WO2012163238A1

WO2012163238A1 - Recycling system and method for treating used etching solution

Info

Publication number: WO2012163238A1
Application number: PCT/CN2012/075862
Authority: WO
Inventors: 施道可
Original assignee: 无锡尚德太阳能电力有限公司; 库特勒自动化系统(苏州)有限公司
Priority date: 2011-05-31
Filing date: 2012-05-22
Publication date: 2012-12-06
Also published as: CN102807294A

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

Handling recycling systems that have used etchant

Technical field and method

The present invention relates to recycling techniques, and more particularly to recycling systems that have used etching fluids ₍ Background of the Invention)

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,

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.

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

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) 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.

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.

Preferably, the treatment of the present invention has used a recirculating system of an acidic etchant, said ionization

Cu ⁺ and C : CuCl ₂ -→ Cu ⁺ +2C1" and CuC! ₂ "→ CuCl + C!

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.

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.

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.

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.

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.

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^^ ■ 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.

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.

Preferably, 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.

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.

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

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.

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.

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.

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.

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 .

Preferably, 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\ ^^' ^ 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. Eight 3⁄47

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.

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.

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.

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.

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. Wherein 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.

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

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

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.

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.

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.

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]+ if -l<-log[Cir < 0,

Cu ⁺ + 2C1"→ [CuCl ₂ ]" if -log[Cl]- < 0, and

[CuCl ₂ ]"→ Cu ⁺ + 2C1" If -log[Cl]- > 0

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 dry ^;? ^王 /口, 3⁄4L— ^ ^尸J

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.

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.

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]+.

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.

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.

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 , and

[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.

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/ 0 ₂ → Cu" + H ₂ 0

Then, the solution enters the second oxidation unit 8b of the oxidation unit 8.

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.

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:

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[CuCl ₂ ]" + 4H ⁺ + 1/2 0 ₂ → 2[CuCl] ⁺ + 2HC1 + 3⁄40;

Cu+ + H ⁺ + 1/4 0 ₂ → Cu ⁺⁺ + H ₂ 0.

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.

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.

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.

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.

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.

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.

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.

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.

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, - 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.

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.

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 .

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.

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.

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.

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.

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.

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.

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.

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.

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.

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 ⁺⁺ + + Cl ₂ → [CuCl] ⁺ ,

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 %.

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^

(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.

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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 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.

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.

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.

Self-extraction of HC1 and chlorine in the etchant, because of the increased oxidation of Cu ⁺⁺ /Cu ⁺ and

The appropriate chemical potential difference of Cu ⁺ /Cu promotes the electrolysis process.

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.

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

A recycling system for treating an acid etchant that has been used, comprising:

An ionization device for decompressing Cu ( I ) in the used acidic etching solution transferred from the etching device;

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);

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;

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;

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;

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. 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. The system of claim 3, wherein HC1 gas is extracted from the first unit and the second unit.

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. 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. 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. 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 +.

The system according to claim 8, wherein the first regeneration unit receives gas from the oxidation device.

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. The system of claim 1 wherein the electrolysis device comprises an electrolysis unit comprising an anode, an electrode, and a current generator.

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. The system of claim 12, wherein the gas treatment device comprises a condenser and a separator, wherein

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

The separator receives residual gas in the condenser and is in a first portion of the separator vv",

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. 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. 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. 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. 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) 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) 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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) 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) 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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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 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. 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

The method according to claim 19, wherein the gas treatment device comprises a condenser and a separator, wherein

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

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

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. A method of regenerating an acid etchant that has been used, comprising the steps of:

a) ionizing and decomposing the Cu(I) complex in the acidic etching solution;

b) oxidizing the decomposed Cu(I) ions to Cu(II) ions;

c) forming a Cu(II) complex,

The etchant that has been used is regenerated into an etchant that can be used.

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. The method of claim 26, further comprising extracting a portion of the acid in the used acidic etchant prior to electrolysis.

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.

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.

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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