WO2014192581A1 - Procédé et dispositif de traitement d'une solution de gravure qui contient de l'iode ainsi que de l'or - Google Patents

Procédé et dispositif de traitement d'une solution de gravure qui contient de l'iode ainsi que de l'or Download PDF

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Publication number
WO2014192581A1
WO2014192581A1 PCT/JP2014/063275 JP2014063275W WO2014192581A1 WO 2014192581 A1 WO2014192581 A1 WO 2014192581A1 JP 2014063275 W JP2014063275 W JP 2014063275W WO 2014192581 A1 WO2014192581 A1 WO 2014192581A1
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iodine
etching solution
potential
cathode
concentration
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PCT/JP2014/063275
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English (en)
Japanese (ja)
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千絵 古堅
広宣 小久保
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アサヒプリテック株式会社
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Priority to CN201480021400.9A priority Critical patent/CN105164317B/zh
Priority to JP2014543381A priority patent/JP5669995B1/ja
Publication of WO2014192581A1 publication Critical patent/WO2014192581A1/fr
Priority to HK16101230.0A priority patent/HK1213303A1/zh

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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
    • C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals

Definitions

  • the present invention relates to a method and apparatus for processing an Au-containing iodine-based etching solution. Specifically, the present invention relates to a technique for efficiently recovering metallic Au from an iodine-containing iodine-based etching solution by electrolysis at a high recovery rate and recovering the iodine (I 3 ⁇ ) concentration to restore the etching ability.
  • Au for example, Au plating
  • Au plating is used for integrated circuit boards such as semiconductors and electronic parts such as terminal terminals and connectors.
  • An iodine-based etchant is widely used as an Au etchant.
  • the iodine-based etching solution is a solution in which iodine (I 2 ) is dissolved in an aqueous solution of potassium iodide (KI), and iodine exists as I 3 ⁇ in the aqueous solution and reacts with the iodine (I 3 ⁇ ). Then, Au is etched (dissolved).
  • the used iodine-based etchant after etching Au contains Au ions (for example, iodide complex [AuI 2 ] ⁇ ). Since Au is an expensive material, various techniques for recovering Au from used iodine-based etching solutions have been proposed. An electrolysis method is widely used as a technique for recovering Au from a used iodine-based etching solution.
  • the electrolysis method is a method in which Au-containing iodine-based etching solution is electrolyzed to deposit Au on the cathode surface and recovered.
  • the used etching solution after recovering Au is discarded without being reused because iodine (I 3 ⁇ ) having etching ability is reduced (I ⁇ ) and the etching ability is reduced. It was.
  • Patent Document 1 discloses a method of recovering iodine (I 3 ⁇ ) by oxidizing Au (I ⁇ ) reduced by recovering Au by performing electrolysis treatment of a used iodine-based etching solution. Techniques have been proposed that allow the etching capacity to be regenerated and reused.
  • the physical properties (composition, iodine concentration, etc.) of the etching solution containing Au vary depending on the iodine concentration in the object to be processed and the iodine-based etching solution. Therefore, while recovering Au in a high yield, It was very difficult to perform the regeneration stably.
  • the present invention has been made paying attention to the above-mentioned circumstances, and the object thereof is to recover the iodine (I 3 ⁇ ) concentration from the Au-containing etching solution at a high recovery rate and preferably to adjust the iodine (I 3 ⁇ ) concentration before use.
  • the purpose is to establish a technique that can recover the etching performance by recovering to almost the same level as the state of the etching solution.
  • the present invention that has solved the above problems is a method of treating an etching solution that recovers the iodine (I 3 ⁇ ) concentration while recovering the Au in the Au-containing iodine-based etching solution by electrolysis. Is carried out while maintaining the cathode potential at ⁇ 0.7 V or more (when the reference potential is the reference electrode Ag / AgCl) and the anode potential at +1.0 V or less (when the reference potential is the reference electrode Ag / AgCl). Has a summary.
  • the electrolysis is performed by diaphragm electrolysis in which a cathode and an anode are partitioned by a diaphragm.
  • the diaphragm electrolysis is performed by supplying the Au-containing iodine-based etchant continuously from the supply source of the Au-containing iodine-based etchant to the cathode side partitioned by the diaphragm and recovering Au.
  • a method of supplying iodine (I 3 ⁇ ) concentration to the partitioned anode side It is also a preferred embodiment that the iodine concentration on the cathode side partitioned by the diaphragm is adjusted to such an extent that re-dissolution of Au deposited on the cathode does not occur.
  • the cathode for electrolysis, the anode, the reference electrode serving as a reference for the electrode potential of the cathode or the anode, and the reference And a power source for controlling the current or the voltage between the electrodes so that the electrode potential on the side where the reference electrode is installed is within a predetermined range based on the potential measured by the electrode, and the reference electrode is not installed
  • the electrode on the side has physical means for adjusting the electrode potential to be within a predetermined range.
  • means for adjusting the wetted area of the electrode on the side where the reference electrode is not installed is preferable.
  • the cathode potential and anode potential during electrolysis are appropriately controlled, so that Au in the Au-containing etching solution can be recovered at a high recovery rate and the iodine (I 3 ⁇ ) concentration is recovered. Then, the etching ability can be regenerated. Further, by partitioning with a diaphragm, Au deposition on the cathode side and iodine (I 3 ⁇ ) concentration recovery on the anode side can be performed more efficiently, so that the electrolysis time can be shortened.
  • the iodine in the Au-containing iodine-based etching solution in which Au deposited on the cathode is newly supplied because the iodine (I 3 ⁇ ) concentration on the cathode side is controlled. (I 3 ⁇ ) prevents re-dissolution and Au can be recovered with good yield.
  • the electrode potential and the anode potential can be easily controlled appropriately.
  • FIG. 1 is a schematic view showing a configuration example of diaphragm electrolysis.
  • FIG. 2 is a schematic view showing another configuration example of diaphragm electrolysis.
  • FIG. 3 is a schematic view showing another configuration example of diaphragm electrolysis.
  • FIG. 4 is a schematic view showing another configuration example of diaphragm electrolysis.
  • FIG. 5 is a schematic diagram showing a configuration example in which the wire connected to the electrode B is moved up and down by the wire length adjusting means.
  • FIG. 6 is a schematic view showing a configuration example in which a plurality of liquid discharge valves are provided on the side surface of the electrolytic cell.
  • FIG. 7 is a schematic diagram illustrating a configuration example in which the liquid contact areas of the electrode A and the electrode B are different.
  • FIG. 8 is a schematic diagram illustrating a configuration example in which a plurality of electrodes B having different liquid contact areas are provided.
  • the inventors of the present invention recovered Au at a high recovery rate from an iodine-based etching solution (Au-containing etching solution) containing Au after etching (used) by electrolysis, and at the same time iodine (I 3 - )
  • Au-containing etching solution iodine-based etching solution
  • I 3 - iodine
  • the concentration of iodine (I 3 ⁇ ) in the Au-containing etching solution is high, re-dissolution of Au deposited and deposited on the cathode surface by electrolysis (hereinafter sometimes referred to as electrodeposition) may occur. all right.
  • the iodine-based etchant before use for etching (hereinafter also referred to as pre-use etchant) has an iodine (I 3 ⁇ ) concentration that exhibits the etching ability in order to exhibit sufficient etching ability. It is set high.
  • the present inventors reduce the concentration of iodine (I 3 ⁇ ) remaining after electrolysis by increasing the voltage at the time of electrolysis and increasing the reduction rate of iodine (I 3 ⁇ ) at the cathode. It was investigated. As a result, re-dissolution of electrodeposited Au was suppressed and Au could be recovered in high yield, but it was found that the following problems occurred.
  • the pH of the regenerated etching solution became unstable, the iodine (I 3 ⁇ ) concentration was low, and the etching ability was insufficient.
  • the pH of the regenerated etching solution varied greatly compared to the pH of the etching solution before use. Specifically, when a high voltage is applied, the cathode potential becomes lower than the potential at which Au deposition occurs and the pH increases due to the reaction (a) above, or the anode potential becomes higher than the potential at which oxidation of I ⁇ occurs. A phenomenon that the pH was lowered by the reaction of (b) occurred.
  • the etching performance of the regenerated etching solution is higher than that of the pre-use etching solution, so that when reused as it is, Au is excessively etched, which causes the etching failure. It becomes.
  • the pH of the regenerated etching solution becomes higher, the etching performance of the regenerated etching solution becomes lower than that of the pre-use etching solution. Become.
  • the present inventors have further studied to achieve a high Au recovery rate, solve the above problems of pH fluctuation and iodine concentration reduction, and provide a reusable regenerated etching solution. It was.
  • the cathode potential during electrolysis or -0.7 V (if the reference potential and the reference electrode Ag / AgCl, the same applies hereinafter) to maintain the above reaction H 2 at the cathode is generated (a ) Can be suppressed, and precipitation of Au and reduction of iodine (I 3 ⁇ ) can be achieved while maintaining a pH of about the same level as the pre-use etching solution.
  • the cathode potential falls below ⁇ 0.7 V, for example, as shown in Experimental Example 3, the pH rises greatly, so that it cannot be reused as an etching solution as it is.
  • a preferred cathode potential is ⁇ 0.5 V or more, preferably ⁇ 0.1 V or less.
  • the anode potential during electrolysis is set to +1.0 V or less (the reference potential is the reference electrode Ag). In the case of / AgCl, it is necessary to control so that the same can be maintained.
  • a preferred anode potential is +0.6 V or less, preferably +0.3 V or more.
  • the means for maintaining the cathode potential and the anode potential at predetermined values is not particularly limited.
  • a power source that controls the current or the voltage between the electrodes so that the electrode potential is in a predetermined range, and the electrode on the side where the reference electrode is not installed is physically adjusted so that the electrode potential is in the predetermined range. It is desirable to have an objective means.
  • the “electrode potential is in a predetermined range” is a range of electrode potentials necessary for a target reaction at the cathode and the anode.
  • the electrode potential in a predetermined range when used in the processing method of the Au-containing etching solution provided in the present invention is a cathode potential of ⁇ 0.7 V or more and an anode potential of +1.0 V or less.
  • the method for adjusting the electrode potential to be within a predetermined range is not particularly limited.
  • a reference electrode (Ag / AgCl) is installed on either the cathode or anode A side, and the potential of the electrode A on the side where the reference electrode is installed is obtained from the reference electrode (Ag / AgCl) and the electrode A. Based on the information, the current or the interelectrode voltage may be controlled so that the desired potential is obtained.
  • the physical means for adjusting the potential of the other electrode B on which the reference electrode is not installed is not particularly limited.
  • a means for adjusting the liquid contact area between the electrode B and a liquid (for example, an electrolyzed liquid) is desirable.
  • the liquid contact area of the electrode B for example, (1) means for changing the liquid contact area of the electrode B immersed in the liquid by moving the electrode B up and down, and (2) several types of electrodes B having different surface areas are prepared.
  • means for appropriately selecting the electrode B to be used so as to obtain a desired potential can be considered.
  • physical means that can be considered other than adjustment of the wetted area for example, (3) Since the overvoltage varies depending on the material of the electrode B, it is also effective to appropriately select and change the material of the electrode B. Any one or a combination of these means may be used to control the potential of the electrode B.
  • the electrode material include stainless steel and titanium as the cathode, and stainless steel as the anode and titanium coated with an oxide (for example, iridium oxide).
  • the specific device configuration for realizing the above (1) and (2) is not particularly limited.
  • a mechanism for automatically raising and lowering the electrode B according to the potential may be provided (see, for example, FIG. 5.
  • Other configurations are omitted, and other configurations may be the same as those in FIGS. 1 to 4 (the same applies to FIGS. 6 to 8).
  • the potential of the electrode B can be adjusted by moving the electrode B up and down to change the liquid contact area.
  • a plurality of liquid discharge valves having different heights from the electrolytic cell bottom may be provided in the electrolytic cell (see, for example, FIG. 6).
  • the liquid surface height of the liquid can be raised and lowered to adjust the liquid contact area with the electrode B.
  • the voltage potential of the electrode B can be adjusted by changing the area of the electrode B in relation to the area of the electrode A (see, for example, FIG. 7).
  • a mechanism is provided in which a plurality of electrodes B having different liquid contact areas are previously installed and connected to a power source via a current control means such as a controller. (See, for example, FIG. 8).
  • the potential of the electrode B can be adjusted by selecting one or a plurality of electrodes B through which a current is passed through the controller so as to obtain a desired potential.
  • the anode potential tends to increase, so the anode area is made larger than the cathode area. It is desirable.
  • the liquid contact resistance of the anode is reduced, and the anode potential can be controlled to the predetermined value.
  • the Au-containing etching solution When the Au-containing etching solution is electrolyzed with the cathode potential and anode potential adjusted to a predetermined value as described above, Au ions can be deposited on the cathode as metallic Au. Further, the reaction (a) in which H 2 is generated at the cathode can be suppressed. Further, the reaction (b) in which O 2 is generated at the anode can be suppressed, and precipitation of I 2 can be prevented. Therefore, the pH of the regeneration etchant is approximately equal to the pH before the etchant used, and iodine (I 3 -) concentration of iodine prior to use etching solution (I 3 -) can be restored to substantially the same concentration.
  • the pH almost equal to that of the pre-use etchant means that the etching ability equivalent to that of the pre-use etchant can be exhibited.
  • the specific amount of change varies somewhat depending on the pH of the etching solution before use, but is generally within a range of ⁇ 0.5 of the pH of the etching solution before use.
  • the iodine (I 3 ⁇ ) concentration substantially equivalent to the pre-use etching solution means an iodine (I 3 ⁇ ) concentration that can dissolve and remove at least unnecessary Au as the etching solution.
  • an iodine (I 3 ⁇ ) concentration that can dissolve and remove at least unnecessary Au as the etching solution.
  • the iodine (I 3 ⁇ ) concentration in the etching solution before use is 100%, if the iodine (I 3 ⁇ ) concentration is within the range of ⁇ 50%, unnecessary Au
  • the iodine (I 3 ⁇ ) concentration be ⁇ 10%, and still more preferable that the iodine (I 3 ⁇ ) concentration be within ⁇ 5%. It is. In order to approach the iodine (I 3 ⁇ ) concentration in the etching solution before use, it is desirable to appropriately control the electrode potential to prevent iodine precipitation and the like.
  • the Au-containing etching solution is supplied to an electrolysis tank in which a cathode and an anode are installed and electrolyzed. At that time, if Au deposited on the cathode is not re-dissolved by I 3 ⁇ generated at the anode, This is desirable because the time required for electrolysis can be shortened. Specifically, it is desirable to perform electrolysis of a diaphragm provided with a diaphragm that can be electrically connected and does not allow an Au-containing etching solution to pass through.
  • the Au-containing etching solution can be adjusted to different liquid qualities in the cathode chamber and the anode chamber by dividing the electrolysis tank into the anode side (anode chamber) and the cathode side (cathode chamber) by the diaphragm.
  • the concentration of iodine (I 3 ⁇ ) in the Au-containing etching solution supplied to the cathode chamber is high, the iodine cannot be sufficiently reduced at the cathode potential, and the precipitated Au may be redissolved.
  • the iodine concentration (I 3 ⁇ ) on the cathode chamber side may be reduced by dilution or the like to such an extent that iodine (I 3 ⁇ ) can be sufficiently reduced at the cathode potential.
  • the above problem is that the Au-containing etching solution is continuously supplied from the supply source of the Au-containing etching solution (for example, an Au-containing etching solution storage tank or etching apparatus) to the electrolysis tank. Often occur when electrolysis is performed continuously.
  • the iodine (I 3 ⁇ ) concentration contained in the Au-containing etching solution supplied to the cathode chamber may not be constant, and when the iodine concentration (I 3 ⁇ ) becomes high, it precipitates. This is because Au is redissolved.
  • the supply amount of the Au-containing etching solution to the cathode chamber is [current (A (ampere))> iodine concentration (of the Au-containing etching solution supplied to the cathode side).
  • the supply amount of the Au-containing etching solution in consideration of the iodine (I 3 ⁇ ) concentration, re-dissolution of the precipitated Au can be suppressed and the Au recovery rate can be increased.
  • the specific iodine (I 3 ⁇ ) concentration in the cathode chamber is not particularly limited, but is preferably 60 mmol / L or less, more preferably 20 mmol / L or less.
  • FIG. 1 is an example of a schematic configuration diagram of diaphragm electrolysis.
  • the diaphragm electrolysis tank is composed of a cathode chamber 2 and an anode chamber 7 partitioned by a diaphragm 5.
  • the diaphragm 5 is a film that can conduct electricity and does not allow liquid to pass through the cathode chamber 2 and the anode chamber 7, and examples thereof include a cation exchange membrane and a microporous film.
  • the cathode chamber 2 is provided with a cathode 3 and a reference electrode 4 (Ag / AgCl).
  • An anode 6 is installed in the anode chamber 7.
  • the cathode potential may be controlled at a constant potential so that the potential difference between the reference electrode 4 and the cathode is measured and fed back to the DC power source 9 so that the cathode potential can be kept constant.
  • the set value of the interelectrode voltage and current may be controlled by a computer so that the cathode potential is maintained within the predetermined range based on the feedback.
  • the used etching solution tank 1 stores an Au-containing etching solution that is used for etching Au and discharged during the manufacturing process of the electronic material.
  • the liquid property of the Au-containing etching solution targeted in the present invention is not particularly limited, and may be basic, neutral, or acidic. However, if the pH of the etching solution is strongly basic or strongly acidic, the object to be plated may be damaged. Therefore, the pH of the etching solution before use is often adjusted to about 1 to 7 in many cases. Therefore, the pH of the Au-containing etching solution after use is generally about 1-7.
  • the concentration of Au in the Au-containing etching solution is not particularly limited.
  • an Au-containing etching solution contains approximately 0.1 to 10 g / L of Au.
  • electrolysis can be performed stably regardless of the concentration of Au.
  • the iodine (I 3 ⁇ ) concentration in the Au-containing etching solution is not particularly limited because it varies depending on the etching conditions and the like, but is generally about 10 to 200 mmol / L.
  • the used etchant tank 1 and the cathode chamber 2 are connected by a pipe line via the pump P1, and the Au-containing etchant is supplied to the cathode chamber 2.
  • the cathode chamber 2 and the anode chamber 7 are connected by a pipe line via a pump P2, and an etching solution (used etching solution) after Au deposition is finished is supplied to the anode chamber 7.
  • an etching solution used etching solution
  • the oxidation of iodine is mainly performed, and the regeneration of the etching ability (recovery of iodine (I 3 ⁇ ) concentration) is performed.
  • the electrolytic solution previously filled in the anode chamber 7 is not particularly limited, and for example, an iodine-based etching solution may be filled.
  • the electrolytic solution previously filled in the anode chamber 7 is not particularly limited as long as it has a property of conducting electricity.
  • the anode chamber 7 may be filled with the iodine-based etching solution before use.
  • Anode chamber 7 and the electric deconstructed etchant tank 8 is connected in line via the pump P3, iodine (I -) is oxidized, iodine (I 3 -) concentration was restored reproduction etchant electrical It is supplied to the decomposed etching solution tank 8.
  • the pH of the regenerated etching solution supplied to the electrolyzed etching solution tank 8 is substantially the same as that of the pre-use etching solution (preferably ⁇ 0.5), and iodine (I) of the iodine-based etching solution previously filled in the cathode chamber. 3 ⁇ ) Although there are some fluctuations depending on the concentration, the iodine (I 3 ⁇ ) concentration is equivalent to the pre-use etching solution (preferably ⁇ 50%). Therefore, the regenerated etching solution can be used as it is for the etching of Au.
  • the Au deposited on the cathode 3 may be recovered from the cathode 3 by any means, and can be easily recovered by scraping means such as a scraper.
  • the cathode potential and the anode potential during electrolysis are appropriately controlled, so that Au can be recovered in a high yield, and the used etching solution has substantially the same pH as the etching solution before use. And can be regenerated to an equivalent iodine concentration.
  • the anode chamber 7 (capacity 300 mL) was provided with an anode 6 (electrode having a titanium surface coated with iridium oxide; surface area 26.4 cm 2 ). Incidentally, it was set to the surface area of the cathode surface area of the anode chamber 7 such that the desired anodic potential is obtained twice (13.2cm 2) (26.4cm 2) .
  • a potassium iodide aqueous solution (iodine-based etching solution A: potassium iodide concentration 80 g / L, iodine (I 3 ⁇ ) concentration: 3 g / L (about 10 mmol / L)) in which iodine is dissolved in advance. Filled. Also in the anode chamber 7, an aqueous potassium iodide solution in which iodine is dissolved in advance (iodine-based etching solution B: potassium iodide concentration 80 g / L, iodine (I 3 ⁇ ) concentration: 40 g / L (about 150 mmol / L)) Filled.
  • iodine-based etching solution A potassium iodide concentration 80 g / L, iodine (I 3 ⁇ ) concentration: 3 g / L (about 10 mmol / L)
  • an Au-containing etching solution (dissolved Au concentration 1.2 g / L, potassium iodide concentration 80 g / L, iodine (I 3 ⁇ ) concentration 40 g / L (about 150 mmol / L)) is used from the used etching solution tank 1. Electrolysis was performed by continuously supplying the cathode chamber 2 while adjusting the supply amount with the pump P1.
  • a direct current power source 9 is measured so that the potential difference between the reference electrode 4 (Ag / AgCl) installed in the cathode chamber 2 and the cathode 3 is measured and the cathode potential is maintained at ⁇ 0.3 V (vs. Ag / AgCl). Controlled the output.
  • the anode potential was maintained at +0.6 V or less (vs. Ag / AgCl) by adjusting the anode area.
  • the supply amount of the Au-containing etching solution is 17 mL / hr based on the iodine (I 3 ⁇ ) concentration, iodine reduction rate, cathode potential ( ⁇ 0.3 V), and current density (9 mA / cm 2 ).
  • the reduction amount of iodine in the cathode chamber 2 was made to exceed the supply amount of the used etching solution.
  • the used etching solution in the cathode chamber 2 in which Au was deposited by electrolysis and the Au concentration decreased was supplied to the anode chamber 7 by the pump P2.
  • the supply amount of the pump P2 was controlled so as to be about the same as the supply amount of the Au-containing etching solution from the pump P1 (17 mL / hr).
  • iodine ions reduced by the reaction in the cathode chamber 2 are oxidized, and iodine (I 3 ⁇ ) is regenerated. Then, the regenerated etching solution whose iodine (I 3 ⁇ ) concentration has been recovered by such an oxidizing action is supplied to the electrolyzed etching solution tank 8 via the pump P3 in substantially the same amount (17 mL / hr).
  • the composition of each of the Au-containing etchant in the used etchant tank 1 and the regenerated etchant in the electrolyzed etchant tank 8 was examined and described in Table 1.
  • the composition of the pre-use etchant was examined in advance before the etchant was used for etching Au.
  • the Au concentration contained in the regenerated etching solution was less than 5 mg / L, and Au could be recovered in a high yield.
  • the pH of the etching solution before use and the pH of the regenerated etching solution are both 3.3, and the iodine (I 3 ⁇ ) concentration of the regenerated etching solution obtained during the electrolysis without changing the pH.
  • the iodine (I 3 ⁇ ) concentration was the same as that of the pre-use etching solution, and the composition was almost the same, so that it was confirmed that it was in a state suitable for reuse.
  • Example 2 Next, the change in pH of the liquid before and after electrolysis in the range of the cathode potential and anode potential specified in the present invention was examined.
  • the following experiment was conducted using an electrolysis test facility having the configuration shown in FIG. In addition, it is the structure similar to the said Experimental example 1 except having supplied the reproduction
  • capacitance 100mL capacity of the cathode chamber 2 and the anode chamber 7 was 100 mL, the surface area of the cathode was 3 cm 2 , and the surface area of the anode was 9 cm 2 .
  • Electrolysis was performed for 1 hour, and the cathode potential, the anode potential, the pH of the cathode chamber and the pH of the anode chamber were examined. The results are shown in Table 2.
  • Example 3 The change in pH in the cathode chamber when the cathode potential range specified in the present invention was outside the range was examined. Except that the cathode potential was changed to -1.0 V (vs. Ag / AgCl), the following experiment was conducted in the same manner as in Experimental Example 2, using the same electrolysis test facility as shown in FIG. Went. The results are shown in Table 3.
  • Example 4 The pH variation in the anode chamber when the anode potential range defined in the present invention was out of the range was examined.
  • the following experiment was conducted using an electrolysis test facility having the configuration shown in FIG. FIG. 3 is a batch type membrane electrolysis.
  • the cathode titanium plate (surface area 2.9 cm 2), the anode using the electrode produced by coating the surfaces of the titanium plate with iridium oxide (surface area 8.8 cm 2).
  • the Au-containing etching solution used in Experimental Example 1 dissolved Au concentration 1.2 g / L, potassium iodide concentration 80 g / L, iodine (I 3 ⁇ ) concentration 40 g / L (approximately 150 mmol / L)
  • the anode chamber 7 was filled with the iodine-based etching solution B in advance.
  • Electrolysis When performing the electrolysis, the electrolysis was performed while adjusting the cathode potential to maintain -0.7 V (vs. Ag / AgCl). Electrolysis was started from +0.48 V (electrolysis time 0 minutes), and the anode potential was raised to +1.89 V (electrolysis time 240 minutes) at the end of electrolysis. Electrolysis was performed for 4 hours, and the change in pH of the anode chamber was examined. The results are shown in Table 4.

Abstract

La présente invention a pour but de créer une technique qui permet de collecter l'or présent dans une solution de gravure usagée qui contient de l'iode, avec un taux de collecte élevé, et qui permet également de rétablir la concentration en iode (I3 -) dans la solution de gravure, afin de restaurer la capacité de gravure de la solution de gravure. La présente invention concerne également un procédé de traitement d'une solution de gravure qui contient de l'iode ainsi que de l'or, ledit procédé comprenant l'électrolyse de la solution de gravure afin de collecter l'or présent dans ladite solution de gravure, et de rétablir la concentration en iode (I3 -), l'électrolyse étant réalisée en maintenant le potentiel de la cathode à -0,7 V ou plus (le potentiel de référence étant le potentiel d'une électrode de référence Ag/AgCl), et le potentiel de l'anode à + 1,0 V ou moins (le potentiel de référence étant le potentiel d'une électrode de référence Ag/AgCl).
PCT/JP2014/063275 2013-05-31 2014-05-20 Procédé et dispositif de traitement d'une solution de gravure qui contient de l'iode ainsi que de l'or WO2014192581A1 (fr)

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CN201480021400.9A CN105164317B (zh) 2013-05-31 2014-05-20 含Au碘系蚀刻液的处理方法以及处理装置
JP2014543381A JP5669995B1 (ja) 2013-05-31 2014-05-20 Ａｕ含有ヨウ素系エッチング液の処理方法、および処理装置
HK16101230.0A HK1213303A1 (zh) 2013-05-31 2016-02-03 碘系蝕刻液的處理方法以及處理裝置

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JP2013-116205 2013-05-31

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HK (1) HK1213303A1 (fr)
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Cited By (2)

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CN105965030A (zh) * 2016-06-20 2016-09-28 昆山鸿福泰环保科技有限公司 一种碘化金废液中金回收工艺
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