WO2012163238A1 - Recycling system and method for treating used etching solution - Google Patents
Recycling system and method for treating used etching solution Download PDFInfo
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- WO2012163238A1 WO2012163238A1 PCT/CN2012/075862 CN2012075862W WO2012163238A1 WO 2012163238 A1 WO2012163238 A1 WO 2012163238A1 CN 2012075862 W CN2012075862 W CN 2012075862W WO 2012163238 A1 WO2012163238 A1 WO 2012163238A1
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- gas
- etching solution
- regeneration
- etchant
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to recycling techniques, and more particularly to recycling systems that have used etching fluids ( Background of the Invention)
- the conventional chloride etching solution must be continuously replaced by a fresh etching solution or a circulating reuse etching solution.
- the recovery of the used etching liquid is mainly the precipitation of copper therein, but it is not preferable to recycle the gas discharged during the etching and the water in the etching liquid.
- the present invention provides a recovery system for treating used etching liquids.
- the system includes an ionization device, an oxidation device, an extraction device, an electrolysis device, and a regeneration device.
- the ionization device is configured to decompose Cu(I) in the used acidic etching solution transferred from the etching device; the oxidation device receives the used acidic etching solution from the ionization device, and the received etching solution
- Cu(I) is oxidized to Cu(II);
- the extraction device continuously or non-continuously receives the used acidic etching solution transferred from the ionizing device at a predetermined ratio, and extracts the acid in the used acidic etching solution
- the electrolysis device receives the used acidic etching solution that has been treated by the extraction device, and precipitates the copper in the used acidic etching solution;
- the regeneration device receives the used etching solution processed by the oxidation device, and adjusts the used Using the pH of the etchant and stabilizing the copper complex in the form of [CuCl] + monochloride so that the received etchant received becomes a reusable etchant;
- the ionization device Extracting the gas and transferring the extracted gas and the gas escaping from the electrolysis device to an oxidizing device, in which the gas is further extracted and the extracted gas is transferred to the regenerating device, and the escaping device is escaping from the regenerative device
- the gas is delivered
- the treatment of the present invention has used a recirculating system of an acidic etchant in which the used acid etchant is decomposed by extracting HCl gas.
- the treatment of the present invention has used a recirculating system of an acidic etchant, said ionization
- the treatment of the present invention has used a recirculating system of an acidic etchant, the ionization apparatus comprising a first unit that has received an acidic etchant, and a first used acidic etchant from the first unit a second unit, and receiving a third unit from the second unit that has used an acidic etchant, wherein the second unit includes more than one subunit and each subunit is coupled to its adjacent subunit for the used etch Liquid can flow from one subunit to an adjacent subunit.
- the treatment according to the present invention has used a recirculating system of an acidic etchant, from the second unit, preferably, the treatment system of the present invention has used an acid etchant recycling system from the first unit and The gas is extracted from the second unit.
- the process of the present invention has used a recirculating system of an acidic etchant, the volume of the used acidic etchant transferred from the ionization device to the oxidizing device and the loop in the ionizing device
- the ratio of the volume of the used etchant used for the cycle is 2 to 1.
- the treatment according to the invention has used a recirculating system of acidic etchant, the volume of gas extracted from the ionization device and the volume of used acidic etchant circulating in the circuit of the ionization device
- the ratio is 1 to 1
- the pressure in the ionization device is between 0.8 atm and 0.95 atm.
- the treatment of the present invention has used a recirculating system of an acidic etchant, the oxidizing means being arranged to oxidize Cu(I) by gas injected therein, and the gas comprises extracting from the ionizing means Gas, gas from the electrolysis device and the etching apparatus.
- the gas is injected at a pressure of between 1.1 and 1.3 atm.
- the treatment of the present invention has used a recycling system of an acidic etchant, said oxidation -J* ⁇ 4 ⁇ 71 Hi J- — /U t fit i . -hh ⁇ 3 ⁇ 4 ⁇ ⁇
- the treatment of the present invention has used a recirculating system of an acidic etching solution which utilizes a resin to extract the acid, and the solution after rinsing the resin is sent to the second oxidizing unit of the oxidizing device.
- the process of the present invention has used a recirculating system of an acidic etchant from the mountain Jl*3 ⁇ 4 AA
- the gas of the apparatus is sent to the first oxidation unit.
- the treatment of the present invention has used a recirculating system of acidic etchant, and the gases from the electrolysis apparatus and the etching apparatus include pure oxygen, chlorine, and atmospheric oxygen.
- the process of the present invention has used a recycling system of an acidic etching solution, the regeneration device comprising a first regeneration unit and a second regeneration unit, the first regeneration unit being used to adjust the pH of the received solution, And the second regeneration unit is used to stabilize the monochloro copper network according to the following chemical reaction
- the treatment of the present invention has used a recirculation system of an acidic etchant, the first regeneration unit receiving gas from the oxidizer.
- the process of the present invention has used a recirculation system of an acidic etchant, the regeneration device being provided with a syringe pump to absorb and re-inject the gas from the first regeneration unit into the second regeneration unit In the solution of the second regeneration unit.
- the treatment of the present invention has used a recirculating system of an acidic etchant, the electrolysis apparatus comprising an electrolysis unit comprising an anode, an electrode and a current generator.
- the process of the present invention has used a recirculating system of an acidic etchant that supplies current at a density of 2 amps per square meter to 7 amps per square meter with a voltage between the electrodes at 1.1 volts. Between 2.8 volts.
- the treatment of the present invention has used a recirculation system of an acidic etchant, and further includes a gas treatment device that extracts gas HC1 and traces of Cl 2 , HCIO from the gas received by the ionization device, HC10 2 , HCIO3, HC10 4 .
- the treatment of the present invention has used a recirculating system of an acidic etchant, wherein the gas Al, ⁇ ⁇ ⁇ J-iL i ⁇ , 3 ⁇ 45 3 ⁇ 43 r+ ⁇ , k ⁇ 3 ⁇ 43 -tac , ⁇ - A h ⁇ 7 ⁇ l ⁇ ⁇ ⁇
- the gas of the third unit and by means of condensation
- the received gas separates the gas HC1 and the traces of Cl 2 , HC10, HC10 2 , HCIO3, HCIO4, and the separated gas is sent to the first unit of the regeneration device, and the separator receives the condenser Residual gas, and in the first part of the separator, absorbs HC1 and traces of Cl 2 , HC10, HC10 2 , HC10 3 , HC10 4 , separated HC1 gas and traces of ci 2 , HC10, HC10 2 , HCIO3, 11 (: 10 4 gas is sent to the second unit of the regeneration unit, wherein the remaining gases include Cl 2 , HC10, HCIO2, HC10 3 ,
- the knife comprises a first separation unit, a second separation unit and a third separation unit, the first separation unit being configured to absorb HC1 and traces of Cl 2 , HC10, HCIO2, HCIO3, HC10 4 gas in the gas from the condenser,
- the second and third units were used to extract HC1 and traces of Cl 2 , HC10, HC10 2 , HC10 3 , HCIO4 gases.
- the treatment of the present invention has used a recirculation system of an acidic etchant, further comprising a water treatment device and a rinsing member, the rinsing member using the etchant from the etching device to obtain pure water, and receiving from the separation The solution of the device.
- a recirculation system of an acidic etchant further comprising a water treatment device and a rinsing member, the rinsing member using the etchant from the etching device to obtain pure water, and receiving from the separation The solution of the device.
- the treatment of the present invention has used a recirculation system of an acidic etchant, the water treatment device comprising a permeation unit and a plurality of temporary storage tanks for treating the solution from the rinsing member to obtain pure Water, the obtained pure water is sent to the first temporary storage tank to be fed into the rinsing member from the first temporary storage tank when necessary, and the permeate of the non-pure water obtained by the permeable member is fed into the first
- the second storage tank is mixed with the solution from the separation device, and the mixed solution is sent to the rinsing member as needed.
- the solution in which the etching solution has been used can be efficiently recovered and the gas in the recycling process can be effectively utilized.
- Another aspect of the present invention provides a method of regenerating an acidic etching solution, comprising the steps of: a) ionizing and decomposing a Cu(I) complex in an acidic etching solution; b) decomposing
- the Cu(I) ion is oxidized to a Cu(II) ion; c) a Cu(II) complex is formed to regenerate the used etching solution into a usable etching solution.
- the complex may be a complex of Cu and C1.
- the method of the present invention for regenerating an acidic etching solution may further comprise the following steps: Step a) A part of the used acidic etching solution after the decompression is electrolyzed to precipitate copper. Alternatively, the acid in the portion of the used acidic etching solution may be extracted prior to electrolysis to facilitate precipitation of copper.
- the decomplexing is carried out in step a) by extracting the HC1 gas in the used acidic etching solution.
- the oxidation in step b) is carried out at least in part by a gas generated by ionization and a gas produced by electrolysis, and atmospheric oxygen or an oxidizing gas of other origin may also participate in the oxidation.
- the used etching solution is regenerated into a usable etching solution by adjusting the pH of the used etching solution and stabilizing the Cu(II) complex, for example, chlorine gas and hydrogen chloride.
- Figure 1 is a schematic structural view showing an etching solution recirculation system of the present invention
- Figure la further shows a schematic structural view of the etching solution recirculation system of the present invention including a gas circuit
- Figure 1b further illustrates a schematic structural view of the etchant recirculation system of the present invention including a water circulation loop;
- Figure 2 shows a schematic of the chemical potential difference of oxidation versus CU / CU + and Cu + /Cu. detailed description
- the present invention is directed to the recovery and regeneration of an acid etchant that has been used, so that the regenerated acidic etchant can be reused as an etchant.
- an acidic etching solution has been used as a reusable acidic etching solution by treatment of five devices such as extraction, ionization, oxidation, electrolysis, and regeneration, and these reusable acidic etching solutions are used after etching.
- Re-enter the recycling and regeneration process to be processed into five reusable acidic etching solutions by extraction, ionization, oxidation, electrolysis and regeneration.
- the recovery and regeneration process includes circulation of the acid etchant that has been used, circulation of the gas released during the process of recovery and regeneration, and circulation of water to the rinsing circuit board.
- FIG. 1 is a schematic block diagram showing the processing of a circulation system in which an etching solution has been used, in accordance with one embodiment of the present invention.
- the figure is mainly intended for the circulation and processing of the used etching solution.
- [CuCl 2 ]- in the solution is decomposed into Cu + and Cr by extracting HCl gas.
- the following chemical reaction is carried out in the ionization apparatus 5:
- Some of the ionizer 5 has been supplied with an etchant at a predetermined ratio to the extraction unit, A3 ⁇ 4 _ "Si" TTrt Jli , ⁇ : n if* Al - ci ⁇ _, ⁇ An ⁇ 7? ⁇ ⁇
- the used etchant that has been sequentially processed in several units of the ionization device 5 is transferred to the oxidizing device 8.
- the oxidizing device 8 Cu(I) is oxidized to Cu(II) due to oxygen 02 enrichment.
- Cu(II) is complexed by injecting chlorine gas and hydrochloric acid separated from the gas transferred from the oxidation device 8 and the gas escaping from the ionization device 5 in the regeneration device 9, That is, CiT is changed to [CuCl]+.
- the used etching liquid transferred from the etching machine 1 to the ionizing device 5 is divided into two parts.
- the solution which accounts for 98.5% to 99.5% of the total amount of the used etching liquid, is sent back to the etching machine 1 after being processed by the oxidation unit 8 and the regeneration unit 9.
- the remaining 0.5% to 1.5% of the etchant has been sent to the electrolysis unit 7 for electrolysis by the acid extraction unit 6.
- S is extracted from the used solution to increase the electrolysis efficiency of the electrolytic unit 7a of the electrolysis device 7.
- the treated used etching liquid in the electrolytic cell 7a is sent to the temporary storage tank 7b. From the temporary storage tank 7b, an etchant has been used as needed to be dosed to the ionization apparatus 5 to dilute the used etching liquid in the ionization apparatus 5.
- the ionization device 5 includes a first unit that receives an used acidic etchant, receives a second unit that has used an acidic etchant from the first unit, and receives a third unit that has used an acidic etchant from the second unit,
- the second unit comprises two subunits and the two subunits are interconnected such that the used etchant can flow from one subunit to an adjacent subunit.
- the second unit includes only two subunits, the actual application is not limited thereto.
- the terms "second unit” and "third unit” refer to two subunits of the second unit previously described in this paragraph.
- Processing is performed in the first unit 5a, the second unit 5b, and the third unit 5c to extract and extract gas from the used etching liquid.
- gas extraction is performed in the first unit 5a to obtain a non-oxidizing etching liquid supplied to the electrolysis device 7, whereby the acid portion in the solution supplied to the electrolysis unit 7a is partially extracted to reduce the acid content in the solution. .
- the acid reduced solution and the stable Cu(I) complex increase the electrolysis efficiency of the electrolytic cell 7a.
- the chemical reaction carried out in the electrolysis unit 7a is shown below:
- [CuCl 2 ]" + e- ⁇ Cu + 2d- further utilizes an etchant that has been used to clean the second portion of the gas from the regeneration device 9.
- the solution from the second unit 5b that has been extracted by gas and hydrochloric acid is passed Going to the third unit 5c to extract the gas again.
- the used etching liquid that has been subjected to gas extraction in the second unit 5b and the third unit 5c of the ionization device 5 is sent to the fourth unit 5d to be from the self-regeneration device 9.
- the gas sent from the second portion 9b absorbs acid and chlorine.
- a loop is formed between the units 5d, 5c and 5b so that the etchant has been used to flow in the loop for a thousand cycles, during which the cycle can be More gas has been extracted from the etching solution, and after several cycles have been performed to effectively reduce the amount of the solution gas, the etching liquid has been used to be transferred to the fourth unit 5d to absorb more acid and chlorine.
- the etchant has been used to be transferred to the first oxidizing unit 8a of the oxidizing device 8.
- the unit 5d is sufficiently rich in acid and chlorine because it sufficiently absorbs the gas sent from the second portion 9b of the regeneration device 9.
- the solution in unit 5d is sent to the second unit 5b, and in units 5b and 5c, these acids and chlorine are released from the used etching solution.
- Atmospheric oxygen, pure oxygen, and chlorine extracted from the electrolytic cell 7a and the temporary storage tank 7b are injected into the first oxidation unit 8a of the oxidation device 8 to perform the following chemical reaction:
- the ratio of the volume of the used acidic etching solution transferred from the ionization device to the oxidation device to the volume of the used etching solution circulating in the circuit in the ionization device is 2 Than 1. Further, preferably, the ratio of the volume of the gas extracted from the ionization device to the volume of the used acidic etching solution circulating in the circuit of the ionization device is 1 to 1, and the pressure in the ionization device is 0.8atm to 0.95atm. According to the arrangement of the present invention, the gas in the used solution can be sufficiently extracted.
- a catalyst may be added to the used etching solution to provide support according to the following chemical reaction:
- the degree of oxidation of the oxidation reaction carried out in the first oxidation unit 8a is 70%, and the oxidation reaction is substantially completed in the second oxidation unit 8b, i.e., substantially 100% oxidation is achieved.
- the used etching liquid transferred from the oxidation device 8 is processed by the regeneration device 9.
- the reproducing device 9 sequentially processes the used etching liquid by two units. In the first regeneration unit 9a, the solution is acidified, and in the second regeneration unit 9b, the copper complex [CuCl] + is stabilized. Then, the solution completely processed by the reproducing device 9 is sent to the head 3 of the etching machine 1, and is ejected from the head 3 to the printed circuit board.
- the solution for etching the circuit board again is enriched in [CuCl 2 ]_ after the etching, and the used etching liquid is sent to the first unit 5a of the ionization device 5 to repeat the entire process as described above again.
- the process of recycling the gas escaping from the etching solution during operation is by gas treatment
- the gas treatment apparatus includes a condenser 28, a separator 29, and a neutralizer 30.
- the excess gas escaping from the ionization unit 5 is sent to the separator 29 via the condenser 28 and then to the neutralizer 30 to ensure complete treatment and reuse of the gas.
- HC1 and atmospheric oxygen from the etching machine 1 pure oxygen and chlorine from the electrolytic unit 7a of the electrolysis device 7, and gas from the temporary storage tank 7b of the electrolysis device 7 can be installed in the oxidation device 8a.
- the syringe is sucked and injected into the used etching liquid of the first oxidation unit 8a of the oxidation device 8.
- the gas escaping from the first oxidizing unit of the oxidizing device 8 and the gas sucked from the first unit 5a, the second unit 5b, and the third unit 5c of the ionizing device 5 are injected into the second oxidizing unit of the oxidizing device 8. Used in the solution in 8b.
- the evolved gas from the second oxidation unit 8b of the oxidation unit 8 is sent to the first regeneration unit 9a of the regeneration unit 9.
- the evolved gas of the first regeneration unit 9a of the regeneration device 9 is absorbed and injected into the second regeneration unit 9b, for example, by a syringe installed in the regeneration device 9a.
- Excess gas escaping from the used etchant that has been processed by the second regeneration unit 9b of the regeneration device 9 is sent to the fourth unit 5d of the ionization device 5 to pass through the ionization device 5 as described above.
- the gas is extracted as much as possible to the second oxidizing unit 8b of the oxidizing unit, and the gas escaping from the fourth unit 5d is sent to the condenser 28.
- the gas is cooled to 5. (:, while chlorine, acid and water vapor condense. After condensation, the condenser 28 contains three parts: liquid condensate at the bottom of the condenser 28, chlorine and hydrogen chloride gas in the middle of the condenser 28, gas at the upper part of the condenser The gas located in the middle of the condenser 28 is sucked and injected into the first regeneration unit 9a of the regeneration device 9. The gas mixture located at the upper portion of the condenser 28 is sent to the separator 29.
- the solution in separator 29 is the condensate in condenser 28 and the solution will be continuously sent to the water treatment unit.
- the separator 29 includes three units, wherein the first separation unit 29a is for absorbing acid, hydrogen chloride gas and traces of C1 2 , HC10, HC10 2 , HC10 3 , HC10 4 gas.
- the second separation unit 29b and the third separation unit 29c are used to extract chlorine and a certain amount of acid.
- the gas is directed to the neutralizer 30 so that it has been used in the treatment of the present invention.
- ⁇ fjg -f ⁇ - ⁇ LA take the mouth w'v knife 7 r, knife - ⁇ ⁇ a- Kenting" i man surgery u acid and chlorine are sent back Go to the second regeneration unit 9b of the regeneration device 9.
- the water treatment apparatus includes a permeating member 42 and three intermediate tanks to keep flushing water circulating in a closed loop without contamination, and the etching liquid drawn from the etching chamber is recovered to the flushing member of the etching apparatus, and only Exceptionally, fresh water is dosed to maintain the level of solution in the rinse module.
- the permeable member 42 divides the incoming rinsing water into a concentrate and a pure portion, the concentrate is introduced into the second temporary storage tank 43 and the pure portion is transferred to the first temporary storage tank 44, and the rinsing member 4 of the rinsing member 4 will be A temporary storage tank 44 receives fresh water.
- the second temporary storage tank 43 also receives the condensate from the separator 29 which is only slightly contaminated with acid.
- a processing apparatus for using an acid etching solution includes an etching machine 1, in an etching machine 1 b 5 ⁇ vit- L 1 port Kil A S4 Jrti v ⁇ r ⁇ i, : ji- EI ⁇ - -fzr ife S4. it; it *il in . 1 hh ⁇ Washing part 4 is cleaned.
- the etching liquid is sent to the first unit 5a of the ionization device 5.
- the etchant has been used to consist of different components such as hydrochloric acid, copper chloride, sodium chloride, sodium percarbonate and water.
- the regenerated usable etching liquid transferred from the second portion 9b of the reproducing device 9 is sent to the etching machine 1.
- the ionization device 5 is connected in parallel with the acid extraction device 6, and the acid extraction device 6 is connected to the electrolysis device 7 including the electrolysis unit 7a and the temporary storage tank 7b, as illustrated in Fig. 1.
- the ionization device 5 is connected in series with the oxidation device 8.
- the oxidation device 8 comprises two units 8a and 8b, wherein the first oxidation unit 8a is connected to a regeneration device 9 comprising a first regeneration unit 9a and a second regeneration unit 9b.
- the second regeneration unit 9b of the regeneration device 9 is connected to the showerhead 3 of the etching machine 1.
- the acid extraction device 6 extracts the acid with a resin, and the solution from which the acid has been extracted is sent to the electrolytic cell 7a, and the solution is rinsed with a solution placed in a temporary storage tank (described below), after rinsing The solution is sent to the second oxidation unit 8b of the oxidation unit 8.
- the electrolysis unit of the electrolysis device 7 includes an anode chamber, a cathode chamber, and an anode membrane and a cathode chamber separated by a cation membrane, each anode chamber having graphite electrodes, each cathode chamber having a copper electrode.
- the cation membrane maintains the Cl 2 and 02 produced at the anode in the anode compartment and only Cu ++ into the cathode compartment to improve the efficiency of the precipitation process.
- Current generator with electrodes between 1.1 and 2.8 V The voltage provides a current with a current density of 2-7 A/dm 2 .
- the system includes a gas treatment device for excess gas.
- the evolved gas of the ionization device 5 is directed to the condenser 28 via a conduit 27.
- the gas treatment device includes a condenser 28, a separator 29 connected to the condenser 28, and a neutralizer 30 connected to the separator.
- the separator 29 includes three separation units 29a, 29b and 29c.
- the system comprises a water treatment device that transfers contaminated water from the flushing unit 4 from the flushing compartments 4b and 4c to the third temporary storage tank 41, the third temporary storage tank 41
- the water therein is fed to the infiltration member 42.
- the permeable member 42 is further attached to the second temporary storage tank 43 and the first temporary storage tank 44, and the temporary storage grooves 43 and 44 are also connected to the rinsing member 4 of the etching machine 1.
- the rinse water in the wash tank 4a enters the storage tank 38 connected to the extraction device 6, and the extraction device 6 is connected to the second oxidation unit 8b of the oxidation device 8.
- the etching machine 1 is preferably connected to the first unit 5a of the ionization device 5 via a conduit 10. If necessary, the used etching liquid can be supplied to the acid extracting device 6 via the connecting conduit 1 from the unit 5a. From the acid extraction unit 6, the etching solution has been used to enter the electrolysis unit 7 via the connecting conduit 12.
- the connecting conduit 12 connects the electrolytic unit 7a of the electrolysis unit 7 to the acid extracting unit 6. In the electrolytic cell 7a, metallic copper is precipitated as pure copper.
- the used etching liquid having reduced the copper concentration is discharged to the temporary storage tank 7b via the connecting pipe 13.
- the solution is preferably dosed to the first oxidation unit 8a of the oxidation unit 8 via the connection conduit 14 to lower the copper concentration.
- the used solution in the first oxidation unit 8a of the oxidation device 8 is a mixture of a solution transferred from the ionization device 5 via the connection conduit 15 and a solution from the temporary storage tank 7b of the electrolysis device 7.
- the used etching liquid is sent to the first regeneration unit 9a of the regeneration device 9 via the connection conduit 16.
- the processing solution 2 which has been completely restored to the original state is fed to the head 3 of the etching machine 1 via the connecting conduit 17.
- Figure la further illustrates the circulation of gas in the system that has been used to recover the etchant.
- gas is supplied from the etching machine 1, the electrolytic unit 7a of the electrolysis device 7, and the temporary storage tank
- the suction is carried out in 7b, and then the sucked gas is injected into the first oxidation unit 8a of the oxidation device 8 through the manifold 20, and the manifold 20 collects the supply conduits 20a, 20b and 20c together.
- the gas respectively extracted from the ionization units 5a, 5b and 5c of the ionization device 5 is injected into the second oxidation unit 8b of the oxidation device 8 via the manifold 21, and the manifold 21 concentrates the supply conduits 20a, 20b and 20c at together.
- the evolved gas in the first oxidation unit 8a will be sucked up and introduced into the second oxidation unit 8b by the connecting conduit 22 by means of a syringe.
- the evolved gas after the treatment with the etching liquid in the second oxidation unit 8b is injected into the first regeneration unit 9a of the regeneration device 9 via the connection conduit 23.
- the escape gas is sent to the second regeneration unit 9b via the connection conduit 24, and then sucked by the internal circuit having the connection conduit 25 and again It is injected into the second regeneration unit 9b.
- the excess gas escaping from the second regeneration unit 9b of the regeneration device 9 is sent to the fourth unit 5d of the oxidation device 5 via the connection conduit 26.
- the excess gas escaping from the fourth unit 5d is absorbed by the gas used by the used etching liquid in the second regeneration unit 9b of the reproducing device 9 and the used etching liquid in the unit 5d not being the ionizing device 5.
- the gas escaping from the fourth unit 5d is guided to the condenser 28 via the connecting pipe 27. In condenser 28, condensation of water and a significant amount of hydrochloric acid and chlorine occurs by cooling the gas.
- reaction construct complex [CuCl]+ is represented by the following formula:
- the gas from the upper portion of the condenser 28 is injected into the first separation unit 29a of the separator 29 through the connection duct 32.
- the gas is purged by the condensate that has been delivered to the separator 29 through the connecting conduit 37.
- the acid and chlorine dissolved in the solution 2a i.e., the condensate
- the connection conduit 34 to adjust the number of the regeneration device 9.
- the pH of the used etching solution in the second regeneration unit % The pH of the used etching solution in the second regeneration unit %.
- Chlorine and acid were extracted from the contaminated gas in the separator 29 in the following manner.
- the acid and chlorine-rich condensate 2a is transferred from the condenser 28 to the second separation unit 2% via the connection conduit 37, and the acid and chlorine dissolved in the solution 2a are released by the suction of the pressure in the reduction unit 29b.
- This pressure is formed by a pump installed in the separator 29) to increase the solubility of the gas in the solution 2a so that the acid and chlorine in the gas from the upper portion of the condenser 28 are sufficiently absorbed.
- the solution 2a saturated with acid and chlorine then overflows from the first separation unit 29a to the second separation unit 29b, thereby repeating the saturation and release cycles. After a certain number of cycles (the number of cycles depends on the feed rate of the condensate from the condenser 28), the solution 2a is sent to the third separation unit 29c for further extraction of acid and chlorine. After the treatment in the third separation unit 29c, the solution 2a flows through the connection conduit 45 to the water treatment.
- the neutralizer 30 After the cleaning in the first separation unit 29a of the separator 29, the excess gas is sent to the neutralizer 30 through the connection conduit 33 to perform the final neutralization treatment of the acid and chlorine by the solution 2b, wherein the solution 2b is NaOH.
- the main reaction is HC1 + NaOH ⁇ H 2 0 + NaCl
- the secondary reaction is HC10 3 + NaOH ⁇ H 2 0 + NaC10 3 , HC10 2 + NaOH ⁇ H 2 0 + NaC10 2 , HC10 + NaOH ⁇ H 2 0 + NaC10 , HC10 + NaOH ⁇ H 2 0 + NaC10 , HC10 + NaOH ⁇ H 2 0 + NaC10 , HC10 4 + NaOH ⁇ H 2 0 + NaC10 4 .
- the etching machine 1 having the cleaning portion includes the rinsing grids 4a, 4b And 4c.
- the contaminated flushing water is transferred from the flushing tank 4a to the temporary storage tank 38 through the connecting duct 40 as needed.
- the water present in the tank 38 is transferred to the extracting device 6 to clean the resin of the extracting device 6, and is finally
- the second oxidation unit 8b of the oxidation unit 8 is guided.
- the acid and chlorine-rich condensate 2a in the condenser 28 is sent to the second separation unit 29b via the connection conduit 37 to extract the dissolved acid and chlorine.
- the solution 2a is guided to the first separation unit 29a via the connection duct 36 to clean the gas sent through the connection duct 32.
- the chlorine and acid-releasing solution 2a is overflowed to the second separation unit 29b to be released again.
- the solution 2a falls into the third separating unit 29c to extract the acid and chlorine again and then flows through the connecting conduit 45 to the temporary storage tank 43, in the temporary storage tank 43, it is infiltrated with The concentrate supplied by unit 42 is mixed.
- the salt concentration of the solution in one of the rinse cells is greater than 1 gram per liter, it is fed to the rinsing compartment 4a via the connecting conduit 47a and/or to the rinsing compartments 4b and 4c via 47b and 47c, as needed.
- 4c continuously receives pure water from the temporary storage tank 44 via the connection duct 50, and the pure water in the permeation unit 42 is sent to the temporary storage tank 44 via the connection duct 49.
- the permeating device 42 receives water from the temporary storage tank 41 via the connecting duct 48, and the temporary storage tank 41 itself receives water from the flushing compartments 4b and 4c of the flushing member 4 via the connecting duct if the total salt concentration is less than 1 g/liter.
- the permeable member 42 has an efficiency of 80%, i.e., it can produce 80% pure water and 20% concentrated water, depending on the total amount to be treated.
- the purified water is sent to the rinse compartment 4c and overflows from the rinse compartment 4c to the rinse compartments 4b and 4a.
- the contaminated water in the rinsing compartment 4a is sent to the temporary storage tank 38 through the conduit 40.
- the extraction device 6 receives the used etching liquid from the ionizing device 5a, and extracts the acid through the resin in the extraction device 6, and the solution from which the acid has been extracted is sent to the electrolysis device 7, and in the temporary storage tank 38.
- the temporarily stored solution is sent to the extraction unit 6 to rinse the resin, and the rinsed liquid is sent to the second oxidation unit 8b of the oxidation unit 8.
- the above-described water circulation device particularly the solution of the rinsing cell 4a, is returned to the used etching liquid after rinsing the resin in the extraction device 6, and the loss due to evaporation of the fourth unit 5d of the ionization device 5 can be compensated for.
- the process or system for processing the used etchant is operated while the etch machine is operating (except for the electrolysis device 7 and the components directly connected thereto), the process or system can be used
- the etching liquid is independently operated in an internal circulation formed by the connection between the second regeneration unit 9b of the regeneration device 9 and the first unit 5a of the ionization device 5 via the connection duct 18.
- the excess gas coming out of the first unit 5a of the ionization device 5 is cleaned by a cycle in a circuit formed by connecting the second unit 5b and the fourth unit 5d via the conduit 19 using the etching liquid.
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Abstract
A recycling system used for treating a used etching solution comprising an ionization device (5), for decomplexing Cu(I) in a used acid etching solution delivered from an etching apparatus; an oxidation device (8), for receiving the used acid etching solution from the ionization device (5) and oxidizing Cu(I) in the received etching solution into Cu(II); an extraction device (6), for continuously or discontinuously receiving, at a preset rate, the used acid etching solution delivered from the ionization device (5) and extracting acid in the used acid etching solution; an electrolysis device (7), for receiving the used acid etching solution that has been treated by the extraction device (6) and precipitating copper in the used acid etching solution; and a regeneration device (9), for receiving the used etching solution that has been treated by the oxidation device (8), adjusting the pH value of the used etching solution, and stabilizing a monochloro copper complex in the form of [CuCl]+, so as to turn the used etching solution received by the regeneration device into a reusable etching solution. The recycling system can sufficiently and effectively recycle a used etching solution.
Description
处理已使用蚀刻液的再循环系统 Handling recycling systems that have used etchant
技术领域 及方法 Technical field and method
本发明涉及回收技术, 尤其涉及处理已使用蚀刻液的再循环系统( 背景技术 The present invention relates to recycling techniques, and more particularly to recycling systems that have used etching fluids ( Background of the Invention)
众所周知, 化学蚀刻处理在金属蚀刻产业中的应用非常普遍, 例如, 在印刷电路板的生产过程中采用化学蚀刻。 在蚀刻机或蚀刻生产线内, 含有 氯及其它量比较少的化学成分的有效蚀刻液,被持续施加到部分由薄铜片形 成的铜组件上, 以按照预先设定的拓朴, 通过选择性蚀刻来获得导电路径, J、 It is well known that chemical etching processes are very common in the metal etching industry, for example, chemical etching is used in the production of printed circuit boards. In an etching machine or etching line, an effective etching solution containing chlorine and other relatively small amounts of chemical components is continuously applied to a copper component formed of a thin copper sheet to pass the selectivity according to a predetermined topology. Etching to obtain a conductive path, J,
在蚀刻过程中, 常规的氯化物蚀刻液必需持续地由新鲜的蚀刻液或循 环再利用的蚀刻液来取代。 现有技术中, 对已使用蚀刻液的回收, 主要是析 出其中的铜, 但对蚀刻过程中所排出的气体以及蚀刻液中水的进行回收利 用, 则不理想。 例如, 申请号为 10/645,278的美国专利申请就描述了一种回 收已使用蚀刻液中的铜的技术。 During the etching process, the conventional chloride etching solution must be continuously replaced by a fresh etching solution or a circulating reuse etching solution. In the prior art, the recovery of the used etching liquid is mainly the precipitation of copper therein, but it is not preferable to recycle the gas discharged during the etching and the water in the etching liquid. For example, U.S. Patent Application Ser.
存在对通过简单有效且经济的方法回收已使用蚀刻液并同时在蚀刻机 器中再次利用它的系统或设备的需求。 发明内容 There is a need for a system or apparatus that recycles an used etchant and reuses it in an etch machine by a simple, efficient, and economical process. Summary of the invention
为达成以上及其它目的, 本发明提出一种处理已使用蚀刻液的回收系 统。 该系统包括电离装置、 氧化装置、 萃取装置、 电解装置、 以及再生装置。 该电离装置用于解络从蚀刻设备传送过来的已使用酸性蚀刻液中的 Cu(I); 该氧化装置接收来自电离装置的已使用酸性蚀刻液, 并将所接收蚀刻液中的 To achieve the above and other objects, the present invention provides a recovery system for treating used etching liquids. The system includes an ionization device, an oxidation device, an extraction device, an electrolysis device, and a regeneration device. The ionization device is configured to decompose Cu(I) in the used acidic etching solution transferred from the etching device; the oxidation device receives the used acidic etching solution from the ionization device, and the received etching solution
Cu(I)氧化为 Cu(II); 该萃取装置以预先设定的比率持续或非持续地接收从该 电离装置传送来的已使用酸性蚀刻液, 并萃取该已使用酸性蚀刻液中的酸; 该电解装置接收已由萃取装置处理过的已使用酸性蚀刻液, 并析出该已使用 酸性蚀刻液中的铜; 该再生装置接收在所述氧化装置处理过的已使用蚀刻 液, 调节该已使用蚀刻液的 PH值, 并稳定单氯的 [CuCl]+形式的铜络合物, 以使其所接收的已使用蚀刻液成为可再使用的蚀刻液; 其中, 在电离装置中
提取气体且将所提取的气体以及从电解装置逸出的气体被传送到氧化装置, 在该氧化装置中进一步提取气体且将所提取的气体传送到再生装置, 而从所 述再生装置逸出的气体被输送到电离装置。 Cu(I) is oxidized to Cu(II); the extraction device continuously or non-continuously receives the used acidic etching solution transferred from the ionizing device at a predetermined ratio, and extracts the acid in the used acidic etching solution The electrolysis device receives the used acidic etching solution that has been treated by the extraction device, and precipitates the copper in the used acidic etching solution; the regeneration device receives the used etching solution processed by the oxidation device, and adjusts the used Using the pH of the etchant and stabilizing the copper complex in the form of [CuCl] + monochloride so that the received etchant received becomes a reusable etchant; wherein, in the ionization device Extracting the gas and transferring the extracted gas and the gas escaping from the electrolysis device to an oxidizing device, in which the gas is further extracted and the extracted gas is transferred to the regenerating device, and the escaping device is escaping from the regenerative device The gas is delivered to the ionization device.
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 在所述电 离装置中通过提取 HC1气体来解络所述已使用酸蚀刻液。 Preferably, the treatment of the present invention has used a recirculating system of an acidic etchant in which the used acid etchant is decomposed by extracting HCl gas.
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 所述电离 Preferably, the treatment of the present invention has used a recirculating system of an acidic etchant, said ionization
Cu+和 C : CuCl2-→ Cu+ +2C1"和 CuC!2"→ CuCl + C! -。 Cu + and C : CuCl 2 -→ Cu + +2C1" and CuC! 2 "→ CuCl + C!
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 所述电离 装置包括接收已使用酸性蚀刻液的第一单元,接收来自所述第一单元的已使 用酸性蚀刻液的第二单元,以及接收来自所述第二单元的已使用酸性蚀刻液 的第三单元, 其中所述第二单元包括不止一个子单元且各子单元与其相邻的 子单元连接以便所述已使用蚀刻液可从一个子单元流入相邻的子单元。 Preferably, the treatment of the present invention has used a recirculating system of an acidic etchant, the ionization apparatus comprising a first unit that has received an acidic etchant, and a first used acidic etchant from the first unit a second unit, and receiving a third unit from the second unit that has used an acidic etchant, wherein the second unit includes more than one subunit and each subunit is coupled to its adjacent subunit for the used etch Liquid can flow from one subunit to an adjacent subunit.
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 由第二单 优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 从所述第 一单元和所述第二单元中提取气体。 Preferably, the treatment according to the present invention has used a recirculating system of an acidic etchant, from the second unit, preferably, the treatment system of the present invention has used an acid etchant recycling system from the first unit and The gas is extracted from the second unit.
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 从所述电 离装置传递到所述氧化装置的已使用酸性蚀刻液的体积与在所述电离装置 中的所述回路内循环的已使用蚀刻液的体积的比为 2比 1。 Preferably, the process of the present invention has used a recirculating system of an acidic etchant, the volume of the used acidic etchant transferred from the ionization device to the oxidizing device and the loop in the ionizing device The ratio of the volume of the used etchant used for the cycle is 2 to 1.
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 从所述电 离装置所提取的气体的体积与在所述电离装置的所述回路中循环的已使用 酸性蚀刻液的体积的比例为 1 比 1 , 且所述电离装置中的压力在 0.8atm到 0.95atm之间。 Preferably, the treatment according to the invention has used a recirculating system of acidic etchant, the volume of gas extracted from the ionization device and the volume of used acidic etchant circulating in the circuit of the ionization device The ratio is 1 to 1, and the pressure in the ionization device is between 0.8 atm and 0.95 atm.
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 所述氧化 装置被设置以通过注入其中的气体对 Cu(I)进行氧化, 而所述气体包括自所 述电离装置提取的气体、 来自所述电解装置以及所述蚀刻设备的气体。 优选 地, 所述气体被以 l.l-1.3atm之间的压力注入。 Preferably, the treatment of the present invention has used a recirculating system of an acidic etchant, the oxidizing means being arranged to oxidize Cu(I) by gas injected therein, and the gas comprises extracting from the ionizing means Gas, gas from the electrolysis device and the etching apparatus. Preferably, the gas is injected at a pressure of between 1.1 and 1.3 atm.
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 所述氧化
-J* ^ 4· 71 Hi J- — /U t fit i . -h h Ί¾ Λ± ^Preferably, the treatment of the present invention has used a recycling system of an acidic etchant, said oxidation -J* ^ 4· 71 Hi J- — /U t fit i . -hh Ί3⁄4 Λ± ^
C ^—tr ^— > I"U亍 Ui^^ ■早1 M'I 干 L» , ^—早 U干 υ ·*Γ ^ ^〃Ι ¾ r¾g ^p jL 中处理过的已使用酸性蚀刻液, 第二氧化单元从该第一氧化单元接收所述已 使用蚀刻液。 C ^-tr ^— >I"U亍Ui^^ ■ Early 1 M'I dry L» , ^—Early U dry · *Γ ^ ^〃Ι 3⁄4 r3⁄4g ^p jL Processed acid etching used And a second oxidation unit receives the used etching liquid from the first oxidation unit.
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 所述萃取 装置利用树脂来萃取酸, 且沖洗所述树脂后的溶液被送往所述氧化装置的第 二氧化单元。 Preferably, the treatment of the present invention has used a recirculating system of an acidic etching solution which utilizes a resin to extract the acid, and the solution after rinsing the resin is sent to the second oxidizing unit of the oxidizing device.
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 来自所述 山 Jl* ¾ AA Preferably, the process of the present invention has used a recirculating system of an acidic etchant from the mountain Jl*3⁄4 AA
设备的气体被送往所述第一氧化单元。 The gas of the apparatus is sent to the first oxidation unit.
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 来自所述 电解装置和所述蚀刻设备的气体包括纯氧、 氯和大气氧。 Preferably, the treatment of the present invention has used a recirculating system of acidic etchant, and the gases from the electrolysis apparatus and the etching apparatus include pure oxygen, chlorine, and atmospheric oxygen.
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 所述再生 装置包括第一再生单元和第二再生单元, 第一再生单元被用于调节所接收的 溶液的 PH值, 而所述第二再生单元被用于根据以下化学反应稳定单氯铜络
Preferably, the process of the present invention has used a recycling system of an acidic etching solution, the regeneration device comprising a first regeneration unit and a second regeneration unit, the first regeneration unit being used to adjust the pH of the received solution, And the second regeneration unit is used to stabilize the monochloro copper network according to the following chemical reaction
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 所述第一 再生单元接收来自所述氧化装置的气体。 Preferably, the treatment of the present invention has used a recirculation system of an acidic etchant, the first regeneration unit receiving gas from the oxidizer.
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 所述再生 装置设置有注射器泵, 以在第二再生单元中将来自第一再生单元的气体吸收 并再次注入到所述第二再生单元的溶液中。 Preferably, the process of the present invention has used a recirculation system of an acidic etchant, the regeneration device being provided with a syringe pump to absorb and re-inject the gas from the first regeneration unit into the second regeneration unit In the solution of the second regeneration unit.
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 所述电解 装置包括包含阳极、 电极和电流生成器的电解单元。 Preferably, the treatment of the present invention has used a recirculating system of an acidic etchant, the electrolysis apparatus comprising an electrolysis unit comprising an anode, an electrode and a current generator.
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 所述电流 生成器以 2安 /平方米到 7安 /平方米的密度提供电流, 其中电极之间的电压 在 1.1伏到 2.8伏之间。 Preferably, the process of the present invention has used a recirculating system of an acidic etchant that supplies current at a density of 2 amps per square meter to 7 amps per square meter with a voltage between the electrodes at 1.1 volts. Between 2.8 volts.
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 还包括气 体处理装置, 所述气体处理装置自从所述电离装置接收的气体中提取气体 HC1和痕量 Cl2, HCIO, HC102, HCIO3, HC104。 Preferably, the treatment of the present invention has used a recirculation system of an acidic etchant, and further includes a gas treatment device that extracts gas HC1 and traces of Cl 2 , HCIO from the gas received by the ionization device, HC10 2 , HCIO3, HC10 4 .
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 其中气体
Al、 τχϋ ^ ^ J-iL i ^ , ¾5 ¾3 r+τ 、k ^ ¾3 -tac ,Ι^- A h ^7 ^l^ ^ ΛΑPreferably, the treatment of the present invention has used a recirculating system of an acidic etchant, wherein the gas Al, τχϋ ^ ^ J-iL i ^ , 3⁄45 3⁄43 r+τ , k ^ 3⁄43 -tac , Ι^- A h ^7 ^l^ ^ ΛΑ
^L -^^ L o ^r'^ ^ yj~ T*7 升丁 , rt\ ^^' ^ ¾ r/| ^ ^tu i¾7 n w、j 第三单元的气体,并通过冷凝的方式从所接收的气体中分离气体 HC1和痕量 Cl2, HC10, HC102, HCIO3, HCIO4, 而所分离的气体被送往所述再生装置的第 一单元, 以及所述分离器接收所述冷凝器中的剩余气体, 并在所述分离器的 第一部分吸收 HC1和痕量 Cl2, HC10, HC102, HC103, HC104, 所分离的 HC1 气体和痕量 ci2, HC10, HC102, HCIO3, 11(:104气体被送往再生装置的第二单 元, 其中剩余气体包括 Cl2, HC10, HCIO2, HC103, HC104o ^L -^^ L o ^r'^ ^ yj~ T*7 升丁, rt\ ^^' ^ 3⁄4 r/| ^ ^tu i3⁄47 nw, j The gas of the third unit, and by means of condensation The received gas separates the gas HC1 and the traces of Cl 2 , HC10, HC10 2 , HCIO3, HCIO4, and the separated gas is sent to the first unit of the regeneration device, and the separator receives the condenser Residual gas, and in the first part of the separator, absorbs HC1 and traces of Cl 2 , HC10, HC10 2 , HC10 3 , HC10 4 , separated HC1 gas and traces of ci 2 , HC10, HC10 2 , HCIO3, 11 (: 10 4 gas is sent to the second unit of the regeneration unit, wherein the remaining gases include Cl 2 , HC10, HCIO2, HC10 3 , HC10 4o
yjJ ά. 八 ¾7 yjJ ά. Eight 3⁄47
Ί ϋ¾υ
刀 器包括第一分离单元、 第二分离单元和第三分离单元, 第一分离单元被用于 吸收来自冷凝器的气体中的 HC1和痕量 Cl2, HC10, HCIO2, HCIO3, HC104气 体, 而第二和第三单元被用来提取 HC1和痕量 Cl2, HC10, HC102, HC103, HCIO4气体。 Ί ϋ3⁄4υ The knife comprises a first separation unit, a second separation unit and a third separation unit, the first separation unit being configured to absorb HC1 and traces of Cl 2 , HC10, HCIO2, HCIO3, HC10 4 gas in the gas from the condenser, The second and third units were used to extract HC1 and traces of Cl 2 , HC10, HC10 2 , HC10 3 , HCIO4 gases.
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 进一步包 括水处理装置以及冲洗部件, 所述沖洗部件用来自蚀刻装置的已使用蚀刻液 以获得纯水, 并接收来自分离装置的溶液。 Preferably, the treatment of the present invention has used a recirculation system of an acidic etchant, further comprising a water treatment device and a rinsing member, the rinsing member using the etchant from the etching device to obtain pure water, and receiving from the separation The solution of the device.
优选地, 本发明所述的处理已使用酸性蚀刻液的再循环系统, 所述水处 理装置包括渗透单元和若干暂存槽,所述渗透单元用以对来自沖洗部件的溶 液进行处理以获得纯水, 所获得的纯水被送入第一暂存槽, 以在需要时从所 述第一暂存槽送入所述沖洗部件,所述渗透部件获得的非纯水的渗透物送入 第二暂存槽, 以与来自所述分离装置的溶液混合, 所混合的溶液根据需要被 送入所述冲洗部件。 Preferably, the treatment of the present invention has used a recirculation system of an acidic etchant, the water treatment device comprising a permeation unit and a plurality of temporary storage tanks for treating the solution from the rinsing member to obtain pure Water, the obtained pure water is sent to the first temporary storage tank to be fed into the rinsing member from the first temporary storage tank when necessary, and the permeate of the non-pure water obtained by the permeable member is fed into the first The second storage tank is mixed with the solution from the separation device, and the mixed solution is sent to the rinsing member as needed.
使用本发明所述的系统, 可有效回收已使用蚀刻液的溶液及有效利用回 收过程中的气体。 With the system of the present invention, the solution in which the etching solution has been used can be efficiently recovered and the gas in the recycling process can be effectively utilized.
本发明另外一个方面还提供一种再生已使用酸性蚀刻液的方法, 包括以 下步骤: a)将已使用酸性蚀刻液中的 Cu(I)络合物电离解络; b)将解络后的 Another aspect of the present invention provides a method of regenerating an acidic etching solution, comprising the steps of: a) ionizing and decomposing a Cu(I) complex in an acidic etching solution; b) decomposing
Cu(I)离子氧化为 Cu(II)离子; c) 形成 Cu(II)络合物, 以使已使用蚀刻液再生 为可使用的蚀刻液。 其中所述络合物可以是 Cu和 C1的络合物。 The Cu(I) ion is oxidized to a Cu(II) ion; c) a Cu(II) complex is formed to regenerate the used etching solution into a usable etching solution. Wherein the complex may be a complex of Cu and C1.
本发明再生已使用酸性蚀刻液的方法还可以包括以下步骤: 将步骤 a)
解络后的已使用酸性蚀刻液的一部分电解以析出铜。 另外, 还可以在电解之 前萃取所述一部分的已使用酸性蚀刻液中的酸, 以有利于铜的析出。 The method of the present invention for regenerating an acidic etching solution may further comprise the following steps: Step a) A part of the used acidic etching solution after the decompression is electrolyzed to precipitate copper. Alternatively, the acid in the portion of the used acidic etching solution may be extracted prior to electrolysis to facilitate precipitation of copper.
优选地,步骤 a)中通过提取已使用酸性蚀刻液中的 HC1气体来进行所述 解络。 优选地, 步骤 b)中的氧化至少部分由电离解络产生的气体和电解产生 的气体来进行, 大气氧或其他来源的氧化性气体也可以参与氧化。 优选地, 步骤 c)中通过调节已使用蚀刻液的 PH值并稳定 Cu(II)络合物, 例如用氯气 和氯化氢, 使已使用蚀刻液再生为可使用的蚀刻液。 附图说明 Preferably, the decomplexing is carried out in step a) by extracting the HC1 gas in the used acidic etching solution. Preferably, the oxidation in step b) is carried out at least in part by a gas generated by ionization and a gas produced by electrolysis, and atmospheric oxygen or an oxidizing gas of other origin may also participate in the oxidation. Preferably, in step c), the used etching solution is regenerated into a usable etching solution by adjusting the pH of the used etching solution and stabilizing the Cu(II) complex, for example, chlorine gas and hydrogen chloride. DRAWINGS
图 1示出了本发明所述蚀刻液再循环系统的示意性结构图; Figure 1 is a schematic structural view showing an etching solution recirculation system of the present invention;
图 la进一步示出了包括气体回路的本发明所述蚀刻液再循环系统的 示意性结构图; Figure la further shows a schematic structural view of the etching solution recirculation system of the present invention including a gas circuit;
图 lb进一步示出了包括水循环回路的本发明所述蚀刻液再循环系统 的示意性结构图; 以及 Figure 1b further illustrates a schematic structural view of the etchant recirculation system of the present invention including a water circulation loop;
图 2示出了氧化对 CU /CU+和 Cu+/Cu的化学势差的示意图。 具体实施方式 Figure 2 shows a schematic of the chemical potential difference of oxidation versus CU / CU + and Cu + /Cu. detailed description
在描述本发明之前, 需要说明的是本发明不限于以下所描述的具体实 施方式。 本领域技术人员可以理解到在不脱离本发明权利要求精神的情况 下, 可对以下所述的具体实施方式进行变更及修改。 Before describing the present invention, it is to be noted that the present invention is not limited to the specific embodiments described below. It will be appreciated by those skilled in the art that changes and modifications may be made to the specific embodiments described below without departing from the spirit of the invention.
简单地说, 本发明旨在对已使用酸性蚀刻液进行回收及再生, 使再生 后的酸性蚀刻液可再次用作蚀刻液。 根据本发明, 已使用酸性蚀刻液分别经 由萃取、 电离、 氧化、 电解、 以及再生等五个装置的处理而成为可再使用的 酸性蚀刻液, 并且这些可再使用的酸性蚀刻液用于蚀刻之后, 再次进入回收 及再生处理过程以被萃取、 电离、 氧化、 电解及再生等五个装置处理成为可 再使用的酸性蚀刻液。 进一步, 该回收及再生的处理过程包括对已使用酸性 蚀刻液的循环、 对回收及再生的处理过程中所释放的气体的循环的、 以及对 沖洗电路板的水的循环。 Briefly stated, the present invention is directed to the recovery and regeneration of an acid etchant that has been used, so that the regenerated acidic etchant can be reused as an etchant. According to the present invention, an acidic etching solution has been used as a reusable acidic etching solution by treatment of five devices such as extraction, ionization, oxidation, electrolysis, and regeneration, and these reusable acidic etching solutions are used after etching. , Re-enter the recycling and regeneration process to be processed into five reusable acidic etching solutions by extraction, ionization, oxidation, electrolysis and regeneration. Further, the recovery and regeneration process includes circulation of the acid etchant that has been used, circulation of the gas released during the process of recovery and regeneration, and circulation of water to the rinsing circuit board.
为简单起见, 在以下说明中, 用 "已使用蚀刻液,, 表示 "已使用酸性
τ τ ί,, 在以下描述中, 可同时参考图 1, la和 lb阅读。 For the sake of simplicity, in the following description, "Is used etchant," means that acidity has been used. τ τ ί,, in the following description, can be read simultaneously with reference to Figure 1, la and lb.
图 1示意了根据本发明的一个实施例, 处理已使用蚀刻液的循环系统 的示意性结构图。该图所示意的主要是对已使用蚀刻液的循环与处理。首先, 在电离装置 5中, 通过提取 HC1气体将溶液中的 [CuCl2]-解络为 Cu+和 Cr。 具体而言, 电离装置 5中进行了如下的化学反应: BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic block diagram showing the processing of a circulation system in which an etching solution has been used, in accordance with one embodiment of the present invention. The figure is mainly intended for the circulation and processing of the used etching solution. First, in the ionization device 5, [CuCl 2 ]- in the solution is decomposed into Cu + and Cr by extracting HCl gas. Specifically, the following chemical reaction is carried out in the ionization apparatus 5:
Cu++ + Cr ^ [CuCl]+ 如果 -l<-log[Cir < 0, Cu ++ + Cr ^ [CuCl]+ if -l<-log[Cir < 0,
Cu+ + 2C1"→ [CuCl2]" 如果 -log[Cl]- < 0, 以及 Cu + + 2C1"→ [CuCl 2 ]" if -log[Cl]- < 0, and
[CuCl2]"→ Cu+ + 2C1" 如果 -log[Cl]- > 0 [CuCl 2 ]"→ Cu + + 2C1" If -log[Cl]- > 0
电离装置 5中部分已使用蚀刻液被按照预先设定的比率供应给萃取装 , A¾ _ "Si" TTrt Jli , 丄厶: n if* Al - ci^ _止、々 An ά7? ^ ^ Some of the ionizer 5 has been supplied with an etchant at a predetermined ratio to the extraction unit, A3⁄4 _ "Si" TTrt Jli , 丄厶: n if* Al - ci^ _, 々 An ά7? ^ ^
JL 0, Τ Λ^ ^ W JL Ό tPJ 干 ^;?^王 /口, ¾L— ^ ^尸 J JL 0, Τ Λ^ ^ W JL Ό tPJ dry ^;? ^王 /口, 3⁄4L— ^ ^尸J
7。 在电解装置 7 中, 这部分已使用蚀刻液中的铜被析出。 通过将部分溶液 从 呙 直 ^ 田平 直 b !¾^王¾肝 旦 I ¾:4丁¾辭 π」 I 个及 明所述的已使用酸性蚀刻液的再循环系统中已使用蚀刻液中铜的浓度。 7. In the electrolysis device 7, this portion has been precipitated using copper in the etching solution. By Guo straight portion of the solution from the flat field B ^ ^ ¾ ¾ liver Wang Dan I ¾:! 4 π D ¾ speech "I have the next one and using an acid etching liquid recirculation system have been used in etching solution The concentration of copper.
经过在电离装置 5的若干单元中依次处理过的已使用蚀刻液被传递到 氧化装置 8。 在氧化装置 8中, 由于氧气 02富集使得 Cu(I)被氧化为 Cu(II)。 The used etchant that has been sequentially processed in several units of the ionization device 5 is transferred to the oxidizing device 8. In the oxidizing device 8, Cu(I) is oxidized to Cu(II) due to oxygen 02 enrichment.
随后通过在再生装置 9中,通过注入从氧化装置 8中传输过来的气体、 以及从电离装置 5中所逸出的气体中所分离出的氯气和盐酸, 对 Cu(II)进行 络合, 亦即, 使 CiT变为 [CuCl]+。 Subsequently, Cu(II) is complexed by injecting chlorine gas and hydrochloric acid separated from the gas transferred from the oxidation device 8 and the gas escaping from the ionization device 5 in the regeneration device 9, That is, CiT is changed to [CuCl]+.
优选地,从蚀刻机 1传送到电离装置 5的已使用蚀刻液被分成两部分。 占所传送来的已使用蚀刻液的全部量的 98.5%到 99.5%的溶液在经过氧化装 置 8和再生装置 9的处理之后, 被送回到蚀刻机 1。 已使用蚀刻液中剩余的 0.5%到 1.5%经过酸萃取装置 6被送往电解装置 7进行电解。在酸萃取装置 6 中, S交被从已使用溶液中萃取以提高电解装置 7的电解单元 7a的电解效率。 电解单元 7a中经过处理的已使用蚀刻液被送往暂存槽 7b。 从暂存槽 7b中, 已使用蚀刻液根据需要被投配给电离装置 5以对电离装置 5中的已使用蚀刻 液进行稀释。 Preferably, the used etching liquid transferred from the etching machine 1 to the ionizing device 5 is divided into two parts. The solution, which accounts for 98.5% to 99.5% of the total amount of the used etching liquid, is sent back to the etching machine 1 after being processed by the oxidation unit 8 and the regeneration unit 9. The remaining 0.5% to 1.5% of the etchant has been sent to the electrolysis unit 7 for electrolysis by the acid extraction unit 6. In the acid extracting device 6, S is extracted from the used solution to increase the electrolysis efficiency of the electrolytic unit 7a of the electrolysis device 7. The treated used etching liquid in the electrolytic cell 7a is sent to the temporary storage tank 7b. From the temporary storage tank 7b, an etchant has been used as needed to be dosed to the ionization apparatus 5 to dilute the used etching liquid in the ionization apparatus 5.
如前所迷, 已使用蚀刻液可由电离装置 3处理, 具体而言是通过依次
在电离装置 5的若千单元中进行处理来提取气体。 电离装置 5包括接收已使 用酸性蚀刻液的第一单元,从所述第一单元接收已使用酸性蚀刻液的第二单 元, 以及从所述第二单元接收已使用酸性蚀刻液的第三单元, 根据本发明的 示例, 所述第二单元包括二个子单元且该两个子单元之间相互连接以便所述 已使用蚀刻液可从一个子单元流入相邻的子单元。 需要说明的是, 尽管在本 发明的示例中,第二单元只包括两个子单元,但实际应用中并不以此为限制。 而且为清楚起见, 在以下描述中, 术语 "第二单元" 和 "第三单元" 指代的 是本段前述的第二单元的两个子单元。 As previously mentioned, the etching solution has been used to be processed by the ionization device 3, in particular by The gas is extracted by processing in a thousand units of the ionization device 5. The ionization device 5 includes a first unit that receives an used acidic etchant, receives a second unit that has used an acidic etchant from the first unit, and receives a third unit that has used an acidic etchant from the second unit, According to an example of the invention, the second unit comprises two subunits and the two subunits are interconnected such that the used etchant can flow from one subunit to an adjacent subunit. It should be noted that although in the example of the present invention, the second unit includes only two subunits, the actual application is not limited thereto. Moreover, for the sake of clarity, in the following description, the terms "second unit" and "third unit" refer to two subunits of the second unit previously described in this paragraph.
在第一单元 5a、 第二单元 5b和第三单元 5c中进行处理以从已使用蚀 刻液中提取和抽取气体。 首先是在第一单元 5a中进行气体提取以获得输送 给电解装置 7的非氧化蚀刻液, 由此, 输送给电解单元 7a的溶液中的酸因 部分被提取而使得溶液中的酸的含量减少。酸被减少的溶液以及稳定的 Cu(I) 络合物, 增加了电解单元 7a的电解效率。 电解单元 7a中所进行的化学反应 口下所示: Processing is performed in the first unit 5a, the second unit 5b, and the third unit 5c to extract and extract gas from the used etching liquid. First, gas extraction is performed in the first unit 5a to obtain a non-oxidizing etching liquid supplied to the electrolysis device 7, whereby the acid portion in the solution supplied to the electrolysis unit 7a is partially extracted to reduce the acid content in the solution. . The acid reduced solution and the stable Cu(I) complex increase the electrolysis efficiency of the electrolytic cell 7a. The chemical reaction carried out in the electrolysis unit 7a is shown below:
[CiiClj + 2c―" ^ Cu + Cr , 和 [CiiClj + 2c―" ^ Cu + Cr , and
[CuCl2]" + e-→ Cu + 2d- 进一步利用已使用蚀刻液以清洗来自再生装置 9的第二部分%的气 体。 来自第二单元 5b且已经过气体和盐酸提取的溶液, 被传递到第三单元 5c以再次提取气体。在电离装置 5的第二单元 5b和第三单元 5c中已进行了 气体提取的已使用蚀刻液被传送到第四单元 5d,以从自再生装置 9的第二部 分 9b所传送来的气体中吸收酸和氯气。 优选地, 在单元 5d, 5c和 5b之间 形成回路, 使已使用蚀刻液在该回路中流动若千个循环, 在循环期间可从已 使用蚀刻液中提取更多的气体,在进行了若干循环从而有效地降低了溶液气 体的量之后, 已使用蚀刻液被传递到第四单元 5d, 以吸收更多的酸和氯气。 [CuCl 2 ]" + e-→ Cu + 2d- further utilizes an etchant that has been used to clean the second portion of the gas from the regeneration device 9. The solution from the second unit 5b that has been extracted by gas and hydrochloric acid is passed Going to the third unit 5c to extract the gas again. The used etching liquid that has been subjected to gas extraction in the second unit 5b and the third unit 5c of the ionization device 5 is sent to the fourth unit 5d to be from the self-regeneration device 9. The gas sent from the second portion 9b absorbs acid and chlorine. Preferably, a loop is formed between the units 5d, 5c and 5b so that the etchant has been used to flow in the loop for a thousand cycles, during which the cycle can be More gas has been extracted from the etching solution, and after several cycles have been performed to effectively reduce the amount of the solution gas, the etching liquid has been used to be transferred to the fourth unit 5d to absorb more acid and chlorine.
在该回路中的若干循环(优选为三个循环)之后, 已使用蚀刻液被传 递到氧化装置 8的第一氧化单元 8a。 在电离装置 5中, 单元 5d因充分地吸 收了来自再生装置 9的第二部分 9b所传送来的气体, 从而饱含酸和氯。 单 元 5d中的溶液被送往第二单元 5b, 并在单元 5b和 5c中, 将这些酸和氯从 已使用蚀刻液中释放。在氧化装置 8的第一氧化单元 8a中,分别从蚀刻机 1、
电解单元 7a和暂存槽 7b中提取的大气氧、 纯氧和氯气被注入到氧化装置 8 的第一氧化单元 8a以进行如下的化学反应: After several cycles (preferably three cycles) in the loop, the etchant has been used to be transferred to the first oxidizing unit 8a of the oxidizing device 8. In the ionization device 5, the unit 5d is sufficiently rich in acid and chlorine because it sufficiently absorbs the gas sent from the second portion 9b of the regeneration device 9. The solution in unit 5d is sent to the second unit 5b, and in units 5b and 5c, these acids and chlorine are released from the used etching solution. In the first oxidizing unit 8a of the oxidizing device 8, respectively, from the etching machine 1, Atmospheric oxygen, pure oxygen, and chlorine extracted from the electrolytic cell 7a and the temporary storage tank 7b are injected into the first oxidation unit 8a of the oxidation device 8 to perform the following chemical reaction:
Cu + H+ + l/ 02→ Cu" + H20 Cu + H + + l/ 0 2 → Cu" + H 2 0
然后, 该溶液进入氧化装置 8的第二氧化单元 8b。 Then, the solution enters the second oxidation unit 8b of the oxidation unit 8.
根据本发明, 优选地, 从所述电离装置传递到所述氧化装置的已使用 酸性蚀刻液的体积与在所述电离装置中的所述回路内循环的已使用蚀刻液 的体积的比为 2比 1。 此外, 优选从所述电离装置所提取的气体的体积与在 所述电离装置的所述回路中循环的已使用酸性蚀刻液的体积的比例为 1 比 1, 且所述电离装置中的压力在 0.8atm到 0.95atm之间。 根据本发明的设置, 可充分将已使用溶液中的气体提取出来。 According to the present invention, preferably, the ratio of the volume of the used acidic etching solution transferred from the ionization device to the oxidation device to the volume of the used etching solution circulating in the circuit in the ionization device is 2 Than 1. Further, preferably, the ratio of the volume of the gas extracted from the ionization device to the volume of the used acidic etching solution circulating in the circuit of the ionization device is 1 to 1, and the pressure in the ionization device is 0.8atm to 0.95atm. According to the arrangement of the present invention, the gas in the used solution can be sufficiently extracted.
从氧化装置 8的第一氧化单元 8a逸出的气体以及分别从电离装置 5a、 5b和 5c中所吸出的气体被注入到第二氧化单元 8b。 在氧化装置 8的第二氧 化单 8b中按照如下的反应完成氧化:
The gas escaping from the first oxidizing unit 8a of the oxidizing device 8 and the gas sucked from the ionizing devices 5a, 5b, and 5c, respectively, are injected into the second oxidizing unit 8b. Oxidation is carried out in the second oxidation unit 8b of the oxidation unit 8 in accordance with the following reaction:
上述反应期间, 如果需要, 可以根据如下的化学反应向已使用蚀刻液投配催 化剂以提供支持: During the above reaction, if necessary, a catalyst may be added to the used etching solution to provide support according to the following chemical reaction:
2[CuCl2]" + 4H+ + 1/2 02 → 2[CuCl]+ + 2HC1 + ¾0; 以及 2[CuCl 2 ]" + 4H + + 1/2 0 2 → 2[CuCl] + + 2HC1 + 3⁄40;
Cu+ + H+ + 1/4 02→ Cu++ + H20. Cu+ + H + + 1/4 0 2 → Cu ++ + H 2 0.
通常,在第一氧化单元 8a中所进行的氧化反应的氧化度为 70%, 而在 第二氧化单元 8b中基本完成氧化反应, 亦即达成基本百分之百的氧化。 Usually, the degree of oxidation of the oxidation reaction carried out in the first oxidation unit 8a is 70%, and the oxidation reaction is substantially completed in the second oxidation unit 8b, i.e., substantially 100% oxidation is achieved.
在完成氧化之后, 从氧化装置 8传送来的已使用蚀刻液由再生装置 9 处理。 再生装置 9依次通过两个单元来处理该已使用蚀刻液。 在第一再生单 元 9a中, 溶液被酸化, 而在第二再生单元 9b中, 铜络合物 [CuCl]+被稳定。 然后, 被再生装置 9中完全处理过的溶液被输送给蚀刻机 1的喷头 3, 从喷 头 3喷向印刷电路板。再次用于蚀刻电路板的溶液,在蚀刻过后富含 [CuCl2]_, 该已使用蚀刻液被送往电离装置 5的第一单元 5a以再次重复如上所述的整 个处理过程。 After the oxidation is completed, the used etching liquid transferred from the oxidation device 8 is processed by the regeneration device 9. The reproducing device 9 sequentially processes the used etching liquid by two units. In the first regeneration unit 9a, the solution is acidified, and in the second regeneration unit 9b, the copper complex [CuCl] + is stabilized. Then, the solution completely processed by the reproducing device 9 is sent to the head 3 of the etching machine 1, and is ejected from the head 3 to the printed circuit board. The solution for etching the circuit board again is enriched in [CuCl 2 ]_ after the etching, and the used etching liquid is sent to the first unit 5a of the ionization device 5 to repeat the entire process as described above again.
在工作期间从蚀刻溶液中逸出的气体的重复利用过程是由气体处理设
备处理的, 该气体处理设备包括冷凝器 28、 分离器 29和中和器 30。 The process of recycling the gas escaping from the etching solution during operation is by gas treatment The gas treatment apparatus includes a condenser 28, a separator 29, and a neutralizer 30.
从电离装置 5逸出的多余气体经过冷凝器 28被送往分离器 29, 然后 到中和器 30, 以确保对气体的完全处理和重复利用。 The excess gas escaping from the ionization unit 5 is sent to the separator 29 via the condenser 28 and then to the neutralizer 30 to ensure complete treatment and reuse of the gas.
为了将气体循环保持在一个封闭的回路(仅例外地, 根据 PH测量器 的指示来将盐酸投配到氧化装置 8的第一氧化单元 8a中) 中, 并避免任何 损失和污染。 根据本发明 , 来自蚀刻机 1的 HC1和大气氧, 来自电解装置 7 的电解单元 7a的纯氧和氯, 以及来自电解装置 7的暂存槽 7b的气体, 可以 由装设在氧化装置 8a中的注射器吸取并注入到氧化装置 8的第一氧化单元 8a的已使用蚀刻液中。 In order to keep the gas circulation in a closed loop (except, the hydrochloric acid is dispensed into the first oxidation unit 8a of the oxidation unit 8 according to the indication of the pH meter), and any loss and contamination are avoided. According to the present invention, HC1 and atmospheric oxygen from the etching machine 1, pure oxygen and chlorine from the electrolytic unit 7a of the electrolysis device 7, and gas from the temporary storage tank 7b of the electrolysis device 7 can be installed in the oxidation device 8a. The syringe is sucked and injected into the used etching liquid of the first oxidation unit 8a of the oxidation device 8.
从氧化装置 8的第一氧化单元中逸出的气体以及从电离装置 5的第一 单元 5a、 第二单元 5b和第三单元 5c中吸出的气体,被注入到氧化装置 8的 第二氧化单元 8b中的已使用溶液中。来自氧化装置 8的第二氧化单元 8b的 逸出气体被送入再生装置 9的第一再生单元 9a。再生装置 9的第一再生单元 9a的逸出气体被吸收并且被注入到第二再生单元 9b, 例如通过在再生装置 9a中所安装的注射器。 The gas escaping from the first oxidizing unit of the oxidizing device 8 and the gas sucked from the first unit 5a, the second unit 5b, and the third unit 5c of the ionizing device 5 are injected into the second oxidizing unit of the oxidizing device 8. Used in the solution in 8b. The evolved gas from the second oxidation unit 8b of the oxidation unit 8 is sent to the first regeneration unit 9a of the regeneration unit 9. The evolved gas of the first regeneration unit 9a of the regeneration device 9 is absorbed and injected into the second regeneration unit 9b, for example, by a syringe installed in the regeneration device 9a.
从已由再生装置 9的第二再生单元 9b处理过的已使用蚀刻液中逸出的 多余气体,被送到电离装置 5的第四单元 5d, 以在电离装置 5中通过如上文 所述的若干循环来将该气体尽可能地提取出来送往氧化装置的第二氧化单 元 8b, 而从第四单元 5d逸出的气体则被送往冷凝器 28。 Excess gas escaping from the used etchant that has been processed by the second regeneration unit 9b of the regeneration device 9 is sent to the fourth unit 5d of the ionization device 5 to pass through the ionization device 5 as described above. The gas is extracted as much as possible to the second oxidizing unit 8b of the oxidizing unit, and the gas escaping from the fourth unit 5d is sent to the condenser 28.
在冷凝器 28中, 气体被冷却到 5。 (:, 而氯、 酸和水蒸气凝结。 冷凝后, 冷凝器 28包含三部分:位于冷凝器 28最底部的液体冷凝物、位于冷凝器 28 中部的氯和氯化氢气体、 位于冷凝器上部的气体混合物。 位于冷凝器 28 中 部的气体被吸取并被注入到再生装置 9的第一再生单元 9a中。 位于冷凝器 28的上部的气体混合物被送往分离器 29。 In the condenser 28, the gas is cooled to 5. (:, while chlorine, acid and water vapor condense. After condensation, the condenser 28 contains three parts: liquid condensate at the bottom of the condenser 28, chlorine and hydrogen chloride gas in the middle of the condenser 28, gas at the upper part of the condenser The gas located in the middle of the condenser 28 is sucked and injected into the first regeneration unit 9a of the regeneration device 9. The gas mixture located at the upper portion of the condenser 28 is sent to the separator 29.
分离器 29中的溶液是冷凝器 28中的凝结物, 并且该溶液将被持续地 送往水处理装置。 分离器 29包括三个单元, 其中第一分离单元 29a用于吸 收酸、氯化氢气体和 C12,HC10,HC102, HC103, HC104气体痕量。 第二分离单 元 29b和第三分离单元 29c被用于提取氯和一定量的酸。 经过在分离器 29 中的处理, 气体被导向中和器 30以便在其被幹放到本发明的处理已使用蚀
trj - f^i] *i、 - - 凡" ^ fjg -f^-^LA 取 Λ口 w'v 刀 7 r, 刀— ^ ^a- 厶 丁 》i人术 u 酸和氯被送回到再生装置 9的第二再生单元 9b。 The solution in separator 29 is the condensate in condenser 28 and the solution will be continuously sent to the water treatment unit. The separator 29 includes three units, wherein the first separation unit 29a is for absorbing acid, hydrogen chloride gas and traces of C1 2 , HC10, HC10 2 , HC10 3 , HC10 4 gas. The second separation unit 29b and the third separation unit 29c are used to extract chlorine and a certain amount of acid. After the treatment in the separator 29, the gas is directed to the neutralizer 30 so that it has been used in the treatment of the present invention. Trj - f^i] *i, - - Where "^ fjg -f^-^LA take the mouth w'v knife 7 r, knife - ^ ^a- Kenting" i man surgery u acid and chlorine are sent back Go to the second regeneration unit 9b of the regeneration device 9.
现在将描述在蚀刻作业之后, 被用于冲洗印刷电路板且从蚀刻机所传 送过来的冲洗水的重复利用过程。 The recycling process of the rinse water used to rinse the printed circuit board and transported from the etching machine after the etching operation will now be described.
该水处理设备包括渗透部件 42和三个中间槽,以保持沖洗水在一个封 闭的回路中循环而没有污染, 并且将从蚀刻室中拖出来的蚀刻液回收到蚀刻 装置的沖洗部件,而仅例外地,新鲜水被投配以维持沖洗模块中的溶液水平。 The water treatment apparatus includes a permeating member 42 and three intermediate tanks to keep flushing water circulating in a closed loop without contamination, and the etching liquid drawn from the etching chamber is recovered to the flushing member of the etching apparatus, and only Exceptionally, fresh water is dosed to maintain the level of solution in the rinse module.
J-β r ΐ ΡΤΠ J^ J止 、- Jr . k 1/ i I El 女 、Ά、 t 4々 J Λ ^ λ 、'τ ,、 _¾t L Λ 叮 , -|/u¾u L»/j、/y ^ zFj 二' i ,i 、 υ ^ , | π 中导向第三暂存槽 41。 从第三暂存槽 41再将沖洗水馈送到渗透部件 42。 渗 透部件 42将进入的沖洗水分成浓缩物和纯净部分, 浓缩物被导入第二暂存 槽 43而纯净的部分将被传送到第一暂存槽 44,沖洗部件 4的冲洗格 4c将从 第一暂存槽 44接收新鲜水。 第二暂存槽 43也接收来自分离器 29的只是被 酸轻微污染的凝结物。 J-β r ΐ ΡΤΠ J^ J, - Jr . k 1/ i I El female, Ά, t 4々J Λ ^ λ , 'τ , , _3⁄4t L Λ 叮, -|/u3⁄4u L»/j, /y ^ z F j The two 'i, i, υ ^ , | π are directed to the third temporary storage slot 41. The flushing water is fed from the third temporary storage tank 41 to the permeating member 42. The permeable member 42 divides the incoming rinsing water into a concentrate and a pure portion, the concentrate is introduced into the second temporary storage tank 43 and the pure portion is transferred to the first temporary storage tank 44, and the rinsing member 4 of the rinsing member 4 will be A temporary storage tank 44 receives fresh water. The second temporary storage tank 43 also receives the condensate from the separator 29 which is only slightly contaminated with acid.
根据图 1, 用于已使用酸蚀刻液的处理设备包括蚀刻机 1, 在蚀刻机 1 b 5 ^ vit- L 1 口 Kil A S4 Jrti v^r^ i, : ji- EI ^- -fzr ife S4. it; it *il in . 1 hh ^ 洗部件 4中被清洗。 蚀刻之后, 蚀刻液被送往电离装置 5的第一单元 5a。 已 使用蚀刻液由不同的成分组成, 例如盐酸、 氯化铜、 氯化钠、 高氢酸钠和水。 从再生装置 9的第二部分 9b传送来的已再生可用的蚀刻液被送往蚀刻机 1。 According to Fig. 1, a processing apparatus for using an acid etching solution includes an etching machine 1, in an etching machine 1 b 5 ^ vit- L 1 port Kil A S4 Jrti v^r^ i, : ji- EI ^- -fzr ife S4. it; it *il in . 1 hh ^ Washing part 4 is cleaned. After the etching, the etching liquid is sent to the first unit 5a of the ionization device 5. The etchant has been used to consist of different components such as hydrochloric acid, copper chloride, sodium chloride, sodium percarbonate and water. The regenerated usable etching liquid transferred from the second portion 9b of the reproducing device 9 is sent to the etching machine 1.
电离装置 5与酸萃取装置 6并行连接, 酸萃取装置 6被连接到包括电 解单元 7a和暂存槽 7b的电解装置 7中, 如图 1所示意的那样。 电离装置 5 与氧化装置 8串行连接。 氧化装置 8包括两个单元 8a和 8b, 其中第一氧化 单元 8a与包括第一再生单元 9a和第二再生单元 9b的再生装置 9连接。 再 生装置 9的第二再生单元 9b被连接到蚀刻机 1的喷头 3。在萃取酸时, 酸萃 取装置 6用树脂将酸萃取处理, 而已经萃取了酸的溶液则送入电解单元 7a, 再利用放在暂存槽(下文描述) 中的溶液来冲洗树脂, 沖洗后的溶液被送往 氧化装置 8的第二氧化单元 8b。电解装置 7的电解单元包括阳极室、阴极室, 阳极室和阴极室之间由阳离子膜间隔开, 每个阳极室具有石墨电极, 每个阴 极室具有铜电极。 该阳离子膜将在阳极产生的 Cl2和 02保持在阳极室, 而仅 让 Cu++到阴极室,以改善析出过程的效率。电流生成器以电极之间 1.1到 2.8 V
的电压提供电流密度为 2-7 A/dm2的电流。 The ionization device 5 is connected in parallel with the acid extraction device 6, and the acid extraction device 6 is connected to the electrolysis device 7 including the electrolysis unit 7a and the temporary storage tank 7b, as illustrated in Fig. 1. The ionization device 5 is connected in series with the oxidation device 8. The oxidation device 8 comprises two units 8a and 8b, wherein the first oxidation unit 8a is connected to a regeneration device 9 comprising a first regeneration unit 9a and a second regeneration unit 9b. The second regeneration unit 9b of the regeneration device 9 is connected to the showerhead 3 of the etching machine 1. In the extraction of the acid, the acid extraction device 6 extracts the acid with a resin, and the solution from which the acid has been extracted is sent to the electrolytic cell 7a, and the solution is rinsed with a solution placed in a temporary storage tank (described below), after rinsing The solution is sent to the second oxidation unit 8b of the oxidation unit 8. The electrolysis unit of the electrolysis device 7 includes an anode chamber, a cathode chamber, and an anode membrane and a cathode chamber separated by a cation membrane, each anode chamber having graphite electrodes, each cathode chamber having a copper electrode. The cation membrane maintains the Cl 2 and 02 produced at the anode in the anode compartment and only Cu ++ into the cathode compartment to improve the efficiency of the precipitation process. Current generator with electrodes between 1.1 and 2.8 V The voltage provides a current with a current density of 2-7 A/dm 2 .
参考图 lb, 系统包括用于多余气体的气体处理装置。 电离装置 5的逸 出气体经由导管 27导向冷凝器 28。 该气体处理装置包括冷凝器 28、 与冷凝 器 28连接的分离器 29、 以及与分离器连接的中和器 30。 分离器 29包括三 个分离单元 29a, 29b和 29c。 Referring to Figure lb, the system includes a gas treatment device for excess gas. The evolved gas of the ionization device 5 is directed to the condenser 28 via a conduit 27. The gas treatment device includes a condenser 28, a separator 29 connected to the condenser 28, and a neutralizer 30 connected to the separator. The separator 29 includes three separation units 29a, 29b and 29c.
根据图 lb、 la和 1, 该系统包括水处理装置, 该水处理装置将冲洗部 件 4中的污染水从冲洗格 4b和 4c中传送到第三暂存槽 41 , 第三暂存槽 41 再将其中的水馈送给渗透部件 42。 渗透部件 42进一步附接第二暂存槽 43 和第一暂存槽 44, 暂存槽 43和 44同样也连接到蚀刻机 1的冲洗部件 4。 沖 洗格 4a中的冲洗水进入与萃取装置 6连接的存储槽 38, 而萃取装置 6连接 到氧化装置 8的第二氧化单元 8b。 According to Figures lb, la and 1, the system comprises a water treatment device that transfers contaminated water from the flushing unit 4 from the flushing compartments 4b and 4c to the third temporary storage tank 41, the third temporary storage tank 41 The water therein is fed to the infiltration member 42. The permeable member 42 is further attached to the second temporary storage tank 43 and the first temporary storage tank 44, and the temporary storage grooves 43 and 44 are also connected to the rinsing member 4 of the etching machine 1. The rinse water in the wash tank 4a enters the storage tank 38 connected to the extraction device 6, and the extraction device 6 is connected to the second oxidation unit 8b of the oxidation device 8.
参考图 1, 蚀刻机 1优选地经由导管 10连接到电离装置 5的第一单元 5a。 如果需要, 从所述的单元 5a, 该已使用蚀刻液可以经由连接导管 1 1投 配给酸萃取装置 6。 从该酸萃取装置 6, 已使用蚀刻液经由连接导管 12进入 电解装置 7。连接导管 12将电解装置 7的电解单元 7a与酸萃取装置 6连接。 在电解单元 7a中, 金属铜被析出为纯净铜。 Referring to Figure 1, the etching machine 1 is preferably connected to the first unit 5a of the ionization device 5 via a conduit 10. If necessary, the used etching liquid can be supplied to the acid extracting device 6 via the connecting conduit 1 from the unit 5a. From the acid extraction unit 6, the etching solution has been used to enter the electrolysis unit 7 via the connecting conduit 12. The connecting conduit 12 connects the electrolytic unit 7a of the electrolysis unit 7 to the acid extracting unit 6. In the electrolytic cell 7a, metallic copper is precipitated as pure copper.
然后, 已降低了铜浓度的已使用蚀刻液经由连接管 13 排放到暂存槽 7b。 从暂存槽 7b, 该溶液优选地经由连接导管 14投配给氧化装置 8的第一 氧化单元 8a, 以降低铜浓度。 Then, the used etching liquid having reduced the copper concentration is discharged to the temporary storage tank 7b via the connecting pipe 13. From the temporary storage tank 7b, the solution is preferably dosed to the first oxidation unit 8a of the oxidation unit 8 via the connection conduit 14 to lower the copper concentration.
氧化装置 8的第一氧化单元 8a内的已使用溶液是经由连接导管 15从 电离装置 5传送来的溶液和从电解装置 7的暂存槽 7b来的溶液的混合物。 分别经由氧化装置 8的第一氧化单元 8a和第二氧化单元 8b的处理之后, 该 已使用蚀刻液经由连接导管 16送往再生装置 9的第一再生单元 9a。 经由再 生装置 9的第一再生单元 9a的处理以及第二再生单元 9b的最后处理之后, 已完全被恢复为原来状态的处理溶液 2经由连接导管 17被馈送到蚀刻机 1 的喷头 3。 The used solution in the first oxidation unit 8a of the oxidation device 8 is a mixture of a solution transferred from the ionization device 5 via the connection conduit 15 and a solution from the temporary storage tank 7b of the electrolysis device 7. After the treatment by the first oxidation unit 8a and the second oxidation unit 8b of the oxidation device 8, respectively, the used etching liquid is sent to the first regeneration unit 9a of the regeneration device 9 via the connection conduit 16. After the processing of the first reproducing unit 9a of the reproducing device 9 and the final processing of the second reproducing unit 9b, the processing solution 2 which has been completely restored to the original state is fed to the head 3 of the etching machine 1 via the connecting conduit 17.
作为本发明的优选实施例, 图 la进一步示出了已使用蚀刻液回收系统 中气体的循环。 As a preferred embodiment of the invention, Figure la further illustrates the circulation of gas in the system that has been used to recover the etchant.
根据本发明, 将气体从蚀刻机 1, 电解装置 7的电解单元 7a和暂存槽
7b中吸取, 然后将吸取的气体通过多支管 20注入到氧化装置 8的第一氧化 单元 8a中, 多支管 20将供应导管 20a、 20b和 20c集聚在一起。 According to the present invention, gas is supplied from the etching machine 1, the electrolytic unit 7a of the electrolysis device 7, and the temporary storage tank The suction is carried out in 7b, and then the sucked gas is injected into the first oxidation unit 8a of the oxidation device 8 through the manifold 20, and the manifold 20 collects the supply conduits 20a, 20b and 20c together.
另一方面, 从电离装置 5的电离单元 5a、 5b和 5c中分别提取的气体 经由总管 21被注入到氧化装置 8的第二氧化单元 8b中, 总管 21将供应导 管 20a、 20b和 20c集聚在一起。 第一氧化单元 8a中的逸出气体将被吸取并 借助注射器由连接导管 22投入到第二氧化单元 8b。第二氧化单元 8b中的已 使用蚀刻液处理之后的逸出气体将经由连接导管 23被注入到再生装置 9的 第一再生单元 9a中。 On the other hand, the gas respectively extracted from the ionization units 5a, 5b and 5c of the ionization device 5 is injected into the second oxidation unit 8b of the oxidation device 8 via the manifold 21, and the manifold 21 concentrates the supply conduits 20a, 20b and 20c at together. The evolved gas in the first oxidation unit 8a will be sucked up and introduced into the second oxidation unit 8b by the connecting conduit 22 by means of a syringe. The evolved gas after the treatment with the etching liquid in the second oxidation unit 8b is injected into the first regeneration unit 9a of the regeneration device 9 via the connection conduit 23.
经过再生装置 9的第一再生单元 9a对其中已使用蚀刻液的处理之后, 逸出气体被经由连接导管 24送入第二再生单元 9b, 并随后借助具有连接导 管 25的内部回路被吸取并再次注入到第二再生单元 9b。 After the first regeneration unit 9a of the regeneration device 9 has processed the etching liquid therein, the escape gas is sent to the second regeneration unit 9b via the connection conduit 24, and then sucked by the internal circuit having the connection conduit 25 and again It is injected into the second regeneration unit 9b.
自再生装置 9的第二再生单元 9b逸出的多余气体经由连接导管 26被 送往氧化装置 5的第四单元 5d。 从第四单元 5d逸出的多余气体是由未被再 生装置 9的第二再生单元 9b内的已使用蚀刻液所利用的气体和未被电离装 置 5的单元 5d中的已使用蚀刻液所吸收的气体组成的。从第四单元 5d逸出 的气体经由连接管 27被导向冷凝器 28。在冷凝器 28中,通过对气体进行降 温, 水和相当数量的盐酸以及氯的凝结发生。 该处理之后, 在柱形体的冷凝 器 28的中部的氯和盐酸借助连接导管 31被注入到再生装置 9的第一再生单 元 9a中, 其中来自冷凝器 28的氯和盐酸被用于才艮据如下式所示的反应构建 络合物 [CuCl]+: The excess gas escaping from the second regeneration unit 9b of the regeneration device 9 is sent to the fourth unit 5d of the oxidation device 5 via the connection conduit 26. The excess gas escaping from the fourth unit 5d is absorbed by the gas used by the used etching liquid in the second regeneration unit 9b of the reproducing device 9 and the used etching liquid in the unit 5d not being the ionizing device 5. The composition of the gas. The gas escaping from the fourth unit 5d is guided to the condenser 28 via the connecting pipe 27. In condenser 28, condensation of water and a significant amount of hydrochloric acid and chlorine occurs by cooling the gas. After this treatment, chlorine and hydrochloric acid in the middle of the condenser 28 of the cylindrical body are injected into the first regeneration unit 9a of the regeneration device 9 by means of the connection conduit 31, wherein chlorine and hydrochloric acid from the condenser 28 are used for the data. The reaction construct complex [CuCl]+ is represented by the following formula:
Cu++ + + Cl2→ [CuCl]+, Cu ++ + + Cl 2 → [CuCl] + ,
另一方面, 来自冷凝器 28上部的气体通过连接导管 32注入到分离器 29的 第一分离单元 29a。 在分离器 29中, 由已通过连接导管 37输送到分离器 29 中的冷凝物清洗气体。 在第二分离单元 29b, 溶解在溶液 2a (亦即冷凝物) 中的酸和氯被吸收, 并且通过连接导管 34注入到再生装置 9的第二再生单 元 9b中,以调节再生装置 9的第二再生单元%中的已使用蚀刻液的 PH值。 On the other hand, the gas from the upper portion of the condenser 28 is injected into the first separation unit 29a of the separator 29 through the connection duct 32. In the separator 29, the gas is purged by the condensate that has been delivered to the separator 29 through the connecting conduit 37. In the second separation unit 29b, the acid and chlorine dissolved in the solution 2a (i.e., the condensate) are absorbed, and injected into the second regeneration unit 9b of the regeneration device 9 through the connection conduit 34 to adjust the number of the regeneration device 9. The pH of the used etching solution in the second regeneration unit %.
从分离器 29中的已污染气体中按照如下的方式提取氯和酸。富有酸和 氯的冷凝物 2a经过连接导管 37从冷凝器 28传送到第二分离单元 2%,通过 降低单元 29b中的压力的抽吸释放溶解在溶液 2a中的酸和氯。 另一方面,
^ A o„ 4r 1 1 ζ·\\ 1 ― ΛΛ rx -rr -、rf -'ά -fci ^ iT ^il ^"一八^ ^ n^
Chlorine and acid were extracted from the contaminated gas in the separator 29 in the following manner. The acid and chlorine-rich condensate 2a is transferred from the condenser 28 to the second separation unit 2% via the connection conduit 37, and the acid and chlorine dissolved in the solution 2a are released by the suction of the pressure in the reduction unit 29b. on the other hand, ^ A o„ 4r 1 1 ζ·\\ 1 ― ΛΛ rx -rr -, rf -'ά -fci ^ iT ^il ^"一八^ ^ n^
(该压力由装设在分离器 29中的泵形成),以增加溶液 2a中气体的溶解度, 使得来自冷凝器 28的上部的气体中的酸和氯被充分地被吸收。 饱含酸和氯 的溶液 2a随后从第一分离单元 29a溢流到第二分离单元 29b,从而重复饱含 与释放循环。 在一定数量的循环(循环的数量取决于来自冷凝器 28的冷凝 物的馈送率)之后, 溶液 2a被输送到第三分离单元 29c以便进一步提取酸 和氯。 在第三分离单元 29c中处理之后, 溶液 2a经连接导管 45流到水处理 (This pressure is formed by a pump installed in the separator 29) to increase the solubility of the gas in the solution 2a so that the acid and chlorine in the gas from the upper portion of the condenser 28 are sufficiently absorbed. The solution 2a saturated with acid and chlorine then overflows from the first separation unit 29a to the second separation unit 29b, thereby repeating the saturation and release cycles. After a certain number of cycles (the number of cycles depends on the feed rate of the condensate from the condenser 28), the solution 2a is sent to the third separation unit 29c for further extraction of acid and chlorine. After the treatment in the third separation unit 29c, the solution 2a flows through the connection conduit 45 to the water treatment.
^ ^ JLA *Fr Λ 4 & A / ΓΠ Ι^ 1 1_ 、 ^ ^ JLA *Fr Λ 4 & A / ΓΠ Ι^ 1 1_ ,
^JL W ¾' Λ ^Έ 丁 、 ζ乡、 丄 ϋ ^JL W 3⁄4' Λ ^Έ丁, ζ乡, 丄 ϋ
在分离器 29的第一分离单元 29a中进行了清洗之后,多余的气体被经 过连接导管 33送到中和器 30,以通过溶液 2b对酸和氯进行最后的中和处理, 其中溶液 2b是 NaOH。在中和器 30中,主要进行的反应是 HC1 + NaOH→H20 + NaCl, 而进行的次要反应是 HC103 + NaOH→ H20 +NaC103 , HC102 + NaOH→ H20 +NaC102 , HC10 + NaOH→ H20 +NaC10 , HC10 + NaOH→ H20 +NaC10 , HC104 + NaOH→ H20 +NaC104。 After the cleaning in the first separation unit 29a of the separator 29, the excess gas is sent to the neutralizer 30 through the connection conduit 33 to perform the final neutralization treatment of the acid and chlorine by the solution 2b, wherein the solution 2b is NaOH. In the neutralizer 30, the main reaction is HC1 + NaOH → H 2 0 + NaCl, and the secondary reaction is HC10 3 + NaOH → H 2 0 + NaC10 3 , HC10 2 + NaOH → H 2 0 + NaC10 2 , HC10 + NaOH → H 2 0 + NaC10 , HC10 + NaOH → H 2 0 + NaC10 , HC10 4 + NaOH → H 2 0 + NaC10 4 .
1 V> 咅" f 太 *日 fl AA ^I ^.女: λ' ΑΑ^^ί ίΤ: i*. ctl -h ^ 1 h 所示意, 具有清洗部分的蚀刻机 1包括冲洗格 4a、 4b和 4c。 被污染的冲洗 水从冲洗格 4a根据需要被经过连接导管 40传送到暂存槽 38。 存在槽 38中 的水被传递到萃取装置 6, 以清洗萃取装置 6的树脂, 并且最终被导向氧化 装置 8的第二氧化单元 8b。冷凝器 28中富含酸和氯的冷凝物 2a被经过连接 导管 37传送到第二分离单元 29b, 以提取所溶解的酸和氯。 在提取之后, 溶 液 2a被经过连接导管 36导向第一分离单元 29a,以便对经过连接导管 32送 来的气体进行清洗。 然后, 被释放了氯和酸的溶液 2a溢流到第二分离单元 29b, 以便再次释放。 在饱含和释放的若干次循环之后, 溶液 2a落入第三分 离单元 29c以便再次提取酸和氯并且然后经由连接导管 45流到暂存槽 43, 在暂存槽 43中 ,它与由渗透单元 42所供应的浓缩物混合。该混合可替代地, 在冲洗格中一个内的溶液的盐浓度大于 1克 /升时,根据需要,经由连接导管 47a被送入冲洗格 4a和 /或经由 47b和 47c送入沖洗格 4b和 4c。 沖洗格 4c 持续地从暂存槽 44经由连接导管 50接收纯水, 而渗透单元 42中的纯水经 由连接导管 49被送入暂存槽 44。
进一步, 渗透装置 42经由连接导管 48从暂存槽 41接收水, 暂存槽 41 自身经由连接导管从沖洗部件 4的冲洗格 4b和 4c接收水,如果总的盐浓 度小于 1克 /升的话。 渗透部件 42具有 80%的效率, 亦即, 其对待处理的总 量, 可以产生 80%的纯水, 20%的浓缩水。 纯净水被送到沖洗格 4c , 并由 沖洗格 4c溢出到冲洗格 4b和 4a。 1 V>咅" f too *day fl AA ^I ^. Female: λ' ΑΑ^^ί ίΤ: i*. ctl -h ^ 1 h It is illustrated that the etching machine 1 having the cleaning portion includes the rinsing grids 4a, 4b And 4c. The contaminated flushing water is transferred from the flushing tank 4a to the temporary storage tank 38 through the connecting duct 40 as needed. The water present in the tank 38 is transferred to the extracting device 6 to clean the resin of the extracting device 6, and is finally The second oxidation unit 8b of the oxidation unit 8 is guided. The acid and chlorine-rich condensate 2a in the condenser 28 is sent to the second separation unit 29b via the connection conduit 37 to extract the dissolved acid and chlorine. The solution 2a is guided to the first separation unit 29a via the connection duct 36 to clean the gas sent through the connection duct 32. Then, the chlorine and acid-releasing solution 2a is overflowed to the second separation unit 29b to be released again. After several cycles of saturating and releasing, the solution 2a falls into the third separating unit 29c to extract the acid and chlorine again and then flows through the connecting conduit 45 to the temporary storage tank 43, in the temporary storage tank 43, it is infiltrated with The concentrate supplied by unit 42 is mixed. Preferably, when the salt concentration of the solution in one of the rinse cells is greater than 1 gram per liter, it is fed to the rinsing compartment 4a via the connecting conduit 47a and/or to the rinsing compartments 4b and 4c via 47b and 47c, as needed. 4c continuously receives pure water from the temporary storage tank 44 via the connection duct 50, and the pure water in the permeation unit 42 is sent to the temporary storage tank 44 via the connection duct 49. Further, the permeating device 42 receives water from the temporary storage tank 41 via the connecting duct 48, and the temporary storage tank 41 itself receives water from the flushing compartments 4b and 4c of the flushing member 4 via the connecting duct if the total salt concentration is less than 1 g/liter. The permeable member 42 has an efficiency of 80%, i.e., it can produce 80% pure water and 20% concentrated water, depending on the total amount to be treated. The purified water is sent to the rinse compartment 4c and overflows from the rinse compartment 4c to the rinse compartments 4b and 4a.
优选地, 冲洗格 4a中污染的水通过导管 40被送入暂存槽 38。 如前文 所述, 萃取装置 6从电离装置 5a接收已使用蚀刻液, 并通过萃取装置 6中 的树脂将酸萃取出来, 已经萃取了酸的溶液被送入电解装置 7, 而暂存槽 38 中的所暂存的溶液则被送往萃取装置 6以冲洗树脂, 冲洗后的液体则送往氧 化装置 8的第二氧化单元 8b。 经由上述水循环装置, 尤其是冲洗格 4a的溶 液在冲洗了萃取装置 6中的树脂之后再回到已使用蚀刻液中, 可补偿经由电 离装置 5的第四单元 5d的蒸发而造成损失。 Preferably, the contaminated water in the rinsing compartment 4a is sent to the temporary storage tank 38 through the conduit 40. As described above, the extraction device 6 receives the used etching liquid from the ionizing device 5a, and extracts the acid through the resin in the extraction device 6, and the solution from which the acid has been extracted is sent to the electrolysis device 7, and in the temporary storage tank 38. The temporarily stored solution is sent to the extraction unit 6 to rinse the resin, and the rinsed liquid is sent to the second oxidation unit 8b of the oxidation unit 8. The above-described water circulation device, particularly the solution of the rinsing cell 4a, is returned to the used etching liquid after rinsing the resin in the extraction device 6, and the loss due to evaporation of the fourth unit 5d of the ionization device 5 can be compensated for.
氯和 HC1的注入将加大氧化对 Cu++/Cu+和 Cu+/Cu的化学势差, 如图 2 所给出的, 其支持蚀刻并改善了生产效率以及生产质量。 The injection of chlorine and HCl will increase the chemical potential difference between Cu ++ /Cu+ and Cu+/Cu, as shown in Figure 2, which supports etching and improves production efficiency and production quality.
自已使用蚀刻液中对 HC1和氯的提取, 因为增大了氧化对 Cu++/Cu+和Self-extraction of HC1 and chlorine in the etchant, because of the increased oxidation of Cu ++ /Cu + and
Cu+/Cu的适当化学势差而促进了电解过程。 The appropriate chemical potential difference of Cu + /Cu promotes the electrolysis process.
如图 1、 la和 lb所示意的, 用于处理已使用蚀刻液的过程或者系统在 蚀刻机工作时运行(除了电解装置 7和直接连接到它的部件) , 该过程或系 统能够通过已使用蚀刻液在再生装置 9的第二再生单元 9b和电离装置 5的 第一单元 5a之间经由连接导管 18所连接而形成的内部循环中,独立地运行。 另一方面, 从电离装置 5的第一单元 5a中出来的多余气体通过已使用蚀刻 液在第二单元 5b和第四单元 5d之间经由导管 19连接而形成的回路中的循 环而被清洗。 As illustrated in Figures 1, la and lb, the process or system for processing the used etchant is operated while the etch machine is operating (except for the electrolysis device 7 and the components directly connected thereto), the process or system can be used The etching liquid is independently operated in an internal circulation formed by the connection between the second regeneration unit 9b of the regeneration device 9 and the first unit 5a of the ionization device 5 via the connection duct 18. On the other hand, the excess gas coming out of the first unit 5a of the ionization device 5 is cleaned by a cycle in a circuit formed by connecting the second unit 5b and the fourth unit 5d via the conduit 19 using the etching liquid.
应当说明的是, 以上具体实施方式仅用以说明本发明的技术方案而非 领域的普通技术人员应当理解,依然可以对本发明的具体实施方式进行修改 或对部分技术特征进行等同替换, 而在不脱离本发明的技术方案的精神下, 其均应涵盖在本发明请求保护的技术方案范围当中。
It should be noted that the above specific embodiments are only for explaining the technical solutions of the present invention, and those skilled in the art should understand that the specific embodiments of the present invention may be modified or equivalently replaced with some technical features. All of the technical solutions claimed in the present invention should be included in the scope of the technical solutions claimed in the present invention.
Claims
1. 一种用于处理已使用酸性蚀刻液的再循环系统, 其包括: A recycling system for treating an acid etchant that has been used, comprising:
电离装置, 其用于解络从蚀刻设备传送来的已使用酸性蚀刻液中的 Cu ( I ) ; An ionization device for decompressing Cu ( I ) in the used acidic etching solution transferred from the etching device;
氧化装置, 其接收来自电离装置的已使用酸性蚀刻液, 并将自所述电离 装置解络出的 Cu(I)氧化为 Cu(II); An oxidizing device that receives an used acidic etching solution from the ionizing device and oxidizes Cu(I) decomposed from the ionizing device to Cu(II);
萃取装置,其以预先设定的比率持续或非持续地接收从所述电离装置传 送来的已使用酸性饯刻液, 并萃取该已使用酸性蚀刻液中的酸; An extraction device that continuously or non-continuously receives the used acidic etching solution transferred from the ionizing device at a predetermined ratio, and extracts the acid in the used acidic etching solution;
电解装置, 其接收已由所述萃取装置处理过的已使用酸性蚀刻液, 并析 出该已使用酸性蚀刻液中的铜; An electrolysis device that receives the used acidic etching solution that has been treated by the extraction device and deposits copper in the used acidic etching solution;
再生装置, 其接收所述氧化装置处理过的已使用蚀刻液, 并调节该已使 用蚀刻液的 PH值以及稳定单氯的 [CuCl]+形式的铜络合物, 从而使所接收的 已使用蚀刻液再生为可使用的蚀刻液; a regenerating device that receives the used etchant treated by the oxidizing device, and adjusts the pH of the used etchant and stabilizes the copper complex of the [CuCl]+ form of monochlorine, thereby allowing the received use The etching solution is regenerated into an etchant that can be used;
其中,在所述电离装置中提取气体且所提取的气体以及从所述电解装置 逸出的气体被传送到所述氧化装置,在所述氧化装置中进一步提取气体且所 提取气体被传送到所述再生装置,且从所述再生装置逸出的气体被输送到所 述电离装置。 Wherein the gas is extracted in the ionization device and the extracted gas and the gas escaping from the electrolysis device are transferred to the oxidation device, in which the gas is further extracted and the extracted gas is delivered to the A regeneration device is described, and gas escaping from the regeneration device is delivered to the ionization device.
2.根据权利要求 1所述的系统, 其中, 所述电离装置包括接收已使用酸 性蚀刻液的第一单元,接收来自所述第一单元的已使用酸性蚀刻液的第二单 元, 以及接收来自所述第二单元的已使用酸性蚀刻液的第三单元, 其中所述 已使用蚀刻液可从一个子单元流入相邻的子单元。 3.根据权利要求 2所述的系统,其中, 由第二单元和第三单元形成所述 已使用酸性蚀刻液可以在其中流通的回路。 2. The system of claim 1 , wherein the ionization device comprises a first unit that receives an used acidic etchant, a second unit that has received an acidic etchant from the first unit, and receives from the second unit A third unit of the second unit that has used an acidic etchant, wherein the used etchant can flow from one subunit to an adjacent subunit. The system according to claim 2, wherein the circuit in which the used acidic etching liquid can flow is formed by the second unit and the third unit.
4. 根据权利要求 3所述的系统,其中,从所述第一单元和所述第二单元 中提取 HC1气体。
4. The system of claim 3, wherein HC1 gas is extracted from the first unit and the second unit.
5. 根据权利要求 1所述的系统,其中,所述氧化装置包括第一氧化单元 和第二氧化单元, 第一氧化单元接收在所述电离装置中处理过的已使用酸性 蚀刻液, 第二氧化单元从该第一氧化单元接收所述已使用蚀刻液。 5. The system of claim 1 wherein the oxidizing device comprises a first oxidizing unit and a second oxidizing unit, the first oxidizing unit receiving the used acidic etchant treated in the ionizing device, the second The oxidizing unit receives the used etchant from the first oxidizing unit.
6. 根据权利要求 5所述的系统,其中,所述萃取装置利用树脂来萃取酸, 且沖洗所述树脂后的溶液被送往所述氧化装置的第二氧化单元。 6. The system according to claim 5, wherein the extraction device extracts acid using a resin, and the solution after rinsing the resin is sent to a second oxidation unit of the oxidation device.
7. 根据权利要求 5所述的系统,其中,来自所述电离装置的气体被送往 所述第二氧化单元, 而来自所述电解装置和所述蚀刻设备的气体被送往所述 第一氧化单元。 7. The system of claim 5 wherein gas from the ionization device is sent to the second oxidation unit and gas from the electrolysis device and the etching device is sent to the first Oxidation unit.
8. 根据权利要求 1所述的系统,其中,所述再生装置包括第一再生单元 和第二再生单元, 第一再生单元被用于调节所接收的溶液的 PH值, 而所述 第二再生单元被用于根据以下化学反应稳定单氯铜络合物 [CuClf: CiT + cr→ cuci+。 8. The system of claim 1 wherein said regeneration device comprises a first regeneration unit and a second regeneration unit, said first regeneration unit being operative to adjust a pH of said received solution, and said second regeneration It is used in the following chemical reaction unit steady according monochloro copper complex [CuClf: CiT + cr → cuci +.
9.根据权利要求 8所述的系统, 其中, 所述第一再生单元接收来自所述 氧化装置的气体。 The system according to claim 8, wherein the first regeneration unit receives gas from the oxidation device.
10.根据权利要求 9所述的系统,其中,所述再生装置设置有注射器泵, 以在第二再生单元中将来自第一再生单元的气体吸收并再次注入到所述第 二再生单元的溶液中。 10. The system according to claim 9, wherein the regeneration device is provided with a syringe pump to absorb and re-inject the gas from the first regeneration unit into the solution of the second regeneration unit in the second regeneration unit in.
11.根据权利要求 1所述的系统, 其中, 所述电解装置包括包含阳极、 电极和电流生成器的电解单元。 11. The system of claim 1 wherein the electrolysis device comprises an electrolysis unit comprising an anode, an electrode, and a current generator.
12.根据权利要求 1所述的系统, 还包括气体处理装置, 所述气体处理 装置自从所述电离装置接收的气体中提取气体 HC1和痕量 Cl2, HCIO, HC102, HC103, HC104。
12. The system according to claim 1, further comprising a gas treatment apparatus, since the gas processing means receiving said gas ionizing means HC1 and extracted trace gases Cl 2, HCIO, HC10 2, HC10 3, HC10 4 .
13.根据权利要求 12所述的系统,其中,所述气体处理装置包括冷凝器 和分离器, 其中, 13. The system of claim 12, wherein the gas treatment device comprises a condenser and a separator, wherein
所述冷凝器接收来自所述电离装置的第三单元的气体, 并通过冷凝的方 式从所接收的气体中分离气体 HC1和痕量 Cl2 HC10, HC102, HCIO3, HCIO4, 而所分离的气体被送往所述再生装置的第一单元, 以及 The condenser receives gas from the third unit of the ionization device and separates the gas HC1 and the traces of Cl 2 HC10, HC10 2 , HCIO3, HCIO4 from the received gas by condensation, and the separated gas a first unit that is sent to the regeneration device, and
所述分离器接收所述冷凝器中的剩余气体, 并在所述分离器的第一部分 vv", The separator receives residual gas in the condenser and is in a first portion of the separator vv",
量 Cl2 HCIO, HC102, HCIO3, HCIO4气体被送往再生装置的第二单元,其中剩 余气体包括 Cl2 HCIO, HCIO2, HCIO3, HC104 The amount of Cl 2 HCIO, HC10 2 , HCIO3, HCIO4 gas is sent to the second unit of the regeneration unit, wherein the remaining gases include Cl 2 HCIO, HCIO2, HCIO3, HC10 4
14.根据权利要求 13所述的系统,其中,所述分离器包括第一分离单元、 第二分离单元和第三分离单元, 第一分离单元被用于吸收来自冷凝器的气体 中的 HC1和痕量 Cl2 HCIO, HC102 HC103, HC104气体, 而第二和第三单元 被用来提取 HC1和痕量 Cl2, HCIO, HC102, HC103, HC104气体。 14. The system of claim 13, wherein the separator comprises a first separation unit, a second separation unit, and a third separation unit, the first separation unit being configured to absorb HC1 in the gas from the condenser and Traces of Cl 2 HCIO, HC10 2 HC10 3 , HC10 4 gas, and the second and third units were used to extract HC1 and traces of Cl 2 , HCIO, HC10 2 , HC10 3 , HC10 4 gases.
15.根据权利要求 14 所述的系统, 进一步包括水处理装置以及冲洗部 件, 所述冲洗部件用来自蚀刻装置的已使用蚀刻液来清洗已被蚀刻的电路 板, 所述水处理装置对来自冲洗部件的溶液进行处理以获得纯水, 并接收来 自所述气体处理装置中的溶液。 15. The system of claim 14, further comprising a water treatment device and a flushing component, the flushing component cleaning the circuit board that has been etched with an etchant from the etching device, the water treatment device pair being flushed The solution of the component is treated to obtain pure water and receives the solution from the gas treatment device.
16.根据权利要求 15所述的系统,其中,所述水处理装置包括渗透单元 和若干暂存槽, 所述渗透单元用以对来自冲洗部件的溶液进行处理以获得纯 水, 所获得的纯水被送入第一暂存槽, 以在需要时从所述第一暂存槽送入所 述冲洗部件, 所述渗透部件中的剩余物送入第二暂存槽, 以与来自所述分离 装置的溶液混合, 所混合的溶液根据需要被送入所述冲洗部件。 16. The system according to claim 15, wherein the water treatment device comprises a permeation unit and a plurality of temporary storage tanks, wherein the permeation unit is configured to treat the solution from the flushing member to obtain pure water, and the obtained pure The water is sent to the first temporary storage tank to be fed into the flushing member from the first temporary storage tank when needed, and the remainder of the permeating member is sent to the second temporary storage tank to The solution of the separation device is mixed, and the mixed solution is fed to the rinsing member as needed.
17. 根据权利要求 15所述的系统,还包括用以中和自分离装置中传送来 的气体的中和装置。
1 。 jfJr S iL L,L I. J- -A-.) 丄 丄 ·<·. .、, -r- it. Tlfli a)提供电离装置,以用于解络从蚀刻设备传送来的已使用酸性蚀刻液中 的 Cu ( I ) ; 17. The system of claim 15 further comprising a neutralization device to neutralize gas delivered from the separation device. 1 . jfJr S iL L,L I. J- -A-.) 丄丄·<·. .,, -r- it. Tlfli a) Providing an ionization device for decommissioning the used acidity transmitted from the etching device Cu ( I ) in the etching solution;
b)提供氧化装置, 以用于接收来自电离装置的已使用酸性蚀刻液, 并 5 将自所述电离装置解络出的 Cu(I)氧化为 Cu(II); b) providing an oxidizing device for receiving the used acidic etching solution from the ionizing device, and oxidizing Cu(I) decomposed from the ionizing device to Cu(II);
c)提供萃取装置,以用于以预先设定的比率持续或非持续地接收从所述 电离装置传送来的已使用酸性蚀刻液, 并萃取该已使用酸性蚀刻液中的酸; c) providing an extraction device for continuously or non-continuously receiving the used acidic etching solution transferred from the ionization device at a predetermined ratio, and extracting the acid in the used acidic etching solution;
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) 衣 JL, 升川丁 》| 。 尸] 千 ·φ^¾^ί¾: ϋ日 J IXJW ¾:'r王 蚀刻液, 并析出该已使用酸性蚀刻液中的铜; ) Clothing JL, Asahi Ding 》 |尸] 千 ·φ^3⁄4^ί3⁄4: Next day J IXJW 3⁄4: 'r king etchant, and precipitate the copper in the acid etching solution;
10 e)提供再生装置,其接收所述氧化装置处理过的已使用蚀刻液, 并调节 该已使用蚀刻液的 PH值以及稳定单氯的 [CuCl]+形式的铜络合物, 从而使所 接收的已使用蚀刻液再生为可使用的蚀刻液; 10 e) providing a regenerating device that receives the used etching solution treated by the oxidizing device, and adjusts the pH of the used etching solution and stabilizes the copper complex in the form of [CuCl] + of monochlorine, thereby The received used etching solution is regenerated into an usable etching solution;
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^仗 1义 3从所 W由,龃¾ 逸出的气体被传送到所述氧化装置,在所述氧化装置中进一步提取气体且所 、 严 -IB Art > ί 2il ?0-- ι I '丄' 丄 d士 《 、A . I , J- tlii.Jfc The gas escaping from the 33 is transferred to the oxidizing device, and the gas is further extracted in the oxidizing device, and --IB Art > ί 2il ?0-- ι I '丄'丄dshi", A. I, J- tlii.
10 ?疋 W" 'l^P ¾^' ■ ¾L g ri\ ¾^-fTit. ^¾— B- , 八 v| ΙΪΗ ^ JL¾£t ffi H'、J ""1 14、低 f —^LS^尸 I 述电离装置。 10 ?疋W" 'l^P 3⁄4^' ■ 3⁄4L g ri\ 3⁄4^-fTit. ^3⁄4— B- , 八 v| ΙΪΗ ^ JL3⁄4£t ffi H', J ""1 14, low f —^ LS^ 尸I describes the ionization device.
19.根据权利要求 18所述的方法,还包括气体处理装置,所述气体处理 装置自从所述电离装置接收的气体中提取气体 HC1和痕量 Cl2, HC10, HC102, 0 HC103, HC104 19. The method of claim 18, further comprising a gas treatment apparatus, since the gas processing means receiving said gas ionizing means HC1 and extracted trace gases Cl 2, HC10, HC10 2, 0 HC10 3, HC10 4
20.根据权利要求 19所述的方法,其中,所述气体处理装置包括冷凝器 和分离器, 其中, The method according to claim 19, wherein the gas treatment device comprises a condenser and a separator, wherein
所述冷凝器接收来自所述电离装置的第三单元的气体, 并通过冷凝的方 5 式从所接收的气体中分离气体 HC1和痕量 Cl2, HC10, HCIO2, HCIO3, HCIO4 而所分离的气体被送往所述再生装置的第一单元, 以及 The condenser receives the gas from the third unit of the ionization device and separates the gas HC1 and the traces of Cl 2 , HC10, HCIO2, HCIO3, HCIO4 from the received gas by a condensing formula Gas is sent to the first unit of the regeneration device, and
所述分离器接收所述冷凝器中的剩余气体, 并在所述分离器的第一部分 吸收 HC1和痕量 Cl2, HC10, HC102, HC103, HC104, 所分离的 HC1气体和痕 量 Cl2, HC10, HCIO2, HC103, HC104气体被送往再生装置的第二单元,其中剩
余 体包括 ¾, HCIO, HCIO2, HCIO3, HCIO40 The separator receives residual gas in the condenser and absorbs HC1 and traces of Cl 2 , HC10, HC10 2 , HC10 3 , HC10 4 , separated HC1 gas and traces in a first portion of the separator Cl 2 , HC10, HCIO2, HC10 3 , HC10 4 gas is sent to the second unit of the regeneration unit, which remains The remaining body includes 3⁄4, HCIO, HCIO2, HCIO3, HCIO40
21.根据权利要求 20所述的方法,其中,所述分离器包括第一分离单元、 第二分离单元和第三分离单元, 第一分离单元被用于吸收来自冷凝器的气体 中的 HC1和痕量 Cl2, HCIO, HC102, HC103, HCIO4气体, 而第二和第三单元 被用来提取 HC1和痕量 Cl2, HCIO, HCIO2, HCIO3, HCIO4气体。 The method according to claim 20, wherein the separator comprises a first separation unit, a second separation unit, and a third separation unit, the first separation unit being configured to absorb HC1 in the gas from the condenser and Traces of Cl 2 , HCIO, HC10 2 , HC10 3 , HCIO4 gas, and the second and third units were used to extract HC1 and traces of Cl 2 , HCIO, HCIO2, HCIO3, HCIO4 gas.
22.一种再生已使用酸性蚀刻液的方法, 包括以下步骤: 22. A method of regenerating an acid etchant that has been used, comprising the steps of:
a)将已使用酸性蚀刻液中的 Cu(I)络合物电离解络; a) ionizing and decomposing the Cu(I) complex in the acidic etching solution;
b)将解络后的 Cu(I)离子氧化为 Cu(II)离子; b) oxidizing the decomposed Cu(I) ions to Cu(II) ions;
c) 形成 Cu(II)络合物, c) forming a Cu(II) complex,
以使已使用蚀刻液再生为可使用的蚀刻液。 The etchant that has been used is regenerated into an etchant that can be used.
23.根据权利要求 22所述的方法, 其中所述络合 4勿是 Cu和 Ci的络合 物。 24.根据权利要求 22或 23所述的方法, 还包括以下步骤: 将步骤 a)解 络后的已使用酸性蚀刻液的一部分电解以析出铜。 23. The method of claim 22, wherein the complex 4 is not a complex of Cu and Ci. The method according to claim 22 or 23, further comprising the step of: electrolyzing a portion of the used acidic etching solution after the step a) to precipitate copper.
25.根据权利要求 26所述的方法,还包括在电解之前萃取所述一部分的 已使用酸性蚀刻液中的酸。 25. The method of claim 26, further comprising extracting a portion of the acid in the used acidic etchant prior to electrolysis.
26.根据权利要求 25所述的方法,其中, 步骤 a)中通过提取已使用酸性 蚀刻液中的 HC1气体来进行所述解络。 The method according to claim 25, wherein in the step a), the decomplexing is performed by extracting an HC1 gas which has been used in an acidic etching solution.
27.根据权利要求 22或 23所述的方法, 其中, 步骤 b)中的氧化至少部 分由电离解络产生的气体和电解产生的气体来进行。 The method according to claim 22 or 23, wherein at least a part of the oxidation in the step b) is carried out by a gas generated by ionization decompression and a gas generated by electrolysis.
28.根据权利要求 22或 23所述的方法, 其中, 步骤 c)中通过调节已使 用蚀刻液的 PH值并稳定 Cu(II)络合物, 使已使用蚀刻液再生为可使用的蚀 刻液。
29.根据权利要求 22所述的方法,其中,使用氯气和氯化氢调节已使用 蚀刻液的 PH值并稳定 Cu(II)络合物。 The method according to claim 22 or 23, wherein in step c), the used etching liquid is regenerated into a usable etching liquid by adjusting the pH value of the used etching liquid and stabilizing the Cu(II) complex. . 29. The method according to claim 22, wherein chlorine gas and hydrogen chloride are used to adjust the pH of the used etching solution and stabilize the Cu(II) complex.
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