daiwa Fine Chemicals Co., Ltd. | Method for forming circuit pattern |
| CN101125719A (en) * | 2007-07-13 | 2008-02-20 | 深圳市中冠环保科技有限公司 | Method for reclaiming hydrochloric acid and metal copper from printed circuit acidic etching waste liquid |
| JP2009252952A (en) * | 2008-04-04 | 2009-10-29 | Fujikura Ltd | Copper charge plating method and printed circuit board manufactured by the method |
| CN101787547A (en) * | 2010-02-09 | 2010-07-28 | 中南大学 | Method for recovering valuable metals from waste printed circuit board |
| CN202558941U (en) * | 2012-01-19 | 2012-11-28 | 库特勒自动化系统(苏州)有限公司 | Recovery system for treatment of acid etching waste system |
| CN103215593A (en) * | 2012-01-19 | 2013-07-24 | 库特勒自动化系统(苏州)有限公司 | Recovery system and recovery method for treatment of acid etching waste system |
| CN103255419A (en) * | 2012-02-15 | 2013-08-21 | 库特勒自动化系统(苏州)有限公司 | Recovery system and recovery method of waste system in photocell wet process |
| CN203834017U (en) * | 2013-12-13 | 2014-09-17 | 陶克（苏州）机械设备有限公司 | Gas circulating device |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5385772A (en) * | 1977-01-10 | 1978-07-28 | Nippon Fuirutaa Kk | Treatment of collecting waste solution as valuable matter |
| JPS62297476A (en) * | 1986-06-17 | 1987-12-24 | Nec Corp | Method and device for regenerating copper chloride etching waste solution |
| DE69219063T2 (en) * | 1991-10-28 | 1997-11-20 | Nittetsu Mining Co Ltd | Process for the regeneration of caustic agents |
| JPH1018062A (en) * | 1996-06-28 | 1998-01-20 | Kyowa Sangyo Kk | Method for regenerating etching solution, device for regenerating etching solution and etching device |
| JP2006527067A (en) * | 2003-04-30 | 2006-11-30 | 株式会社荏原製作所 | Wastewater treatment method and apparatus |
| CN1780794A (en) * | 2003-04-30 | 2006-05-31 | 株式会社荏原制作所 | Method and apparatus for treating waste water |
| SE531697C2 (en) * | 2007-07-11 | 2009-07-07 | Sigma Engineering Ab | Etching and recycling process |
| JP2010090452A (en) * | 2008-10-09 | 2010-04-22 | Trinity Resources Technology Holding Inc | Method for recycling copper resource in production process |
| CN101798131A (en) * | 2009-02-09 | 2010-08-11 | 深圳市蓝水晶环保有限公司 | High-efficiency electroplating wastewater treatment and resource utilization device |
| CN101560030A (en) * | 2009-05-14 | 2009-10-21 | 中国海洋大学 | Method for realizing resource utilization of copper-containing waste water by electrolysis-electrodialysis united technology |
| CN101988199A (en) * | 2009-08-04 | 2011-03-23 | 章晓冬 | Micro-etching solution cyclic regeneration and copper reclamation device |
| CN101748430B (en) * | 2009-09-23 | 2014-10-29 | 王红华 | Copper recovery system of printed board acid etching waste solution and etching solution regeneration method |
| CN101768742B (en) * | 2009-12-31 | 2011-07-27 | 惠州市雄越保环科技有限公司 | Regenerated acidic etching solution, copper recycling method and special device thereof |
| CN201793745U (en) * | 2010-09-26 | 2011-04-13 | 佛山市三水侨锋电路版有限公司 | Etching waste liquid regeneration and copper recovery processing system |
| CN201914992U (en) * | 2010-12-14 | 2011-08-03 | 惠州市雄越保环科技有限公司 | Micro-etching waste liquid treatment system for printed circuit board (PCB) factories |
| 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 |
| CN202201979U (en) * | 2011-08-30 | 2012-04-25 | 广州市吉弛环保科技有限公司 | Acidity etching liquid recycling and copper recovering device |
| CN102912375B (en) * | 2012-11-06 | 2016-01-13 | 孟辉 | Method and the special purpose device thereof of copper is reclaimed from acidic etching liquid |
| CN103225079B (en) * | 2013-05-03 | 2015-03-18 | 苏州晶瑞化学有限公司 | Electronic industry etching process waste acid reusing and resource recycling process |
-
2014
- 2014-01-02 CN CN201420001773.7U patent/CN203741422U/en not_active Withdrawn - After Issue
- 2014-01-02 CN CN201410001343.XA patent/CN103757664B/en active Active
- 2014-01-02 CN CN201410001129.4A patent/CN103966608B/en active Active
- 2014-01-02 CN CN201410001530.8A patent/CN103757635B/en active Active
- 2014-01-02 CN CN201420001658.XU patent/CN203741421U/en not_active Expired - Lifetime
- 2014-01-02 CN CN201420001975.1U patent/CN203741423U/en not_active Expired - Lifetime
- 2014-01-02 CN CN201420000816.XU patent/CN203743090U/en not_active Expired - Fee Related
- 2014-01-02 CN CN201410001324.7A patent/CN103757634B/en active Active
- 2014-01-02 CN CN201420001494.0U patent/CN203834017U/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050258134A1 (en) * | 2002-05-20 | 2005-11-24 | Daiwa Fine Chemicals Co., Ltd. | Method for forming circuit pattern |
| CN101125719A (en) * | 2007-07-13 | 2008-02-20 | 深圳市中冠环保科技有限公司 | Method for reclaiming hydrochloric acid and metal copper from printed circuit acidic etching waste liquid |
| JP2009252952A (en) * | 2008-04-04 | 2009-10-29 | Fujikura Ltd | Copper charge plating method and printed circuit board manufactured by the method |
| CN101787547A (en) * | 2010-02-09 | 2010-07-28 | 中南大学 | Method for recovering valuable metals from waste printed circuit board |
| CN202558941U (en) * | 2012-01-19 | 2012-11-28 | 库特勒自动化系统(苏州)有限公司 | Recovery system for treatment of acid etching waste system |
| CN103215593A (en) * | 2012-01-19 | 2013-07-24 | 库特勒自动化系统(苏州)有限公司 | Recovery system and recovery method for treatment of acid etching waste system |
| CN103255419A (en) * | 2012-02-15 | 2013-08-21 | 库特勒自动化系统(苏州)有限公司 | Recovery system and recovery method of waste system in photocell wet process |
| CN203834017U (en) * | 2013-12-13 | 2014-09-17 | 陶克（苏州）机械设备有限公司 | Gas circulating device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104914626A (en) * | 2015-06-04 | 2015-09-16 | 深圳市华星光电技术有限公司 | Liquid crystal alignment method |
| CN104914626B (en) * | 2015-06-04 | 2018-12-18 | 深圳市华星光电技术有限公司 | LCD alignment method |
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 |
| CN103757635A (en) | 2014-04-30 |
| CN203741421U (en) | 2014-07-30 |
| CN103966608B (en) | 2018-05-22 |
| CN103757664A (en) | 2014-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN203834017U (en) | Gas circulating device | |
| CN105177583B (en) | A kind of zero-emission acidic etching waste liquid circulation regeneration method and system | |
| CN106145047B (en) | The system and method that ozone preparation and circulation of tail gas utilize | |
| CN105039989B (en) | A kind of acid chlorization system copper-containing etching waste solution electrodeposition decopper(ing) and regeneration method | |
| CN111560615B (en) | Method for on-line recovery of copper and chlorine from acidic etching waste liquid and regeneration of etching liquid | |
| CN109252168A (en) | A kind of devices and methods therefor of efficient activated acid etching solution | |
| CN106007110A (en) | Low-salt wastewater recycled treatment and recycling method | |
| CN107012466A (en) | A kind of acidic etching liquid method for recycling and system | |
| CN202643846U (en) | Etching waste liquid treatment system of printing plate | |
| CN108358356A (en) | A method of it recycling copper from cupric brown oxide waste liquid and recycles sulfuric acid | |
| CN107140727A (en) | A kind of method that chlorine-contained wastewater purification is discharged in Zinc Hydrometallurgy Process | |
| TW589224B (en) | Process and system for exhaust gas treatment | |
| CN106702387A (en) | On-line alkaline ammonium sulfate etching waste liquid cyclic regeneration system | |
| CN103451675B (en) | Printed circuit board etching waste liquid processes system and method | |
| CN103628092A (en) | Printing plate etching waste liquid treatment system and method | |
| CN102807294A (en) | Recirculation system for treating used etching liquid | |
| CN114534501A (en) | Electrodialysis device and method for separating nitric acid and acetic acid | |
| CN207551975U (en) | A kind of high-concentration salt-containing wastewater removal device | |
| CN210683950U (en) | Acid etching solution recycling and regenerating device | |
| CN113684490A (en) | System and method for producing hydrogen by electrolyzing salt-containing wastewater and coupling carbon fixation | |
| CN207391167U (en) | A kind of alkali etching line washing section waste water reclamation system | |
| CN213061051U (en) | Chlorine treatment device of acid etching waste liquid online copper recovery system | |
| CN214087709U (en) | Water system for preparing weak-acid hypochlorous acid from etching waste liquid | |
| CN112962110B (en) | Method for refining by-product salt after incineration | |
| JPH08276187A (en) | Method for electrochemical processing of sulfite-containing solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |