CN103966608B - Gas circulation method in a kind of gas-recycling plant and device - Google Patents
Gas circulation method in a kind of gas-recycling plant and device Download PDFInfo
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- CN103966608B CN103966608B CN201410001129.4A CN201410001129A CN103966608B CN 103966608 B CN103966608 B CN 103966608B CN 201410001129 A CN201410001129 A CN 201410001129A CN 103966608 B CN103966608 B CN 103966608B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The present invention provides gas circulation methods in a kind of gas-circulating system being connected with etching liquid equipment and device.The pernicious gas generated in etching liquid regenerative process can effectively be handled by condensation phase, washing stage and electrodialysis stage.The present invention protrusion effect be：Etching liquid regeneration cell construction is simple, compact, can provide the accelerator and reaction gas of needs for regenerative process well；Entire regenerative process need not add the additive of any regeneration；Stability and the flexibility of etching process are improved, etch process will be substantially improved；Finally discharged without pernicious gas, it is environmentally protective.
Description
Technical field
The present invention relates to a kind of gas-recycling plants and gas circulation method being connected with etching liquid equipment, belong to resource again
Utilize field.
Background technology
In worldwide, electric appliance and electronic industry is one of fastest-rising industry, and printed circuit board (PCB) is as electric appliance and electronic
The important component of product, yield also increasingly increase.Conventional acid etching processing is that printed circuit board (PCB) is put into etching machine
Reaction is etched in interior etching solution.The removal limited time of copper on printing plate, and part may be because of some organically
Or other antacid antibody prevent and establish conductor with acidic etching liquid, are restricted so as to cause the time.
Under normal conditions, the rate of 30 to 60 microns of copper of removal per minute can be achieved on.But due to the saturation of copper
And to maintain an acceptable processing speed, the replacement that etching solution must be regular so will result in substantial amounts of discarded erosion
Carve liquid.
In the prior art, the regeneration of etching solution need to add additive according to following etching reaction（Such as hydrogen peroxide H2O2, it is smelly
Oxygen O3, sodium chlorate NaClO3）It could realize：
Cu+2HCl+H2O2→CuCl2+2H2O；
Cu+2HCl+1/3O3→CuCl2+H2O；
Cu+2HCl+1/3NaClO3→CuCl2+1/3NaCl+H2O；
In addition, there are the unmatched phenomenon of chemistry, nothings between the amount of etch copper and the amount of reclaiming for conventional etching processes
By the supply for being etching solution, discharge or copper recovery system, cause etching solution regeneration and copper recycling it is ineffective.Meanwhile
The processing of exhaust gas is also a big problem.
The content of the invention
In view of the problems of the above-mentioned prior art, the purpose of the present invention is to propose to a kind of gas being connected with etching liquid equipment
Body circulation device and gas circulation method.
The purpose of the present invention will be achieved by the following technical programs：
A kind of gas-recycling plant, the exhaust gas circulating device are connected with etching solution equipment, the exhaust gas circulating device bag
Include the first electricity-electric dialyzator, a washer and a condenser, the etching solution equipment connect a reactor and with the reactor
The electrolytic cell of connection；
The reactor includes a Ge Yu overflow chambers and first, second, third overflow chamber, and the etching solution is from pre- overflow chamber
Sequentially enter three overflow chambers after outflow；
A compartments and B compartments are equipped in the electrolytic cell, the A compartments include first anode room, medial compartment, the first cathode
Room；Cationic membrane is equipped between the first anode room and medial compartment, be equipped between the medial compartment and the first cathode chamber it is cloudy from
Sub- film；The B compartments include second plate room and the second cathode chamber；
The electrolytic cell further includes the first cache slot and the second cache slot, and the entrance of first cache slot pre- overflows with described
Flow chamber connects, and the outlet of first cache slot is connected with first overflow chamber, first cache slot also with the electrolysis
The first cathode chamber in slot and the connection of the second cathode chamber, the first anode room are connected with the second cache slot, the medial compartment and
Second overflow chamber connects, and the second plate room is connected with the first overflow chamber；
Gas piping is additionally provided between the reactor and electrolytic cell and connects the two, the 3rd overflow chamber
Outlet is connected to etching liquid pool or etching solution nozzle in the etching machine；
The waste gas outlet of 3rd overflow chamber is connected with the entrance of the condenser, to make the exhaust gas of the 3rd overflow chamber
Condenser is flowed by pipeline, the gas vent of the condenser and the gas access of washer connect, the condenser it is cold
Condensate outlet is connected by pipeline with the first overflow chamber；
Cleaning solution outlet in the washer is connected with the medial compartment import of the first electricity-electric dialyzator, and first electricity-
The medial compartment outlet of electric dialyzator is connected with cathode chamber inlet by pipeline, another entrance of the cathode chamber outlet and washer
End connection；
The Anode chamber inlets connection of first electricity-electric dialyzator in the outlet of first cache slot and gas-recycling plant,
The outlet of anode chamber is connected with the entrance of the first cache slot, to make in the first cache slot etching solution by obtaining in wash solution
Ion after be back in the first cache slot；
The washer is additionally provided with whole gas vent, for discharging the gas finally generated.
Preferably, the gas piping being equipped between the reactor and electrolytic cell specifically includes：The first of the A compartments is cloudy
The gas vent of the first anode room of pole room, the second cathode chamber of B compartments and A compartments passes through gas piping and the first overflow chamber
Gas access connects, and the gas vent of the second plate room of the B compartments is connected with the gas access of the second overflow chamber.
Preferably, the inside reactor pipeline includes：Excessively outlet and the second overflow of the gas of first overflow chamber
The gas access connection of room, the excess air outlet of second overflow chamber are connected with the gas access of the 3rd overflow chamber.
Preferably, first, second, third overflow chamber when by injection gas, is both needed to use magnetic by one in the reactor
The injection pumping of stone package.
Preferably, the gas O generated in the anode chamber of the A compartments2。
Preferably, the gas generated in the B compartments anode chamber is O2、HClO3、HCl。
Preferably, the exhaust gas includes O2、HClO3、HCl。
Gas circulation method in a kind of gas-recycling plant, including following condensation phase, washing stage and electrodialysis stage：
Condensation phase：Enter condenser by pipeline by the gas of the 3rd overflow chamber to be condensed, process is condensed
Substance enters the first overflow chamber by pipeline；
Washing stage：The excess air generated after condenser processing is carried out by the sodium hydroxide solution in washer clear
It washes；
The electrodialysis stage：Sodium hydroxide solution after flushing first passes through the medial compartment in the first electricity-electric dialyzator, then
It enters after cathode chamber is regenerated and returns to washer, wherein, anion will be migrated by cationic membrane to anode chamber, cation
It is migrated by anionic membrane to cathode chamber, the indoor solution of anode is cycled with the solution in the first cache slot, the electric osmose
The anion in analysis stage includes Cl-、ClO-、ClO3 -, it is cationic to include Na+。
Preferably, the gas of the condensation phase includes water vapour, hydrochloric acid, perchloric acid and complex copper.
Preferably, following reaction occurs for the anode chamber in the electrodialysis stage with the acid in offer system, H2O+2(xCl-,
xOCl-,xClO3 -)→2(xHCl,xHOCl,xHClO3)+1/2O2+2e-, the cathode chamber pass through it is following reaction generate washer in
Sodium hydroxide solution：2H2O+2Na++2e-→H2+2Na++2OH-。
Certainly, the volatilization of the solution such as some vapor and acid, copper can be also generated in the anode chamber of more than A compartments and B compartments
Ingredient.
The present invention protrusion effect be：
1st, cell construction is simple, compact, can provide the accelerator and reaction gas of needs for regenerative process well；
2nd, entire regenerative process need not add the additive of any regeneration；It is finally discharged without pernicious gas, green ring
It protects.
Just attached drawing in conjunction with the embodiments below, the embodiment of the present invention is described in further detail, so that of the invention
Technical solution is more readily understood, grasps.
Description of the drawings
Fig. 1 is the structure diagram for the gas-recycling plant that the present invention is connected with etching solution regenerative system, including drift
The wash water circulatory system.
Fig. 2 is reaction structure schematic diagram of the etching solution of the present invention in reactor.
Specific embodiment
Present invention is disclosed a kind of devices that can be with regenerated acidic etching solution and for being cycled to gas.
As shown in Figure 1 and Figure 2, the processing for the etching solution 2 that printed circuit board (PCB) 3 sprays in etching machine 1 by nozzle 4.Then
Receive the rinsing of rinsing module 5.Through overetch, etching solution 2 becomes acidic etching waste liquid, is sent to reactor 6, may in waste liquid
Include following chemical substance：Hydrochloric acid, copper chloride, sodium chloride, sodium perchlorate and water.By processing, carry out the regeneration of autoreactor 6
Acidic etching liquid 2 will be sent in the nozzle 4 of etching machine 1.
Specifically, the reactor 6 being connected with etching machine includes 3 overflow chambers and a Ge Yu overflow chambers 6a, 3 overflows
Room is respectively the first overflow chamber 6b, the second overflow chamber 6c, the 3rd overflow chamber 6d.Simultaneous reactions device 6 is connected again with electrolytic cell 7, institute
Electrolytic cell 7 is stated to be made of electricity-electrodialysis system 7a, electrolysis system 7b and the first cache slot 7c, the second cache slot 7d.In reactor
3rd overflow chamber 6d of last time overflow is connected with the nozzle 4 in etching machine.
Regenerated acidic etching solution and recycle copper detailed process be：
Containing [CuCl2]-Useless acidic etching liquid enter at the pre- overflow chamber 6a in the reactor；
Sub-fraction give up acidic etching liquid by pipeline 9 from pre- overflow chamber by the first cache slot 7c of injection electrolytic cell 7
In, remaining useless acidic etching liquid will be flowed in the first overflow chamber 6b；
The useless acidic etching liquid entered in the first cache slot 7c is injected the electrolysis system of the electrolytic cell 7 by pipeline 16
Copper is precipitated in the cathode chamber of system 7b and electricity-electrodialysis system 7a, for reducing copper content, realizes chemical regeneration, and then becomes low
Copper content acidic etching liquid）, 17 return by the road in the first cache slot 7c.
The low copper containing amount acidic etching liquid 19 is returned in the first overflow chamber 6b of the reactor by the road again, with this
To balance the concentration of copper in useless acidic etching liquid 2；
The useless acidic etching liquid 2 and low copper containing amount acidic etching liquid in the first overflow chamber 6b are entered, after mixing, wherein one
Part is injected by pipeline 10 in the anode chamber of the electrolysis system, is returned after reaction by pipeline 12；Another part will
Flow to the second overflow chamber 6c；
The useless acidic etching liquid in the second overflow chamber 6c is entered, a portion passes through pipeline 11 and the electricity-electric osmose
The medial compartment of analysis system 7a is connected, and is returned after reaction through pipeline 13, and another part will continue towards the 3rd overflow chamber 6d and carry out again
Regenerating oxidation reaction once.
Finally, the acidic etching liquid after regeneration returns to the nozzle 4 of etching machine 1 eventually by pipeline 20, starts a new round
Xun Huan.
Reactor is mainly that the Cu (I) for etching material generation is oxidized to Cu (II) in the present invention.Three are included in reactor
Secondary overflow and once pre- overflow, for reducing flow velocity and improving the reaction time by increasing one cycle to each overflow.Often
A overflow all includes the injection pumping wrapped up with magnetite, and benefit is when gas/liquid mixture passes through magnetic field, can be selected
Property passes through two kinds of copper complexs.In addition, it is contemplated that concentration is 3% or so diamagnetism Cu (I) complex compounds and concentration is 97% or so
Paramagnetism Cu (II) complex compound different concentration and magnetic signature, it can increase sucking in copper complex Cu (I) and injection pumping
Gas collision probability.Then, Cu (I) complex compound is forced out flowing through outside the solution for spraying pumping, and solution is because of jet pump
Gas in Pu and be layered, thus optimize the oxidation reaction that Cu (I) arrives Cu (II).
Useless acidic etching liquid after etching process in etching machine contains Cu (I), will all be sent in reactor
Pre- overflow chamber, wherein sub-fraction will be by the first cache slot of injection 7c, and the cathode chamber that the first cache slot 7c is connected to electrolytic cell is used
To recycle etch copper.Remaining major part, which will continue to flow into, passes through first time overflow, first time overflow and electrolytic cell in reactor
B compartments anode chamber continue solution cycling, oxidation reaction rely on perchlorate presence, in addition by means of magnetic jet pump
Pu is proceeded by from the cathode chamber of etching machine, the AB compartments gas extracted and the oxygen extracted from A compartments anode chamber.In addition,
Solution in electrolytic cell cache slot after copper removal will be added to first time overflow, and the dense of copper in useless acidic etching liquid is reduced with this
Degree.
By first time overflow partial regeneration and by the useless acidic etching liquid of copper removal will flow to second of overflow carry out Cu
(I) chemical oxidation reaction of Cu (II) is arrived, therefore, the medial compartment of the A compartments of second of overflow and electrolytic cell starts the cycle over solution,
Pass through H+Ion and Cl-The movement of ion, etching solution is because the generation of HCl becomes abundant.In addition, by matching somebody with somebody the jet pump that is magnetic
The inside at Pu is cycled, and the oxygen that the anode chamber in A, B compartment in electrolytic cell generates will be extracted and be injected into etching solution
It goes to complete following oxidation reaction：[CuCl2]-+H++1/4O2→[CuCl]++Cl-+1/2H2O。
The regeneration of useless acidic etching liquid will be completed after third time overflow in reactor, second of overflow injection solution
The remaining excess air O from electrolytic cell afterwards2It is reinjected into, Cu++Copper ion changes into complex copper [CuCl]+So as to complete
Oxidation reaction, complex copper [CuCl]+From the oxidation of Cu (I).
In the present invention, the acidic etching liquid that gives up is in the residence time Jing Guo overflow each time, especially second and third time
At least 1 minute.In addition, injection pumping flow per minute is twice of its specific spillway discharge, come with this for chemical reaction and
Regeneration provides the complete time.
In the present invention, the capacity of B compartments is no more than the 10% of entire cell capacity in electrolytic cell, is avoided with this in system
Cl2Concentration it is excessive.
The present invention should meet copper recycling and realize etching solution regeneration again, it is necessary to use an electrolysis for being furnished with cache slot
Slot, electrolysis and electricity-electrodialytic combination can not only recycle copper, can also generate the oxygen needed for useless acidic etching liquid regeneration,
Acid H+With etching accelerator perchloric acid.
To keep the concentration of copper in regeneration cycle etching machine at reactor in optimum level, in electrolytic cell cache slot
The relatively low etching solution of the content of copper is carried out first time overflow by according to the demand of system copper control device in injection reactor.
First cache slot cycles etching solution with the cathode chamber of electrolytic cell in itself, and in cathode chamber, copper is electrolysed.Meanwhile sub-fraction
It will be stored in from the indoor spent etching solution of the pre- overflow of etching machine reactor in the cache slot of electrolytic cell, because what it was included
The concentration of copper is rising, and rate is 1.5% to 3%, it is contemplated that and the energy needed for electrolysis Cu (I) is be electrolysed Cu (II) 1/2, according to
The rate for causing electrolysis is improved 1.5% to 3% by equation below, this characteristic：[CuCl]++2e-→Cu+Cl-、[CuCl2]-+e-→
Cu+2Cl-。
Concrete example：
One etching machine for being equipped with the pumping that a flow velocity is 18,000l/h, can etch 30kg copper, etching solution per hour
The concentration of middle copper is about 145g/l<Common 2,610kg Cu (II)>, according to following reaction [CuCl]++3Cl-+Cu→2
[CuCl2]-, the Cu (I) of 60kg can be generated by etching 30kg copper per hour.Therefore, will be included in the pre- overflow chamber of reative cell
The solution of 97,7% Cu (II) and 2,27% Cu (I).
On the other hand, lack oxydant in the useless acidic etching liquid containing Cu (I) copper, possess the erosion that can reduce cathode
The advantages of carving speed, so as to improve the efficiency of copper recycling.
In this invention, cathode chamber includes a cathode titanium plates in electrolytic cell and an anionic membrane, current density are arrived 1
10A/m2Between.By liquid need to keep low speed, and the voltage between cathode and anode is no more than 10V, to avoid because of fever
Caused by loss.
It is chemically reacted as follows according in cathode chamber：[CuCl]++2e-→Cu+Cl-、[CuCl2]-+e-→Cu+2Cl-, will
Metallic copper and chlorion are obtained, they can be moved to the medial compartment of the anode chamber of B compartments and A compartments.
It is worth noting that, the form of gained copper depends on the content of copper in cathode solution：When in cathode solution copper it is dense
Degree is less than 20g/l, and current density is more than 5A/dm2When, copper will be electrolysed in the form of copper powders, and when the concentration of copper is higher than
20g/l, current density are less than 5A/dm2When, copper will be electrolysed in the form of compact copper coin.
In order to generate the oxygen and acidity H realized needed for useless acidic etching liquid regeneration by electrolytic cell+, the A of electrolytic cell every
There are three cell, an anode chamber, a medial compartment, a cathode chambers for room tool.Medial compartment and anode chamber are by a cationic membrane
It separates and cathode chamber is separated by an anionic membrane.Anode chamber includes sulfuric acid（H2SO4）Solution and titanium plate electrode, sulfuric acid are suitable
Between concentration is 10% to 20%, current density is 1 to 5A/dm2.According to the chemical reaction of anode chamber：H2O→1/2O2+2H+, will produce
Raw oxygen O2, oxygen O2It will be extracted and be injected into the useless acidic etching liquid in the first time overflow in reactor.In electric field
Under the action of, H+Form into medial compartment and in the solution acidity HCl, subsequent medial compartment solution and second of overflow in reactor
It is cycled.
To generate the accelerator perchlorate that can be accelerated cathode copper rate by means of electrodialytic membranes, the B compartments of electrolytic cell
Comprising two boothes, an anode chamber and a cathode chamber, according to following chemical reaction, anode will generate perchlorate, acid
And oxygen：
Cl-+3H2O→ClO3 -+6H++6e-
H2O→2H++1/2O2+2e-
In short, regenerated acid etching liquid will continuously be supplied to the spray boom of etching machine completely, by etch process, again
It is returned to as useless etching solution in reactor.Sub-fraction solution in reactor Nei Yu overflow chambers will be introduced directly into electrolytic cell
Cathode chamber, by being electrolysed to reduce the concentration of copper in solution, it is continuous that remaining major part will pass through in reactor other two
The processing of cell.The two cells are connected with electrolyzer anode chamber, and Cu (I) is oxidized to Cu (II) by the oxygen of generation, generates HCl
For being acidified production solution, etching accelerator perchlorate is also added into solution.The 3rd Room in reactor will be supplied to
Etching machine spray boom is rich in [CuCl2]-Complete regenerated etching acid solution, so as to repeat the etching and recycling in another cycle.
Secondly, the present invention improves stability and the flexibility of etching process, will substantially improve etch process.Conventional etch
There are the unmatched phenomenon of chemistry between the amount of etch copper and the amount of reclaiming, the either supply of etching solution, discharges for technique
Or copper recovery system.To obtain stable progress of etching, it is necessary to the concentration of Cu (I) is kept below 0,01%, so as to can just carry
For a good etching result.Therefore, the present invention in, etching machine and electrolytic cell synchronous operation, with this come continue offer needed for
Regenerated etching solution, and from the influence of fluctuation.Therefore, any regenerative process having a negative impact to etching process
Interruption will not occur.
According to the following metallic copper illustrated, etch 1kg：
(1) 2kg copper existing in the form of Cu (I) is generated according to equation below：[CuCl]++3Cl-+Cu→2[CuCl2]-。
(2) in etching machine while the etch copper of recycling 1kg, the oxygen O of 251.8gr will be generated in tank house2,
The HCl of 574.44gr.
(3) Cu (I) of the 2kg generated in etching machine is regenerated, according to equation below, needs the oxygen O of 251.8gr2With
The HCl of 574.44gr, [CuCl2]-+H++1/4O2→[CuCl]++Cl-+1/2H2O。
Therefore, the gas and the amount of acid that are generated in electrolytic process are equal to the amount needed for regeneration.In above-mentioned illustration, regeneration
Amount of reagent needed for 2kg Cu (I) is equal to accelerator compartment in electrolytic cell（B compartments）The amount that anode generates, accelerator compartment must
Must and etching machine run simultaneously with this come the balance between ensureing to etch and recycling.In addition, electrolytic cell need to include two compartments,
Middle accelerator compartment must work while etching material and reducing and enough reagents are provided for continuous regenerative process with this.
The substantive distinguishing features of the present invention are the acidic etching liquids in the cistern for handle useless acidic etching liquid technique,
By recycling and handling respectively, by the nozzle for directly feeding etching machine and then spray on a printed circuit.It is meanwhile used
And/or useless acidic etching liquid will be collected, and be then passed through useless acidic etching liquid treatment process/system processing, be re-used as afterwards
The etching solution of high quality is supplied to the nozzle of etching machine.This treatment process includes two steps：One be etching solution regeneration and
Copper recycles, the other is the processing for the flushing water that exhaust gas and etching machine Rinse section generate.
The recovery processing of excess air and washings is divided into two independent processing systems.
The gas that etching machine and recovery system generate includes vapor substantially, hydrochloric acid, perchloric acid and is dragged out compound
Copper.Before rinsing unit is entered, these gases are first imported into condenser, by water and the material condensation deviate from, these substances
The first overflow chamber that will be sent in reactor.Condenser is one and is divided into four sections of cylinder by liquid drop separator, wherein wrapping
Include 5 cooler pans.The gas that third time overflow generates in reactor will be sucked by the wind turbine of condenser, be imported into cylinder bottom
Portion.After 3 liquid drop separators and 5 cooler pans so that square temperature is less than 10 DEG C on the cylinder for gas, so as to reach
To good condensation effect.It is larger from the temperature higher density of higher outlet discharge on the top of cylinder there are two gas outlet
The wind turbine being attached thereto is sucked the condensation for carrying out a new round by gas, and the gas relatively low from the density of relatively low outlet discharge will
Into washer for first cylinder of washing.
Washing is divided into two steps.The first step, i.e. first cylinder for washing, gas enter eminence, solution from lower
The direction of rinsing then in contrast, from high to low.Via a special nozzle, solution is sprayed in the form of spraying for rinsing,
Intermolecular contact is improved with this.In addition, this cylinder for washing, what first segment was made of comprising one baton round
Separating layer, this layer are also for optimizing the contact of gas liquid.It it is one on nozzle there are one nozzle on plastic layer
Liquid drop separator.The second step of washing need to be by means of spraying pumping and nozzle, and gas will pass through four separation in this cylinder
The processing of layer：First layer, baton round, second layer liquid drop separator, third layer, baton round, the 4th layer, liquid drop separator.Two
Pumping sucking is sprayed from the first in vivo gas of washing cylinder, the bottom of second cylinder of injection, then in cylinder
Middle part and top are rinsed respectively be subject to from nozzles spray liquid.
Final washed rear clean gas completely will be released to outside.
During cleaning used solution be sodium hydroxide solution, concentration 1,5%~8%, temperature between 5 DEG C~20 DEG C,
PH value is 7~8, reaches complete neutralization with this.
Following chemical reaction will occur in rinse stage：
HCl+NaOH→NaCl+H2O key reactions
Cl2+ 2NaOH → NaCl+NaOCl is almost negligible
3Cl2+6NaOH→5NaCL+NaClO3+3H2O is almost negligible
In rinse stage, sodium hydroxide solution will progressively reach the pH value boundary of solution, it is necessary to pass through electricity-electrodialytic three
Realize regeneration in a room.
Used sodium hydroxide solution will be then directed to the cathode of dialyzer by the medial compartment of electricity-electric dialyzator
Washer is sent in room again by regenerating completely, and the anode chamber of the electricity-electric dialyzator and the cache slot of electrolytic cell carry out solution
Cycling.
In the medial compartment of electricity-electric dialyzator, the anion in sodium hydroxide cleaning solution will be swum by cationic membrane to
Anode chamber and cation (Na+) will be swum by anionic membrane to cathode chamber.
Anion in the medial compartment of electricity-electric dialyzator, sodium hydroxide solution（Cl-…）To be swum by cationic membrane to
Anode chamber.It is and cationic（Na+）It will be swum by anionic membrane to cathode chamber.To system be formed according to following reaction in anode chamber
The acid of middle loss, such as (HCl, HOCl, HClO3..)。
H2O+2(xCl-,xOCl-,xClO3 -)→2(xHCl,xHOCl,xHClO3)+1/2O2+2e-。
From medial compartment flow to cathode chamber useless sodium hydroxide solution will be endowed in cathode chamber the sodium from medial compartment from
According to following reaction, the sodium hydroxide solution used in washer will be formed in cathode chamber for son：
2H2O+2Na++2e-→H2+2Na++2OH-
It describes to include electricity-electricity to the circulatory system of washings in etching machine, the circulatory system in the lower present invention below in conjunction with Fig. 2
Dialyzer 23, electric dialyzator 22 and permeator 21；
Separating in the rinsing room 5 has between 5a between the first cleaning, the second cleaning 5c between 5b, the 3rd cleaning, between three cleanings
It is inside both provided with to spray to cleaning solution into the cleaning sprayer of product.
Rinse the branch pipeline 24a flow directions electricity-electricity of washings highly polluted at 5a between first cleaning in room 5 by pipeline 24
The medial compartment of dialyzer 23 is then in charge of 25b back between the first cleaning at 5a by pipeline 25.Electricity-electric dialyzator 23
Anode chamber and cathode chamber are connected by the branch pipeline 31a, 31b of pipeline 31 with the first cache slot 7c of electrolytic cell 7, and pass through pipeline
32 branch pipeline 32a, 32b realizes the cycling of useless acidic etching liquid.Pass through the electric field of 23 inner foundation of electricity-electric dialyzator, anion
It will be swum by cationic membrane to anode chamber, meanwhile, cation is swum by cationic membrane to cathode chamber, and then, anode chamber generates acid,
Cathode chamber recycles copper, so as to reduce in rinsing room 5 pollution level of washings at 5a between first cleaning.
By the 24b that is in charge of of pipeline 24, contaminated washings are sent to the sun of electric dialyzator 22 at 5a between the first cleaning
Pole room, cathode chamber and the medial compartment for having concentrate solution, then 25 25b that is in charge of is returned by the road.On the one hand, this will purify second
On the other hand salt content in solution is transferred between the first cleaning at 5a, and between the first cleaning by the washings between cleaning at 5b
5a reduces saliferous rate by electricity-electric dialyzator 23 in itself.
First time washings can be completed above and the medial compartment of electricity-electric dialyzator 23 is cycled, effects of ion trip
To anode chamber and cathode chamber, the cycling of anode chamber and cathode chamber with the first cache slot 7c progress solution, so as to reduce rinsing
Saliferous rate in water.Meanwhile the water of first time rinse stage and the medial compartment of electric dialyzator 22 are cycled, and are cleaned from second
Salinity is obtained in water, such water is cycled so that ion is swum to medial compartment between 22 anode of electric dialyzator and cathode.
Finally, the solution that saliferous rate reduces in the cycling will be imported into permeator 21, be cleaned from what permeator 21 generated
Water afterwards will be supplied to the last one rinse stage, and the solution of concentration will be restored to second of rinse stage.
According to the design of water treatment unit, the minimum 7cm of width of cathode chamber in electricity-electric dialyzator and electric dialyzator, from
And it can easily recycle cathode copper from these rooms.
In this invention, a permeator 21 is connected with electric dialyzator 22.It rinses in room 5 and is contaminated between second cleaning at 5b
Washings pass through pipeline 28 import permeator 21.Wherein, purified water imports the 3rd cleaning of rinsing room 5 by pipeline 30
Between at 5c.Concentrating part 29 will be imported between the second cleaning at 5b by the road.Finally, between the second cleaning at 5b electricity is given by pipeline 26
The dilution chamber of dialyzer 22 provides washings, the washings after therefrom being diluted further through pipeline 27.The permeator is
Product of the prior art, concrete principle will herein be described in detail.
Gas handling system described in detail below.
In the excess air that extraction etching machine 1 generates, the gas of electrolytic cell A compartment 7a and B compartment 7b cathode chambers, and pass through
Pipeline 36 is injected a gas into reactor 6 at first overflow chamber 6b, and this invention is proved to be particularly advantageous in this regard.This
Outside, from electrolytic cell 7 anode chamber's extraction of A compartments 7a gas, by pipeline 38, be equally also implanted into the of reactor 6
In one overflow chamber 6b, this will provide support to the regeneration of useless acidic etching liquid.The injection of these mixed gas, it is especially chloride
Ingredient can increase oxidation-reduction pair Cu++/Cu+And Cu+Chemical potential between/Cu, so as to improve the speed of etching and quality.
The excess air generated at pre- overflow chamber 6a and the first overflow chamber 6b, B compartments 7b places cathode chamber generation in electrolytic cell 7
Mixed gas be introduced into reactor second via pipeline 37 by the gas of anode chamber at pipeline 39 and B compartments 7b and overflow
At flow chamber 6c, so as to support the regeneration of useless acidic etching liquid 2.
Treated useless acidic etching liquid at first overflow chamber 6b in reactor 6 is overflow by the gas of injection extraction, first
Volatile gas will be inhaled into and pass through pipeline 39 and refill at the second overflow chamber 6c at flow chamber 6b, so as to aid in again
The regeneration of useless acidic etching liquid.
At 3rd overflow chamber 6c excessive gas by by the road 40 by the 3rd overflow chamber 6d of injection reactor 6, finally
Gas will be imported into condenser 33 via pipeline 41.
By treated the condensate 2c of condenser 33 by the road 43 by the first overflow chamber 6b of injection reactor 6, with
This makes up system because solution loss caused by being dragged out and evaporating.
By condensation process, excessive gas 42 is imported into washer 34 by the road, by the cleaning of cleaning solution 2b, ingredient
Essentially sodium hydroxide solution and clear water, afterwards completely clean gas will be discharged via pipeline 46.
To regenerate wash solution 2b, solution is imported into electricity-electric dialyzator 35 in gas-circulating system by by the road 44
Medial compartment then enters the cathode chamber of electric dialyzator 35 via pipeline 47.Finally, regenerated cleaning solution 2b is returned via pipeline 45
It returns in washer 34, so as to start new cycling.Meanwhile copper content is relatively low in the first cache slot 7c of electrolytic cell 7
31c by the road is entered the anode chamber of electric dialyzator 35 by acidic etching liquid 2a, to obtain the ion in wash solution 2b, Ran Houjing
Pipeline 32c is returned in the first cache slot 7c.
The present invention is not limited to aforementioned embodiments, those skilled in the art are under the enlightenment of the technology of the present invention marrow, also
Other changes may be made, but as long as the function and the present invention of its realization are same or similar, the protection model of the present invention should all be belonged to
It encloses.
Claims (4)
1. a kind of gas-recycling plant, it is characterised in that：The gas-recycling plant is connected with etching solution equipment, and the gas follows
Loop device includes the first electricity-electric dialyzator, a washer and a condenser, the etching solution equipment connect a reactor and with institute
State the electrolytic cell of reactor connection；
The reactor includes a Ge Yu overflow chambers and first, second, third overflow chamber, and the etching solution is flowed out from pre- overflow chamber
Sequentially enter three overflow chambers afterwards；
A compartments and B compartments are equipped in the electrolytic cell, the A compartments include first anode room, medial compartment, the first cathode chamber；Institute
It states and cationic membrane is equipped between first anode room and medial compartment, anionic membrane is equipped between the medial compartment and the first cathode chamber；
The B compartments include second plate room and the second cathode chamber；
The electrolytic cell further includes the first cache slot and the second cache slot, the entrance of first cache slot and the pre- overflow chamber
Connection, the outlet of first cache slot is connected with first overflow chamber, first cache slot also in the electrolytic cell
The first cathode chamber and the connection of the second cathode chamber, the first anode room connects with the second cache slot, the medial compartment and second
Overflow chamber connects, and the second plate room is connected with the first overflow chamber；
Gas piping is additionally provided between the reactor and electrolytic cell and connects the two, the outlet of the 3rd overflow chamber
The etching liquid pool or etching solution nozzle being connected in the etching solution equipment；
The waste gas outlet of 3rd overflow chamber is connected with the entrance of the condenser, and the exhaust gas to make the 3rd overflow chamber passes through
Pipeline flows into condenser, and the gas vent of the condenser and the gas access of washer connect, the condensate of the condenser
Outlet is connected by pipeline with the first overflow chamber；
Cleaning solution outlet in the washer is connected with the medial compartment import of the first electricity-electric dialyzator, first electricity-electric osmose
The medial compartment outlet of parser is connected with the cathode chamber inlet of the first electricity-electric dialyzator by pipeline, first electricity-electric dialyzator
Cathode chamber outlet and washer another arrival end connect；
The Anode chamber inlets connection of first electricity-electric dialyzator, anode in the outlet of first cache slot and gas-recycling plant
The outlet of room is connected with the entrance of the first cache slot, to make etching solution in the first cache slot by obtain in wash solution from
It is back to after son in the first cache slot；
The washer is additionally provided with whole gas vent, for discharging the gas finally generated；
The gas piping being equipped between the reactor and electrolytic cell specifically includes：The first cathode chamber, the B compartments of the A compartments
The second cathode chamber and A compartments first anode room gas vent pass through the gas access of gas piping and the first overflow chamber connect
It connects, the gas vent of the second plate room of the B compartments is connected with the gas access of the second overflow chamber；
The inside reactor pipeline includes：The excess air outlet of first overflow chamber and the gas access of the second overflow chamber
Connection, the excess air outlet of second overflow chamber are connected with the gas access of the 3rd overflow chamber；
First, second, third overflow chamber is when by injection gas in the reactor, the jet pump wrapped up by one with magnetite
Pu, injection pumping flow per minute are twice of its specific spillway discharge.
2. a kind of gas-recycling plant as described in claim 1, it is characterised in that：It is produced in the first anode room of the A compartments
Raw gas is O2。
3. a kind of gas-recycling plant as described in claim 1, it is characterised in that：It is generated in the B compartments second plate room
Gas be O2、HClO3、HCl。
4. a kind of gas-recycling plant as described in claim 1, it is characterised in that：Gas bag in the gas-recycling plant
Include O2、HClO3、HCl。
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 | 2013-12-13 | ||
| CN201310681244.6 | 2013-12-13 | ||
| CN2013106812446 | 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 CN103966608A (en) | 2014-08-06 |
| CN103966608B true CN103966608B (en) | 2018-05-22 |
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ID=50524948
Family Applications (9)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 |
| CN201420001975.1U Expired - Lifetime CN203741423U (en) | 2013-12-13 | 2014-01-02 | Electrolytic cell for regeneration of acidic etching solution |
| CN201410001129.4A Active CN103966608B (en) | 2013-12-13 | 2014-01-02 | Gas circulation method in a kind of gas-recycling plant and device |
| 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 |
| CN201420001773.7U Withdrawn - After Issue CN203741422U (en) | 2013-12-13 | 2014-01-02 | Rinsing water circulation system |
| 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 |
| 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 |
|---|---|---|---|
| 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 |
| CN201420001975.1U Expired - Lifetime CN203741423U (en) | 2013-12-13 | 2014-01-02 | Electrolytic cell for regeneration of acidic etching solution |
Family Applications After (6)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 |
| CN201420001773.7U Withdrawn - After Issue CN203741422U (en) | 2013-12-13 | 2014-01-02 | Rinsing water circulation system |
| 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 |
| CN201420001494.0U Expired - Lifetime CN203834017U (en) | 2013-12-13 | 2014-01-02 | Gas circulating device |
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| Country | Link |
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| CN (9) | CN103757664B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103757664B (en) * | 2013-12-13 | 2017-04-05 | 陶克（苏州）机械设备有限公司 | Electrolysis bath, using etching solution generating apparatus and the renovation process again of the electrolysis bath |
| 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 |
| CN104914626B (en) * | 2015-06-04 | 2018-12-18 | 深圳市华星光电技术有限公司 | LCD alignment method |
| CA2999115A1 (en) * | 2015-09-18 | 2017-03-23 | 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 |
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- 2014-01-02 CN CN201420000816.XU patent/CN203743090U/en not_active Expired - Fee Related
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- 2014-01-02 CN CN201420001773.7U patent/CN203741422U/en not_active Withdrawn - After Issue
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103757635B (en) | 2016-11-23 |
| CN203834017U (en) | 2014-09-17 |
| CN103757634A (en) | 2014-04-30 |
| CN103757635A (en) | 2014-04-30 |
| CN203741421U (en) | 2014-07-30 |
| CN203741422U (en) | 2014-07-30 |
| CN103966608A (en) | 2014-08-06 |
| CN203741423U (en) | 2014-07-30 |
| CN103757634B (en) | 2016-04-20 |
| CN203743090U (en) | 2014-07-30 |
| CN103757664B (en) | 2017-04-05 |
| CN103757664A (en) | 2014-04-30 |
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