CN203741421U - Equipment capable of regenerating acidic etching solution - Google Patents
Equipment capable of regenerating acidic etching solution Download PDFInfo
- Publication number
- CN203741421U CN203741421U CN201420001658.XU CN201420001658U CN203741421U CN 203741421 U CN203741421 U CN 203741421U CN 201420001658 U CN201420001658 U CN 201420001658U CN 203741421 U CN203741421 U CN 203741421U
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- China
- Prior art keywords
- chamber
- compartment
- overflow
- overflow chamber
- electrolyzer
- Prior art date
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- Expired - Lifetime
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- 238000005530 etching Methods 0.000 title claims abstract description 128
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 49
- 230000001172 regenerating effect Effects 0.000 title abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 95
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052802 copper Inorganic materials 0.000 claims abstract description 67
- 239000007788 liquid Substances 0.000 claims description 47
- 239000007789 gas Substances 0.000 claims description 25
- 238000000909 electrodialysis Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000005086 pumping Methods 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 23
- 230000008569 process Effects 0.000 abstract description 21
- 230000008929 regeneration Effects 0.000 abstract description 15
- 238000011069 regeneration method Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 50
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 239000007921 spray Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 6
- 230000008439 repair process Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- HCYMZEJARFUTIM-UHFFFAOYSA-L [Cl-].[Na+].Cl(=O)(=O)(=O)[O-].[Na+] Chemical compound [Cl-].[Na+].Cl(=O)(=O)(=O)[O-].[Na+] HCYMZEJARFUTIM-UHFFFAOYSA-L 0.000 description 1
- 229940069428 antacid Drugs 0.000 description 1
- 239000003159 antacid agent Substances 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 230000005408 paramagnetism Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- 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 utility model discloses equipment capable of regenerating an acidic etching solution and recovering copper. The equipment comprises a reactor and an electrolytic tank which are connected with each other, wherein the reactor comprises a pre-overflow chamber, a first overflow chamber, a second overflow chamber and a third overflow chamber; the electrolytic tank comprises a compartment A and a compartment B; the compartment A comprises a first anode chamber for generating reactive gas, a first cathode chamber for recovering copper and an intermediate chamber located between the first anode chamber and the first cathode chamber; the compartment B comprises a second anode chamber for generating reactive gas and an accelerant and a second cathode chamber for recovering copper. The equipment has the remarkable effects that the electrolytic tank is simple and compact in structure and capable of favorably providing the accelerant and reactive gas required in a regeneration process; any additives for regeneration are not needed to be added in the whole regeneration process; the stability and flexibility of an etching process are improved, and the etching process is greatly improved.
Description
Technical field
The utility model relates to a kind of acidic etching liquid reclaim equiment, belongs to resource reutilization and non-ferrous metal and reclaims 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.Conventional acid etching processing is that the etching solution that printed circuit board (PCB) is put into etching machine carries out etching reaction.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.
Under normal circumstances, 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.
Utility model content
In view of the defect that above-mentioned prior art exists, the purpose of this utility model is to propose a kind of specific equipment of processing used etching solution and reclaiming copper, and this etching solution is used for Etched Printed Circuit plate in etching machine.
Principle of the present utility model is: in etching process, by electrochemical reaction mechanism [CuCl]
++ 3Cl
-+ Cu=>2[CuCl
2]
-, in spent etching solution, can produce a large amount of compound [CuCl
2]
-, regenerative process is by compound [CuCl
2]
-be oxidized to compound [CuCl]
+, because [CuCl]
+be one to the active chemical element of etching reaction.
The purpose of this utility model will be achieved by the following technical programs:
A kind of acidic etching liquid reclaim equiment, comprising:
One reactor being connected with the etching liquid pool in etching machine, described reactor comprises a Ge Yu overflow chamber and first, second, third overflow chamber, described etching solution enters according to the order of sequence three overflow chambers from flow out pre-overflow chamber,
One electrolyzer being connected with described reactor, in described electrolyzer comprises, be provided with electricity-electrodialysis system A compartment and in be provided with the B compartment of electrolytic system, described A compartment comprises for generation of reactant gases O
2first anode chamber; For reclaiming the first cathode compartment of copper, and be placed in described first anode chamber and and the first cathode compartment between intermediate chamber; Described B compartment comprises for generation of reactant gases O
2with accelerator ClO
3 -second anode chamber, and for reclaiming the second cathode compartment of copper;
Described electrolyzer also comprises the first buffer memory groove and the second buffer memory groove, the entrance of described the first buffer memory groove is connected with described pre-overflow chamber, the outlet of described the first buffer memory groove is connected with described the first overflow chamber, described the first buffer memory groove is also communicated with the first cathode compartment and the second cathode compartment in described electrolyzer, described first anode chamber is communicated with the second buffer memory groove, described intermediate chamber is communicated with the second overflow chamber, described second anode chamber is communicated with the first overflow chamber, between described reactor and electrolyzer, be also provided with gas piping and both are coupled together, the outlet of described the 3rd overflow chamber is connected in etching liquid pool or the etching solution shower nozzle in described etching machine.
Preferably, between described first anode chamber and intermediate chamber, be provided with only for positively charged ion and enter into the cationic membrane in intermediate chamber from described first anode chamber, between described intermediate chamber and the first cathode compartment, be provided with only for negatively charged ion and enter into the anionic membrane in intermediate chamber from described the first cathode compartment.
Preferably, in described the first cathode compartment and the second cathode compartment, be provided with titanium plate electrode, current density is 1 to 10A/dm
2between.
Preferably, indoor sulphuric acid soln and the titanium plate electrode of comprising of the described first anode, the suitable concentration of sulfuric acid is between 10% to 20%, current density is 1 to 5A/dm
2.
Preferably, the gas piping being provided with between described reactor and electrolyzer specifically comprises: the pneumatic outlet of the first anode chamber of the first cathode compartment of described A compartment, the second cathode compartment of B compartment and A compartment is connected with the gas inlet of the first overflow chamber by gas piping, and the pneumatic outlet of the second anode chamber of described B compartment is connected with the gas inlet of the second overflow chamber.
Preferably, described inside reactor pipeline comprises: the excess air outlet of described the first overflow chamber is connected with the gas inlet of the second overflow chamber, and the excess air outlet of described the second overflow chamber is connected with the gas inlet of the 3rd overflow chamber.
Preferably, the solution of the middle storage of described the second buffer memory groove is H
2sO
4, by the indoor H of the first anode in pumping and electricity-electrodialysis system
2sO
4solution circulates.
Outstanding effect of the present utility model is:
1, cell construction is simple, compact, can be well for regenerative process provides the accelerator and the reactant gases that need;
2, whole regenerative process does not need to add the additive of any regeneration use;
3, improve stability and the handiness of etching process, will greatly improve etch process.
Below just accompanying drawing in conjunction with the embodiments, is described in further detail embodiment of the present utility model, so that technical solutions of the utility model are easier to understand, grasp.
Brief description of the drawings
Fig. 1 is the utility model regenerated acidic etching solution and the structural representation that reclaims copper equipment.
Fig. 2 is the utility model regenerated acidic etching solution and reclaims in copper equipment the Structure and Process schematic diagram in reactor in the time that copper is reclaimed.
Fig. 3 is the utility model regenerated acidic etching solution and reclaims in copper equipment the Structure and Process schematic diagram in electrolyzer in the time that copper is reclaimed.
Fig. 4 is the utility model regenerated acidic etching solution and reclaims in copper equipment in the time that copper is reclaimed the Structure and Process schematic diagram in electrolyzer B compartment.
Fig. 5 is the utility model regenerated acidic etching solution and reclaims in copper equipment in the time that copper is reclaimed the Structure and Process schematic diagram in electrolyzer A compartment.
Embodiment
The utility model disclosed a kind of can regenerated acidic etching solution and reclaim equipment and the method for copper.
As shown in Figures 1 to 5, printed circuit board (PCB) 3 is in the processing of the interior etching solution 2 spraying through nozzle 4 of etching machine 1.Then receive the rinsing of rinsing module 5.Through etching, etching solution 2 becomes acidic etching waste liquid, is sent to reactor 6, in waste liquid, may include following chemical substance: hydrochloric acid, cupric chloride, sodium-chlor, sodium perchlorate and water.Through processing, the regenerated acidic etching solution 2 that carrys out autoreactor 6 will be sent in the shower nozzle 4 of etching machine 1.
Concrete, the described reactor being connected with etching machine 6 comprises 3 overflow chambers and a 6a of Ge Yu overflow chamber, 3 overflow chambers are respectively the first 6b of overflow chamber, the second 6c of overflow chamber, the 3rd 6d of 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 3rd 6d of 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 of pre-overflow chamber in described reactor;
The useless acidic etching liquid of sub-fraction is injected into from pre-overflow chamber by pipeline 9 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, carrys out the concentration of copper in the useless acidic etching liquid 2 of balance with this;
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, returns by pipeline 12; 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, after reaction, return through pipeline 13, another part carries out regenerating oxidation reaction again by continuing to flow to the 3rd 6d of overflow chamber.
Finally, the acidic etching liquid after regeneration is finally got back to the nozzle 4 of etching machine 1 by pipeline 20, starts the circulation of a new round.
Concrete,
Containing [CuCl
2]
-useless acidic etching liquid enter in a reactor, generate [CuCl by electric chemical formula (1) (4) (5) oxidation
2]
+,
2CuCl
2-+2H
++1/2O
2→2CuCl
++2Cl
-+H
2O； （1），
2CuCl
2 -+1/3ClO
3 -+2H
+→2CuCl
++H
2O+7/3Cl
- （4）；
2CuCl
2-+Cl
2+4H
+→2CuCl
++HCl （5）。
One electrolyzer being connected with described reactor comprises one electricity-electrodialysis system and an electrolytic system, described electricity-electrodialysis system and electrolytic system by electric chemical formula (2) for required reactant gases is provided in described reactor:
H
2O→2H
++1/2O
2+2e
- （2），
Described electrolytic system by electric chemical formula (3) (7) (8) for accelerator is provided in described reactor:
Cl
-+3H
2O→ClO
3 -+6H
++6e
- （3），
2Cl
-→Cl
2+2e
- （7）；
Cl
2+6H
2O→2ClO
3 -+12H
++12e
- （8）。
[the CuCl obtaining in described reactor
2]
+being recycled to acidic etching liquid uses in station.
Further, in described electricity-electrodialysis system and electrolytic system, reclaim copper according to electric chemical formula (6),
CuCl
++2e
-→Cu+Cl
- （6）。
Further, described electricity-electrodialysis system provides extra acidic solution by electric chemical formula (9) for acidic etching liquid,
2H
++2Cl
-→2HCl （9）。
In the utility model, 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 in the time that 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).
Contain Cu (I) through the useless acidic etching liquid in etch processes after etching machine, 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 the gas that pumping is extracted from the cathode compartment 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, reduce the concentration of copper in the acidic etching liquid that gives up with this.
Carry out the chemical oxidation reaction of Cu (I) to Cu (II) 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, 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, spray the internal recycling of pumping by being furnished with magnetic, in electrolyzer A, B compartment in the oxygen that produces of anolyte compartment in etching solution, gone be drawn out of and be injected into 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 utility model, 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, provides the complete time taking this as chemical reaction with regeneration.
In the utility model, in electrolyzer, the capacity of B compartment is no more than 10% of whole electrolyzer capacity, avoids Cl in system with this
2concentration excessive.
The utility model should meet copper and reclaim and 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 the concentration that keeps copper in reprocessing cycle etching machine is in optimum level at reactor,, be injected into and in reactor, carry out overflow for the first time according to the demand of system copper control device from the lower etching solution of the content of electrolyzer buffer memory buried copper.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 improves 1.5% to 3%:[CuCl by the speed that makes electrolysis]
++ 2e
-→ Cu+Cl
-, [CuCl
2]
-+ e
-→ Cu+2Cl
-.
Concrete example:
One is equipped with a flow velocity is 18, the etching machine of the pumping of 000l/h, per hour can etching 30kg copper, in etching solution, the concentration of copper is approximately 145g/l< totally 2,610kg Cu (II) >, according to following reaction [CuCl]
++ 3Cl
-+ Cu → 2[CuCl
2]
-, etching 30kg copper per hour can produce the Cu (I) of 60kg.Therefore, in the pre-overflow chamber of reaction chamber, will obtain comprising the solution of the Cu (I) of 97,7% Cu (II) and 2,27%.
On the other hand, in the useless acidic etching liquid that contains Cu (I) copper, lack oxydant, have the advantage of the etching speed that can reduce negative electrode, thereby improve the efficiency that copper reclaims.
In the utility model, 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 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.
It should be noted that the form of gained copper depends on the content of copper in cathode solution: when the concentration of copper in cathode solution is less than 20g/l, 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.
Realize useless acidic etching liquid regenerate required oxygen and acid H in order to produce by electrolyzer
+, the A compartment of electrolyzer has three cells, an 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.Chemical reaction according to 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, an 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 Cu (I) is oxidized to Cu (II) by the oxygen of generation, produce HCl be used for acidifying produce solution, 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 utility model 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 utility model, 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 ensure etching with this and reclaim between balance.In addition, electrolyzer need comprise two compartments, and wherein accelerator compartment must work provide enough reagent taking this as continuous regenerative process when etching material reduces.
A substantive distinguishing features of the present utility model 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 subsequently through useless acidic etching liquid treatment process/system processing, be re-used as afterwards high-quality etching solution and offer the nozzle of etching machine.
The utility model is not limited to aforementioned embodiments; those skilled in the art are under the enlightenment of the utility model technical spirit; also may make other and change, but as long as function and the utility model of its realization are same or similar, all should belong to protection domain of the present utility model.
Claims (7)
1. an acidic etching liquid reclaim equiment, is characterized in that: comprises,
One reactor being connected with the etching liquid pool in etching machine, described reactor comprises a Ge Yu overflow chamber and first, second, third overflow chamber, described etching solution enters according to the order of sequence three overflow chambers from flow out pre-overflow chamber,
One electrolyzer being connected with described reactor, in described electrolyzer comprises, be provided with electricity-electrodialysis system A compartment and in be provided with the B compartment of electrolytic system, described A compartment comprises for generation of reactant gases O
2first anode chamber; For reclaiming the first cathode compartment of copper, and be placed in described first anode chamber and and the first cathode compartment between intermediate chamber; Described B compartment comprises for generation of reactant gases O
2with accelerator ClO
3 -second anode chamber, and for reclaiming the second cathode compartment of copper;
Described electrolyzer also comprises the first buffer memory groove and the second buffer memory groove, the entrance of described the first buffer memory groove is connected with described pre-overflow chamber, the outlet of described the first buffer memory groove is connected with described the first overflow chamber, described the first buffer memory groove is also communicated with the first cathode compartment and the second cathode compartment in described electrolyzer, described first anode chamber is communicated with the second buffer memory groove, described intermediate chamber is communicated with the second overflow chamber, described second anode chamber is communicated with the first overflow chamber, between described reactor and electrolyzer, be also provided with gas piping and both are coupled together, the outlet of described the 3rd overflow chamber is connected in etching liquid pool or the etching solution shower nozzle in described etching machine.
2. acidic etching liquid reclaim equiment according to claim 1, it is characterized in that: between described first anode chamber and intermediate chamber, be provided with only for positively charged ion and enter into the cationic membrane in intermediate chamber from described first anode chamber, between described intermediate chamber and the first cathode compartment, be provided with only for negatively charged ion and enter into the anionic membrane in intermediate chamber from described the first cathode compartment.
3. acidic etching liquid reclaim equiment according to claim 1, is characterized in that: in described the first cathode compartment and the second cathode compartment, be provided with titanium plate electrode, current density is 1 to 10A/dm
2between.
4. acidic etching liquid reclaim equiment according to claim 1, is characterized in that: indoor sulphuric acid soln and the titanium plate electrode of comprising of the described first anode, and the suitable concentration of sulfuric acid is between 10% to 20%, current density is 1 to 5 A/dm
2.
5. acidic etching liquid reclaim equiment according to 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.
6. acidic etching liquid reclaim equiment according to claim 1, it is characterized in that: described inside reactor pipeline comprises: the excess air outlet of described the first overflow chamber is connected with the gas inlet of the second overflow chamber, the excess air outlet of described the second overflow chamber is connected with the gas inlet of the 3rd overflow chamber.
7. acidic etching liquid reclaim equiment according to claim 1, is characterized in that: the solution of the middle storage of described the second buffer memory groove is H
2sO
4, by the indoor H of the first anode in pumping and electricity-electrodialysis system
2sO
4solution circulates.
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| CN201420001658.XU CN203741421U (en) | 2013-12-13 | 2014-01-02 | Equipment capable of regenerating acidic etching solution |
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| CN201310681244.6 | 2013-12-13 | ||
| CN201310681244 | 2013-12-13 | ||
| CN201420001658.XU CN203741421U (en) | 2013-12-13 | 2014-01-02 | Equipment capable of regenerating acidic etching solution |
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| CN203741421U true CN203741421U (en) | 2014-07-30 |
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| CN201420001494.0U Expired - Lifetime CN203834017U (en) | 2013-12-13 | 2014-01-02 | Gas circulating device |
| CN201420000816.XU Expired - Fee Related CN203743090U (en) | 2013-12-13 | 2014-01-02 | Magnetic jet pump |
| 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 |
| CN201420001658.XU Expired - Lifetime CN203741421U (en) | 2013-12-13 | 2014-01-02 | Equipment capable of regenerating acidic etching solution |
| CN201410001530.8A Active CN103757635B (en) | 2013-12-13 | 2014-01-02 | Electrolysis bath and use regenerated acidic etching solution equipment and the renovation process of this electrolysis bath |
| CN201420001773.7U Withdrawn - After Issue CN203741422U (en) | 2013-12-13 | 2014-01-02 | Rinsing water circulation system |
| CN201410001129.4A Active CN103966608B (en) | 2013-12-13 | 2014-01-02 | Gas circulation method in a kind of gas-recycling plant and device |
| CN201410001324.7A Active CN103757634B (en) | 2013-12-13 | 2014-01-02 | A kind of rinse water recycle system and rinse water circulation means |
| CN201420001975.1U Expired - Lifetime CN203741423U (en) | 2013-12-13 | 2014-01-02 | Electrolytic cell for regeneration of acidic etching solution |
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| 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 |
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| CN201410001530.8A Active CN103757635B (en) | 2013-12-13 | 2014-01-02 | Electrolysis bath and use regenerated acidic etching solution equipment and the renovation process of this electrolysis bath |
| CN201420001773.7U Withdrawn - After Issue CN203741422U (en) | 2013-12-13 | 2014-01-02 | Rinsing water circulation system |
| CN201410001129.4A Active CN103966608B (en) | 2013-12-13 | 2014-01-02 | Gas circulation method in a kind of gas-recycling plant and device |
| CN201410001324.7A Active CN103757634B (en) | 2013-12-13 | 2014-01-02 | A kind of rinse water recycle system and rinse water circulation means |
| CN201420001975.1U Expired - Lifetime CN203741423U (en) | 2013-12-13 | 2014-01-02 | Electrolytic cell for regeneration of acidic etching solution |
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Family Cites Families (27)
| 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 |
| JP3881614B2 (en) * | 2002-05-20 | 2007-02-14 | 株式会社大和化成研究所 | Circuit pattern forming method |
| 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 |
| CN101125719B (en) * | 2007-07-13 | 2011-02-09 | 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 |
| 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 |
| CN101787547B (en) * | 2010-02-09 | 2011-06-15 | 中南大学 | Method for recovering valuable metals from waste printed circuit board |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN203834017U (en) * | 2013-12-13 | 2014-09-17 | 陶克（苏州）机械设备有限公司 | Gas circulating device |
-
2014
- 2014-01-02 CN CN201420001494.0U patent/CN203834017U/en not_active Expired - Lifetime
- 2014-01-02 CN CN201420000816.XU patent/CN203743090U/en not_active Expired - Fee Related
- 2014-01-02 CN CN201410001343.XA patent/CN103757664B/en active Active
- 2014-01-02 CN CN201420001658.XU patent/CN203741421U/en not_active Expired - Lifetime
- 2014-01-02 CN CN201410001530.8A patent/CN103757635B/en active Active
- 2014-01-02 CN CN201420001773.7U patent/CN203741422U/en not_active Withdrawn - After Issue
- 2014-01-02 CN CN201410001129.4A patent/CN103966608B/en active Active
- 2014-01-02 CN CN201410001324.7A patent/CN103757634B/en active Active
- 2014-01-02 CN CN201420001975.1U patent/CN203741423U/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103757664A (en) * | 2013-12-13 | 2014-04-30 | 陶克（苏州）机械设备有限公司 | Electrolytic tank, etching liquid regeneration equipment using same and regeneration method |
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| CN105506728B (en) * | 2014-09-29 | 2019-10-15 | 盛美半导体设备（上海）有限公司 | The device of precipitating metal ion from electrochemical polish liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103966608B (en) | 2018-05-22 |
| CN203741422U (en) | 2014-07-30 |
| CN103966608A (en) | 2014-08-06 |
| CN103757664A (en) | 2014-04-30 |
| CN103757635B (en) | 2016-11-23 |
| CN203741423U (en) | 2014-07-30 |
| CN103757635A (en) | 2014-04-30 |
| CN203834017U (en) | 2014-09-17 |
| CN103757634B (en) | 2016-04-20 |
| CN103757634A (en) | 2014-04-30 |
| CN203743090U (en) | 2014-07-30 |
| CN103757664B (en) | 2017-04-05 |
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Address after: 215000, No. 6, Taishan Road, hi tech Zone, Jiangsu, Suzhou, 2 Patentee after: KUTTLER ENVIRONMENTAL TECHNOLOGY (SUZHOU) CO.,LTD. Address before: 215022 No. 8, Yip Yip Road, Suzhou, Jiangsu Patentee before: TOC (SUZHOU) MACHINERY CO.,LTD. |
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