WO2020204003A1 - Appareil d'électrolyse et procédé d'électrolyse - Google Patents

Appareil d'électrolyse et procédé d'électrolyse Download PDF

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Publication number
WO2020204003A1
WO2020204003A1 PCT/JP2020/014682 JP2020014682W WO2020204003A1 WO 2020204003 A1 WO2020204003 A1 WO 2020204003A1 JP 2020014682 W JP2020014682 W JP 2020014682W WO 2020204003 A1 WO2020204003 A1 WO 2020204003A1
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WIPO (PCT)
Prior art keywords
electrolytic solution
electrolytic
drainage
electrolytic cell
liquid supply
Prior art date
Application number
PCT/JP2020/014682
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English (en)
Japanese (ja)
Inventor
大輔 手塚
明 曾澤
Original Assignee
Ｊｘ金属株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2019069358A external-priority patent/JP6929320B2/ja
Priority claimed from JP2019069347A external-priority patent/JP6962960B2/ja
Priority claimed from JP2019069346A external-priority patent/JP2020164960A/ja
Priority claimed from JP2019069355A external-priority patent/JP7002494B2/ja
Priority claimed from JP2019069353A external-priority patent/JP6967032B2/ja
Application filed by Ｊｘ金属株式会社 filed Critical Ｊｘ金属株式会社
Priority to CN202080024892.2A priority Critical patent/CN113631762B/zh
Publication of WO2020204003A1 publication Critical patent/WO2020204003A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing
    • 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 an electrolytic device and an electrolytic method.
  • the electrolytic solution is supplied from the lower part on one end side in the longitudinal direction of the electrolytic cell, and the electrolytic solution is discharged from the upper part on the other end side. Is being done. Keeping the liquid composition and additive concentration in the electrolytic cell uniform is one of the important techniques for improving the quality of electrolytic copper and the electrolytic performance, for example, and various methods have been studied so far.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2007-204779
  • the electrolytic solution is supplied from one end side in the longitudinal direction of the electrolytic cell to the upper layer portion and the lower layer portion of the electrolytic cell, and the liquid on the opposite end side.
  • a method of draining liquid from the upper layer has been proposed.
  • Patent Document 2 proposes a method in which an electrolytic solution is supplied from the upper part of one end in the longitudinal direction of an electrolytic cell toward the side surface and drained from the lower part of the other end. There is.
  • Patent Document 3 and Japanese Patent No. 5227404 Patent Document 4
  • Patent Document 4 provide a method of supplying an electrolytic solution from the bottom of the electrolytic cell or the side of the electrolytic cell. Has been proposed.
  • the electrolytic solution is supplied from below the electrolytic cell and from the side of the cathode, and the electrolytic solution is discharged from the electrolytic cell discharge port at the upper part of the electrolytic cell, whereby electrolysis on the drain side is performed. It is possible to prevent an increase in the copper concentration at the bottom of the tank.
  • the liquid supply side is supplied from above as in the conventional case, a dead space in which the electrolytic solution is not supplied is generated below the electrolytic cell on the liquid supply side, and the mixed state in the electrolytic cell can be sufficiently improved. It cannot be said that there is.
  • the mixed state of the electrolytic cell in the electrolytic cell can be improved by supplying the electrolytic cell from the bottom of the electrolytic cell and the side of the electrolytic cell.
  • Patent Document 4 by forcibly convection of the electrolytic solution from the lower side to the upper side, there is a possibility that a problem of cathode contamination due to winding up of the palace may occur.
  • the present disclosure provides an electrolyzer and an electrolysis method capable of improving the mixed state of the electrolytic solution supplied into the electrolytic cell while suppressing the hoisting of the ridge.
  • the electrolyzer according to the embodiment of the present invention is an electrode composed of a plurality of anode plates and a plurality of cathode plates alternately arranged at intervals along the longitudinal direction of an electrolytic tank containing an electrolytic solution.
  • An electrolytic solution supply unit (liquid supply pipe) that supplies the electrolytic solution from the liquid supply port) toward the second side wall side of the electrolytic tank facing the first side wall, and a liquid supply pipe provided on the second side wall side to supply the electrolytic solution.
  • the supply port is arranged at a height within 400 mm from the liquid level of the electrolytic solution. Further, it is preferable that the discharge port is arranged in a range of 100 mm upward and 300 mm downward, starting from the lower end of the electrode. Further, it is preferable that the electrolytic solution supply unit supplies the electrolytic solution into the electrolytic cell so that the supply flow rate of the electrolytic solution is 20 to 100 L / min.
  • the electrolytic solution supply unit extends in the longitudinal direction of the electrolytic cell in the vicinity of the liquid level of the electrolytic solution, and the length of the electrolytic solution supply unit extends so as to supply the electrolytic solution to the spaces between the anode plate and the cathode plate, respectively. It is preferable that a plurality of supply ports are arranged along the direction.
  • Electrodes arranged at intervals along the longitudinal direction of the electrolytic solution containing the electrolytic solution are immersed in the electrolytic solution, and the electrolytic solution is placed.
  • An electrolyzer that electrolyzes while circulating and is a liquid supply pipe extending along a first side wall extending in the longitudinal direction of the electrolytic tank and having a plurality of liquid supply ports arranged at intervals from each other, and liquid supply.
  • a trough that extends along the first side wall so as to accommodate the pipe stores the electrolytic solution supplied from the plurality of liquid supply ports, overflows the electrolytic solution, and supplies the electrolytic solution into the electrolytic tank.
  • It has a plurality of drainage ports extending along a second side wall facing the side wall of 1 and arranged below the gutter and spaced apart from each other, and electrolysis in the electrolytic tank from the drainage port.
  • It is an electrolytic device including a drainage pipe for draining liquid.
  • the electrolytic apparatus it is preferable to further include an auxiliary pipe connected to the central portion in the longitudinal direction of the liquid supply pipe to supply the electrolytic solution to the liquid supply pipe. Further, it is preferable to further provide an auxiliary pipe connected to the tip of the liquid supply pipe on the downstream side in the longitudinal direction to supply the electrolytic solution to the drainage pipe. Further, it is preferable that the gutter portion is provided with an opening for overflowing the electrolytic solution, and the opening is arranged at a height within 50 mm from the liquid surface of the electrolytic solution.
  • the drainage box having a bottom surface below the liquid level of the electrolytic solution, the outlet of the drainage pipe is connected to the bottom surface, and the electrolytic solution in the drainage pipe can be pumped up. ..
  • the drainage box is provided with a notch for sending foreign matter in the electrolytic solution in the electrolytic cell to the drainage box on the side wall on the side of the electrolytic cell in contact with the electrolytic solution.
  • it is provided with a drainage section for discharging the electrolytic solution in the drainage box to the outside of the electrolytic cell, and is arranged between the drainage box and the drainage section to raise the liquid level of the electrolytic solution in the drainage box.
  • an adjusting plate for adjusting the difference in the height of the electrolytic solution in the electrolytic cell.
  • the drainage pipe is provided with at least two pipes.
  • the electrolyzer accommodates an electrolytic solution, and electrolyzes electrodes arranged at intervals along the longitudinal direction in the electrolytic solution.
  • a supply provided with a tank and a plurality of liquid supply ports for supplying the electrolytic solution toward the second side wall side extending along the first side wall extending in the longitudinal direction of the electrolytic tank and facing the first side wall.
  • It is provided at one end and has a drainage section that drains the electrolytic solution to the outside of the electrolytic tank, and a bottom surface that is connected to the drainage section and the drainage pipe and is below the liquid level of the electrolytic solution. It is an electrolyzer equipped with a drainage box to which the outlet of the pipe is connected and capable of pumping the electrolytic solution in the drainage pipe.
  • the opening area of the drainage port is larger than the opening area of the liquid supply port.
  • the diameter of the drainage pipe is larger than the diameter of the liquid supply pipe.
  • the drainage box is provided with a notch on the side wall on the side in contact with the electrolytic solution for sending foreign matter in the electrolytic solution in the electrolytic cell to the drainage box.
  • an adjusting plate which is arranged between the drainage box and the drainage section, is provided to adjust the difference between the height of the electrolyte level in the drainage box and the height of the electrolyte in the electrolytic cell. It is preferable to prepare.
  • electrodes arranged at intervals along the longitudinal direction of the electrolytic solution containing the electrolytic solution are immersed in the electrolytic solution. It is an electrolyzer that electrolyzes while circulating, and extends along the first side wall of the electrolytic tank extending in the longitudinal direction, and faces the first side wall from a plurality of liquid supply ports arranged at intervals from each other.
  • It is provided with a drainage pipe for draining the electrolytic solution from the drainage port and a drainage section for draining the electrolytic solution drained by the drainage pipe to the outside of the electrolytic tank, and the liquid supply pipe is at least upstream of the electrolytic tank.
  • It is an electrolytic device provided with two or more piping portions capable of independently supplying an electrolytic solution to the side and the downstream side.
  • the ends of the piping portions are arranged so as to partially overlap each other in the electrolytic cell.
  • the ratio of the total opening area of the liquid supply port in the area where one piping part overlaps with the other piping part is 1/4 or more with respect to the total opening area of the liquid supply port provided in one piping part. It is preferably arranged in.
  • the diameter of the drainage pipe is larger than the diameter of the liquid supply pipe. Further, it is connected to the drainage part and the drainage pipe, and has a bottom surface below the liquid level of the electrolytic solution, and the outlet of the drainage pipe is connected to the bottom surface so that the electrolytic solution in the drainage pipe can be pumped up. It is preferable to further include a drainage box.
  • electrodes arranged at intervals along the longitudinal direction of the electrolytic solution containing the electrolytic solution are immersed in the electrolytic solution. It is an electrolyzer that electrolyzes while circulating, and extends along the first side wall of the electrolytic tank extending in the longitudinal direction, and faces the first side wall from a plurality of liquid supply ports arranged at intervals from each other.
  • It is provided with a drainage pipe for draining the electrolytic solution from the drainage port of the above and a drainage section for draining the electrolytic solution drained by the drainage pipe to the outside of the electrolytic tank, and the drainage pipe runs along the longitudinal direction. It is an electrolytic device provided with at least two or more pipes.
  • the electrolyzer according to the embodiment of the present invention is provided with a bottom surface below the liquid level of the electrolytic solution, the outlet of the drainage pipe is connected to the bottom surface, and the electrolytic solution in the drainage pipe can be pumped up. It is preferable to further include a liquid box. Further, it is preferable that the drainage pipe includes at least two or more pipes, that is, a first pipe capable of collecting the electrolytic solution on the upstream side in the longitudinal direction and a second pipe capable of collecting the electrolytic solution on the downstream side in the longitudinal direction. .. Further, it is preferable that the diameter of the drainage pipe is larger than the diameter of the liquid supply pipe. Further, it is preferable that the opening area of the drainage port is larger than the opening area of the liquid supply port.
  • the drainage box is provided with a notch on the side wall on the side in contact with the electrolytic solution for sending foreign matter in the electrolytic solution in the electrolytic cell to the drainage box.
  • an adjusting plate which is arranged between the drainage box and the drainage section, is provided to adjust the difference between the height of the electrolyte level in the drainage box and the height of the electrolyte in the electrolytic cell. It is preferable to prepare. Further, it is preferable that the drainage box is provided with a dividing wall for dividing the bottom surface to which the outlet of the drainage pipe is connected into a plurality of regions.
  • the electrolysis method according to the embodiment of the present invention is an electrode composed of a plurality of anode plates and a plurality of cathode plates alternately arranged at intervals along the longitudinal direction of the electrolytic solution containing the electrolytic solution.
  • This is an electrolysis method including supplying and discharging an electrolytic solution from below the second side wall of the electrolytic tank facing the first side wall to the outside of the electrolytic tank.
  • the electrolytic solution is supplied from a liquid supply pipe extending along the first side wall and having a plurality of liquid supply ports, and the liquid supply pipe is housed therein.
  • the electrolytic solution supplied from the liquid supply pipe is stored in the trough extending along the side wall of the gutter, and the stored electrolytic solution overflows from the upper part of the gutter to be supplied into the electrolytic cell and extends along the second side wall.
  • the electrolytic cell is discharged to the outside of the electrolytic cell by providing a bottom surface below the surface of the electrolytic cell, and the electrolytic cell in the electrolytic cell is discharged to the bottom surface. It is preferable to include pumping the electrolytic solution in the drainage pipe and discharging it to the outside of the electrolytic cell by a drainage box to which the outlet of the liquid drainage pipe is connected.
  • the electrolytic solution can be supplied into the electrolytic cell at least two pieces capable of independently supplying the electrolytic solution to the upstream side and the downstream side of the electrolytic cell. It is preferable to include supplying the electrolytic solution from a plurality of liquid supply ports provided in the liquid supply pipe provided with the above-mentioned piping unit toward the second side wall side.
  • discharging the electrolytic solution to the outside of the electrolytic cell causes the electrolytic solution to be drained through a drainage pipe provided with at least two or more pipes along the longitudinal direction. It is preferable to include the above.
  • an electrolyzer and an electrolyzing method capable of improving the mixed state of the electrolytic solution supplied into the electrolytic cell while suppressing the hoisting of the palace.
  • FIG. 1 It is the schematic which shows an example of the electrolytic apparatus which concerns on 1st Embodiment of this invention. It is a top view schematic of the electrolytic apparatus which concerns on 2nd Embodiment of this invention. It is the schematic which shows the positional relationship between the liquid supply pipe and the liquid drainage pipe when the electrolytic apparatus which concerns on 2nd Embodiment of this invention is seen from the side. It is explanatory drawing which shows the arrangement position in the electrolytic cell of a drainage box and a drainage pipe. It is a top view which shows the liquid supply part and the drainage box. It is sectional drawing which shows the state that the electrolytic solution flows from a drainage box to a liquid supply part. FIG.
  • FIG. 7A is a schematic top view of the electrolyzer according to the third embodiment of the present invention
  • FIG. 7B is a schematic cross-sectional view of the electrolyzer according to the third embodiment of the present invention. It is a figure. It is explanatory drawing which shows the liquid supply port provided in the liquid supply pipe, and the drainage port provided in the drainage pipe. It is a top view which shows the liquid supply part and the drainage box. It is a side schematic view which shows the notch part provided in the drainage box.
  • FIG. 11A is a schematic top view of the electrolyzer according to the fourth embodiment of the present invention
  • FIG. 11B is a schematic cross-sectional view of the electrolyzer according to the fourth embodiment of the present invention. It is a figure.
  • 17 (a) and 17 (b) are cases where the Cu concentration and the Nikawa concentration at 9 points on the electrode orthogonal plane along the longitudinal plane of the electrolytic cell were measured using the electrolyzer of FIG. 1 (Example 1).
  • 17 (c) and 17 (d) are shown in FIG. 16 (A)
  • FIGS. 17 (e) and 17 (f) are shown in FIG. 16 (B) when the electrolytic device (Comparative Example 1) shown in FIG. 16 (A) is used.
  • 6 is a graph showing a Cu concentration distribution and a Nikawa concentration distribution when the electrolytic apparatus shown (Comparative Example 2) is used.
  • 18 (a) and 18 (d) are the electrolytic cells of Example 1, FIGS.
  • FIGS. 18 (c) and 18 (f) are the electrolytic cells of Comparative Example 1
  • FIGS. 18 (c) and 18 (f) are the electrolytic cells of Comparative Example 2.
  • It is a table which shows the result of sampling the electrolytic solution of 9 points.
  • 19 (a) and 19 (b) show three electrode parallel surfaces (first sheet) along the short side direction of the electrolytic cell when the electrolytic device having the configuration shown in FIG. 1 is used (Example 1).
  • 25th, 49th is a graph showing the average value of the distribution of Cu concentration and Nikawa concentration.
  • 20 (a) and 20 (b) show Cu when 9 points are measured for each of 3 electrode parallel surfaces (1st, 25th, 49th) along the short side direction of the electrolytic cell.
  • FIG. 21 (a) shows the simulation result of the Cu concentration distribution in the central portion along the longitudinal direction of the electrolytic cell according to the second embodiment
  • FIG. 21 (b) shows the central portion of the electrolytic cell according to the present embodiment
  • 21 (c) shows the simulation result of the central cross-section Nikawa concentration distribution along the longitudinal direction of the electrolytic cell according to this embodiment
  • FIG. 21 (d) shows the present.
  • It is explanatory drawing which shows the cross electrode cross-section Nikawa concentration distribution of the central part of the electrolytic cell which concerns on Example.
  • the electrolyzer according to the first embodiment of the present invention includes a rectangular parallelepiped electrolytic cell 1 for accommodating an electrolytic solution.
  • the size of the electrolytic cell 1 is, for example, the length (inner diameter in the longitudinal direction X) of 5200 to 5900 mm, the width (inner diameter in the lateral direction Y) of 1095 to 1110 mm, and the depth of 1275 to 1510 mm.
  • the electrolytic tank 1 includes a first side wall 11 extending in a direction parallel to the longitudinal direction X, a second side wall 12 facing the first side wall 11, and a first side wall 11 and a second side wall 11 at one end in the longitudinal direction X.
  • a third side wall 13 extending perpendicularly to the side wall 12, and a fourth side wall 14 extending perpendicularly to the first side wall 11 and the second side wall 12 at the other end of the longitudinal direction X and facing the third side wall 13. And have.
  • an electrolytic cell extending along the longitudinal direction X of the electrolytic cell 1 at a height close to or near the liquid level of the electrolytic cell housed in the electrolytic cell 1 is supplied.
  • Section 2 (hereinafter, also referred to as “liquid supply pipe”) 2 is arranged.
  • the electrolytic solution supply unit 2 can be configured by piping or the like.
  • a plurality of supply ports (hereinafter, also referred to as “liquid supply ports”) 21a, 21b, 21c ... 21x are preferably provided in the electrolytic solution supply unit 2 along the longitudinal direction X at equal intervals.
  • the plurality of supply ports 21a, 21b, 21c ... 21x have a height within 400 mm, more preferably a height within 200 mm, and further preferably 50 mm from the electrolytic solution surface. It is preferably placed at a height within.
  • an electrolytic solution discharge portion (hereinafter, also referred to as “drainage pipe”) 3 extending along the longitudinal direction X is arranged.
  • the electrolyte discharge unit 3 can be composed of a pipe or the like.
  • a plurality of discharge ports (hereinafter, also referred to as “drainage ports”) 31a, 31b, 31c ... 31x are provided in the electrolytic solution discharge unit 3 along the longitudinal direction X at predetermined intervals. ..
  • the plurality of discharge ports 31a, 31b, 31c ... 31x are preferably arranged at equal intervals so as to be relatively lower than the plurality of supply ports 21a, 21b, 21c ... 21x.
  • the electrolytic solution supply unit 2 and the electrolytic solution discharge unit 3 are arranged so that the electrolytic solution flows from the upper side to the lower side from the first side wall 11 side to the second side wall 12 side. Since the liquid flows from the top to the bottom, the mixed state of the electrolytic solution, especially the mixed state of metal ions and additives in the electrolytic cell, is improved while suppressing the hoisting of the deposits on the bottom of the electrolytic cell 1. can do.
  • the discharge ports 31a, 31b, 31c ... 31x may involve the bottom of the electrolytic cell 1 and the like. May cause clogging or malfunction. Therefore, the discharge ports 31a, 31b, 31c ... 31x are preferably arranged in a range of 100 mm upward and 300 mm downward, more preferably 100 mm upward, starting from the lower end of the electrode of the electrolytic cell 1. , Arranged below in a range of 100 mm.
  • the electrolytic solution is supplied to the supply port 21a on the most upstream side of the first side wall 11 side, and faces the first side wall 11 via the supply ports 21b, 21c ... 21x, respectively. It is supplied toward the second side wall 12 side of the electrolytic cell 1.
  • the electrolytic solution supplied toward the second side wall 12 side is discharged from the discharge port 31x side on the most downstream side of the second side wall 12 side via the plurality of discharge ports 31a, 31b, 31c ... It is discharged to the outside of 1.
  • the passivation phenomenon when electrolytic refining is performed using a material having a high current density or a high impurity concentration for the anode plate is more efficient. Can be suppressed.
  • one supply port 21a, 21b, 21c ... 21x and one discharge port 31a, 31b, 31c ... 31x are arranged.
  • the supply port 21a, 21b, 21c ... 21x and the discharge port 31a, 31b, 31c ... 31x in the space corresponding to the size of the space between the anode plate and the cathode plate. A plurality of them may be arranged. Further, the supply ports 21a, 21b, 21c ... 21x and the discharge ports 31a, 31b, 31c ...
  • the number of 31x may be larger than the number of the electrolytic cell 1 from the central side in the longitudinal direction to the liquid supply side.
  • the configuration of the anode plate and the cathode plate is not particularly limited.
  • the anode plate serves as an anode for electrolytic refining or electrowinning, and is composed of a crude metal plate material.
  • the cathode plate serves as a cathode for electrolytic refining or electrowinning, and is composed of a plate-shaped metal having excellent conductivity.
  • the electrolytic solution contained in the electrolytic cell 1 is an acidic aqueous solution containing a metal to be purified, and can contain an additive for smoothing the surface of the metal electrodeposited on the surface of the cathode plate.
  • a mixed aqueous solution of copper sulfate and sulfuric acid mixed with an additive such as Nikawa or thiourea can be used as the electrolytic solution.
  • the electrolytic solution supply unit 2 supplies the electrolytic solution into the electrolytic cell 1 so that the supply flow rate of the electrolytic solution is 20 to 100 L / min. If the supply flow rate of the electrolytic solution is less than 20 L / min, the additive may be decomposed before being distributed in the electrolytic cell 1, and the smoothness of the electrodeposited metal may be impaired or passivation may occur.
  • the supply flow rate of the electrolytic solution is preferably high from the viewpoint of electrolytic efficiency, but if the supply flow rate of the electrolytic solution exceeds 100 L / min, the ridges in the electrolytic cell 1 may be rolled up and adhere to the surface of the cathode plate. ..
  • the electrolytic solution is supplied from the upper side of the first side wall 11 and discharged from the lower side of the second side wall 12, and the supply flow rate is 20 to 100 L / L.
  • the supply flow rate of the electrolytic solution is preferably 30 to 90 L / min, more preferably 30 to 70 L / min, and even more preferably 50 to 70 L / min.
  • the electrolytic device of FIG. 1 is provided with a circulation mechanism of an electrolytic solution (not shown).
  • the recirculation mechanism adds additives such as nikawa and thiourea to the electrolytic solution discharged from the discharge port 31x of the electrolytic cell 1, adjusts the necessary components and the temperature, and supplies the adjusted electrolytic solution to the supply port 21a. Circulates into the electrolytic cell 1.
  • the electrolyzer is provided with a power feeding mechanism (not shown).
  • the power feeding mechanism includes a power supply device and wiring for applying a direct current between the anode plate and the cathode plate.
  • the electrolytic solution is supplied from the width (X) direction of the electrolytic cell 1, that is, from the first side wall 11 side to the second side wall 12 side of the electrolytic cell 1.
  • the installation positions of the supply ports 21a, 21b, 21c ... 21x on the first side wall 11 side are relative to those of the discharge ports 31a, 31b, 31c ... 31x on the second side wall 12 side.
  • the so-called “horizontal insertion top insertion bottom removal method” is adopted, which is configured so as to be upward.
  • the risk of winding up the palace is reduced. Therefore, even if the supply flow rate of the electrolytic solution is increased, the mixed state of the electrolytic solution can be improved while suppressing the hoisting of the palace, and the electrodeposition efficiency of the electrodeposited object can be improved as compared with the conventional case. Further, since additives such as Nikawa, which affect the surface texture of the electrodeposited material, can be uniformly distributed throughout the electrolytic cell, an electrodeposited material having uniform quality can be obtained in the entire electrolytic cell 1.
  • a metal such as copper can be electrodeposited on a plurality of cathode plates.
  • refining blister copper will be described as an example of electrolysis using the electrolytic device according to the embodiment of the present invention.
  • a blister copper plate having a purity of about 99 mass% is used as an anode plate
  • a copper plate having a purity of about 99.99 mass% or a stainless steel plate is used as a cathode plate
  • a plurality of anode plates and a plurality of cathode plates are alternately arranged.
  • the electrode plates are arranged in the electrolytic cell 1 at a predetermined distance from the bottom surface of the electrolytic cell 1 at intervals in the thickness direction.
  • an electrolytic solution obtained by adding additives such as nikawa and thiourea to a mixed aqueous solution of copper sulfate and sulfuric acid is supplied from a plurality of supply ports 21a, 21b, 21c ... 21x of the electrolytic solution supply unit 2. Then, the electrolytic solution is circulated by the recirculation mechanism.
  • a direct current is applied between the anode plate and the cathode plate using the power feeding mechanism, and the copper of the anode plate is eluted as ions in the electrolytic solution and electrodeposited on the cathode plate.
  • the electrolytic solution is supplied into the electrolytic cell 1 from above the first side wall 11 of the electrolytic cell 1 facing the side surfaces of the anode plate and the cathode plate, and the second side wall 1 of the electrolytic cell 1 facing the first side wall 11 is supplied.
  • a liquid flow is generated so that the electrolytic solution is discharged to the outside of the electrolytic cell 1 from below the side wall 12.
  • an increase in the concentration of metal ions such as copper ions in the lower part of the electrolytic cell 1 can be suppressed, and the metal ions can be more uniformly dispersed in the liquid, so that the current density is high or It is possible to more efficiently suppress the passivation phenomenon when electrolytic purification is performed using a material having a high impurity concentration for the anode plate.
  • the electrolyzer according to the second embodiment of the present invention has electrodes (not shown) arranged at intervals along the longitudinal direction of the electrolytic tank 1 containing the electrolytic solution.
  • the liquid supply pipes 2 having the liquid supply ports 21a, 21b ... 21x and the liquid supply pipes 2 extend along the first side wall 11 so as to accommodate the liquid supply pipes 2 inside, and a plurality of liquid supply ports 21a, 21b ...
  • a gutter 4 for storing the electrolytic solution supplied from 21x, overflowing the stored electrolytic solution and supplying it into the electrolytic tank 1, and a second side wall 12 facing the first side wall 11 extend along the second side wall 12.
  • a plurality of drainage ports 31a, 31b ... 31x arranged below the gutter 4 and spaced apart from each other are provided, and electrolysis in the electrolytic tank 1 is provided from the drainage ports 31a, 31b ... 31x.
  • a drainage pipe 3 for draining the liquid is provided.
  • a liquid supply pipe extending along the longitudinal direction X of the electrolytic cell 1 at the liquid level of the electrolytic cell contained in the electrolytic cell 1 or at a height close to the liquid level. 2 is arranged.
  • the liquid supply pipe 2 is connected to a liquid supply unit 20 arranged above the third side wall 13 of the electrolytic cell 1.
  • the liquid supply unit 20 includes a liquid supply main pipe (not shown) capable of supplying the electrolytic solution to other electrolytic cells other than the electrolytic cell 1 shown in FIGS. 2 and 3, and a liquid supply from the main supply pipe.
  • a branch pipe (not shown) for branching the electrolytic solution to the pipe 2 can be provided.
  • the liquid supply pipe 2 preferably supplies the electrolytic solution into the electrolytic cell 1 so that the supply flow rate of the electrolytic solution is 20 to 100 L / min. If the supply flow rate of the electrolytic solution is less than 20 L / min, the additive may be decomposed before being distributed in the electrolytic cell 1, and the smoothness of the electrodeposited metal may be impaired or passivation may occur.
  • the supply flow rate of the electrolytic solution is preferably high from the viewpoint of electrolytic efficiency, but if the supply flow rate of the electrolytic solution exceeds 100 L / min, the ridges in the electrolytic cell 1 may be rolled up and adhere to the surface of the cathode plate. ..
  • the electrolytic device by setting the supply flow rate to 20 to 100 L / min, the mixed state of the electrolytic solution supplied into the electrolytic cell 1 is further improved while suppressing the hoisting of the ridge. It is possible to carry out more efficient electrolytic purification.
  • the supply flow rate of the electrolytic solution is preferably 30 to 90 L / min, more preferably 30 to 70 L / min, and even more preferably 50 to 70 L / min.
  • a plurality of liquid supply ports 21a, 21b ... 21x are preferably provided at equal intervals along the longitudinal direction X at the upper portion of the liquid supply pipe 2.
  • the number of the plurality of liquid supply ports 21a, 21b ... 21x is not particularly limited.
  • the gutter portion 4 is arranged above the first side wall 11 of the electrolytic cell 1, accommodates the liquid supply pipe 2 inside, and extends along the longitudinal direction of the first side wall 11. There is.
  • the gutter portion 4 has a concave shape for storing the electrolytic solution supplied from the plurality of liquid supply ports 21a, 21b ... 21x of the liquid supply pipe 2.
  • the gutter portion 4 has a first wall portion 42 fixed on the first side wall 11 and extending along X in the longitudinal direction of the first side wall 11, and a first wall portion 42. It can be provided with a second wall portion 43 facing each other at regular intervals, a plurality of beam portions 44 supporting the first wall portion 42 and the second wall portion 43, and a bottom surface invisible from FIG. ..
  • the beam portion 44 is spaced apart from the first wall portion 42 and the second wall portion 43 so as to be able to support the first wall portion 42 and the second wall portion 43.
  • the number of beam portions 44 is not particularly limited as long as they are provided and a plurality of beams are arranged.
  • the distance between the first wall portion 42 and the second wall portion 43 is not particularly limited as long as it has a distance that does not collide with the electrode inserted into the electrolytic cell 1.
  • the gutter portion 4 can be formed of a material having corrosion resistance to an electrolytic solution, for example, stainless steel (SUS), vinyl chloride, fiber reinforced plastic (FRP), or the like.
  • a plurality of openings 41a, 41b, 41x are formed above the gutter portion 4.
  • the electrolytic solution is supplied from the plurality of liquid supply ports 21a, 21b ... 21x of the liquid supply pipe 2 and temporarily stored inside the gutter portion 4.
  • a part of the electrolytic solution stored inside the gutter portion 4 overflows from the openings 41a, 41b, 41x and flows into the electrolytic cell 1.
  • the electrolytic solution supplied from the liquid supply pipe 2 is temporarily stored inside the gutter portion 4 and then supplied into the electrolytic cell 1, resulting in a difference generated in the elongated liquid supply pipe 2. Since the pressure is made uniform in the gutter portion 4, the electrolytic solution can be supplied evenly over the entire electrolytic cell 1. Further, since the electrolytic solution is once stored in the gutter portion 4, the components of the electrolytic solution and the additive can be made uniform along the longitudinal direction of the electrolytic cell 1, so that the liquid is supplied into the electrolytic cell. It is possible to improve the mixed state of the electrolytic solution as a whole.
  • the electrolytic solution is supplied into the electrolytic cell 1 by overflow, the power of a pump or the like for extracting and discharging the electrolytic solution from the inside of the gutter portion 4 to the outside of the gutter portion 4 becomes unnecessary, and the device can be simplified. You can plan.
  • the electrolytic solution overflowing from the gutter portion 4 collides with the liquid level of the electrolytic solution and bubbles are generated. It may occur and affect electrolysis.
  • the electrolytic solution in the electrolytic cell 1 flows into the gutter portion 4 side, and the liquid supply is smooth. It may not proceed to.
  • the heights of the openings 41a, 41b, ... 41x of the gutter portion 4 are arranged at a height within 400 mm, more preferably within 200 mm, and further preferably within 50 mm from the liquid level of the electrolytic solution. It is preferable to be done.
  • the width of the gutter portion 4 along the depth direction of the electrolytic cell 1 can be appropriately changed according to the pipe diameter of the liquid supply pipe 2 and the device scale of the electrolytic cell 1.
  • the width of the gutter portion 4 along the depth direction is 50 to 100 mm, but in order to make the pressure bias of the electrolytic solution supplied to the gutter portion 4 more uniform.
  • the width of the gutter portion 4 along the depth direction of the gutter portion 4 may be made larger than 100 mm.
  • the electrolytic solution fixed on the first side wall 11 and supplied from the liquid supply unit 20 is supplied from the upstream side along the longitudinal direction of the electrolytic cell 1.
  • An auxiliary pipe 5 for supplying to the downstream side is provided.
  • the auxiliary pipe 5 is connected to the central portion in the longitudinal direction of the liquid supply pipe 2 via the supply portions 51 and 52 arranged in the central portion in the longitudinal direction of the electrolytic cell 1.
  • the electrolytic solution supplied from the liquid supply unit 20 flows into the liquid supply pipe 2 via the supply units 51 and 52 of the auxiliary pipe 5.
  • a large amount of the electrolytic solution supplied to the liquid supply pipe 2 flows out from the drainage port 31a side on the third side wall 13 side of the electrolytic cell 1 near the liquid supply unit 20, and the drainage liquid on the fourth side wall 14 side.
  • the electrolytic solution may not flow out sufficiently as it goes to the mouth 31x.
  • the electrolytic solution is also supplied from the longitudinal central portion of the liquid supply pipe 2 via the auxiliary pipe 5, so that the electrolytic solution is sufficiently supplied to the longitudinal central portion of the liquid supply pipe 2. Therefore, the electrolytic solution can be supplied more uniformly over the entire electrolytic cell 1.
  • the tip of the liquid supply pipe 2 provided with the liquid supply port 21x that minimizes the supply amount of the electrolytic solution is fixed on the first side wall 11 further below the auxiliary pipe 5.
  • An auxiliary pipe 6 extending in the longitudinal direction of the first side wall 11 and having a tip connected to the tip of the liquid supply pipe 2 is arranged.
  • a supply unit 61 is provided at the tip of the auxiliary pipe 6, and the electrolytic solution supplied from the liquid supply unit 20 via the supply unit 61 is supplied to the tip of the auxiliary pipe 6.
  • the electrolytic solution is also supplied from the distal end portion of the liquid supply pipe 2 in the longitudinal direction via the auxiliary pipe 6, so that the electrolytic solution can be supplied more uniformly over the entire electrolytic cell 1.
  • a drainage section 30 for discharging the electrolytic solution in the electrolytic cell 1 to the outside of the electrolytic cell 1 and a drainage box 32 connected to the drainage section 30 are provided above the fourth side wall 14 side of the electrolytic cell 1 and a drainage box 32 connected to the drainage section 30.
  • a plurality of drainage pipes 3a, 3b, and 3c are connected to the drainage box 32, respectively.
  • the drainage pipes 3a, 3b, and 3c are arranged below the liquid supply pipe 2, are fixed on the second side wall 12, extend along the second side wall 12, and are spaced from each other.
  • a plurality of drainage ports 31a to 31x arranged along the longitudinal direction of the electrolytic cell 1 are provided.
  • the drainage pipe 3a provided with the drainage ports 31a, 31b, 31c capable of draining the electrolytic solution in the electrolytic solution tank 1 on the upstream side of the electrolytic tank 1, that is, the side close to the liquid supply unit 20.
  • a drainage pipe 3b provided with drainage ports 31d, 31e, 31f capable of draining the electrolytic solution near the center of the electrolytic tank 1 and an electrolytic solution on the side close to the drainage box 32 of the electrolytic tank 1 can be drained.
  • Three drainage pipes 3c having drainage ports 31g and 31x are arranged vertically separated from each other.
  • the arrangement of the drainage pipes 3a, 3b, and 3c is not limited to the arrangement shown in FIG.
  • the drainage pipe 3a having the longest pipe length is arranged at a position closest to the bottom of the electrolytic cell 1, and the drainage pipe 3c having the shortest pipe length is arranged into three drainage pipes 3a and 3b.
  • the drainage pipes 3a, 3b, and 3c are each provided with drainage ports 31a to 31x at the tip portions on the opposite side to the one end side connected to the drainage box 32, respectively.
  • the drainage ports 31a to 31x are uniformly provided over the entire one drainage pipe.
  • the lengths of the electrolytic tanks 1 along the longitudinal direction can be shortened, so that the pressure loss can be reduced and the drainage ports 31a to 31x can be reduced. It becomes easier to drain the electrolytic solution in each region where the is arranged more efficiently. As a result, uneven drainage in the longitudinal direction of the electrolytic cell 1 is less likely to occur.
  • the drainage ports 31a, 31d, and 31g at the most advanced portions of the drainage pipes 3a, 3b, and 3c are located farthest from the drainage box 32, they flow through the drainage pipes 3a, 3b, and 3c. Due to the resistance and pressure loss of the electrolytic solution, the solution may not be sufficiently drained.
  • the tip portions of the drainage ports 31a to 31x of the drainage pipes 3a, 3b, and 3c, that is, the drainage port 31c and the drainage port 31d, and the drainage port 31f and the drainage port 31g are mutually connected. By arranging them so as to overlap each other, it is possible to configure the drainage pipes 3a, 3b, and 3c so that the drainage can be sufficiently performed even at the tips thereof. As a result, it is possible to prevent uneven drainage of the electrolytic cell 1 in the longitudinal direction.
  • the pipe diameters of the drainage pipes 3a, 3b and 3c are larger than the pipe diameters of the liquid supply pipe 2 and the auxiliary pipes 5 and 6.
  • the pipe diameters of the liquid supply pipe 2 and the auxiliary pipes 5 and 6 may be the same or different.
  • the pipe diameters of the drainage pipes 3a, 3b, and 3c should be 1.5 times or more, more preferably 2 times or more, still more preferably 4 times or more larger than the pipe diameters of the liquid supply pipes 2 and the auxiliary pipes 5 and 6. Can be done.
  • the drainage ports 31a to 31x are preferably arranged in a range of 100 mm upward and 300 mm downward, more preferably 100 mm upward, starting from the lower end of the electrode housed in the electrolytic cell 1. It is arranged in a range of 100 mm below.
  • the opening area of the drainage ports 31a, 31b ... 31x provided in the drainage pipes 3a, 3b, 3c is larger than the opening area of the liquid supply ports 21a, 21a, 21c ... 21x provided in the liquid supply pipe 2. It is preferably formed in.
  • each opening area of the drainage ports 31a to 31x is increased by 1 to 400 times, more typically 100 to 200 times, with respect to each opening area of the liquid supply ports 21a to 21x. be able to.
  • the electrolytic solution in the electrolytic cell 1 can be efficiently drained from the drainage ports 31a to 31x.
  • the shapes, hole diameters (slit diameters), and intervals of the liquid supply ports 21a to 21x and the liquid drainage ports 31a to 31x can be appropriately adjusted according to the size of the electrolytic cell 1.
  • a drainage unit 30 for draining the electrolytic solution to the outside of the electrolytic cell 1 is arranged on the fourth side wall 14 side of the electrolytic cell 1.
  • a drainage box 32 is connected to the drainage unit 30.
  • the drainage unit 30 is provided with a discharge port 300 for draining the electrolytic solution in the electrolytic cell 1.
  • a discharge pipe 301 connected to the discharge port 300 is provided below the discharge port 300 in order to discharge the electrolytic solution to the outside of the electrolytic cell 1.
  • the drainage box 32 includes a bottom surface 32a that is below the liquid level LS of the electrolytic solution. As shown in FIG. 5, outlets 3A, 3B, and 3C of the drainage pipes 3a, 3b, and 3c are connected to the bottom surface 32a, respectively. As shown in FIG. 6, the electrolytic solution discharged from the electrolytic cell 1 into the drainage pipes 3a, 3b, and 3c has a height of the liquid level LS of the electrolytic solution and the liquid level ls of the electrolytic solution in the drainage box 32. It is pumped by the difference H.
  • the drainage box 32 is arranged between the drainage unit 30 and the drainage pipes 3a, 3b, and 3c, and the height of the liquid level of the electrolytic solution LS and the electrolytic solution flowing into the drainage box 32.
  • the electrolytic solution is sent from below the electrolytic tank 1 to the outside of the electrolytic tank 1 without using the power of a pump or the like and suppressing the entrainment of the drainage deposits on the bottom of the electrolytic tank 1. Can be extracted.
  • the height of the upper end of the side wall 32b on the side of the drainage box 32 in contact with the electrolytic solution is arranged so as to be several mm to several tens of mm above the liquid level LS of the electrolytic solution in the electrolytic cell 1. ..
  • the drainage box 32 is provided with a notch 33 for sending foreign matter in the electrolytic solution in the electrolytic cell 1 to the drainage box 32 on the side wall 32b on the side in contact with the electrolytic cell housed in the electrolytic cell 1. Is preferable.
  • the cutout portion 33 has a shape in which the opening width AW of the electrolytic cell 1 decreases from the upper side to the lower side.
  • the cutout portion 33 may have various shapes such as a V-shape, a U-shape, and a trapezoidal shape, but the specific shape is not particularly limited.
  • the electrolytic solution containing foreign matter such as dust accumulated near the liquid level LS of the electrolytic cell in the electrolytic cell 1 can be overflowed from the notch 33 and discharged. , It is possible to suppress the retention of dust near the liquid level LS of the electrolytic solution in the electrolytic cell 1.
  • an adjusting plate 35 is arranged between the drainage box 32 and the drainage portion 30 so as to block the electrolytic solution flowing from the drainage box 32 to the drainage portion 30. Is placed.
  • the electrolytic solution collected in the draining box 32 via the draining pipe 3 (3a, 3b, 3c) overflows from the upper end of the adjusting plate 35 and drains the liquid portion 30. Flow to.
  • the adjusting plates 35 having different sizes, it is possible to change the height h of the adjusting plate 35 from the bottom surface 32a of the drainage box 32.
  • the height h of the adjusting plate 35 By changing the height h of the adjusting plate 35, it is possible to adjust the height difference H between the liquid level LS of the electrolytic solution in the electrolytic cell 1 and the liquid level ls of the electrolytic solution in the drainage box 32. ..
  • the head pressure difference due to the height difference H between the liquid level LS of the electrolytic solution and the liquid level ls of the electrolytic solution in the electrolytic cell 1 is adjusted, and the electrolytic cell 1 is supplied regardless of the amount of liquid supplied.
  • the height of the liquid level LS of the electrolytic solution inside can be kept constant.
  • the drainage box 32 is provided with a dividing wall 37 for dividing the bottom surface 32a to which the outlets 3A, 3B, and 3C of the drainage pipes 3a, 3b, and 3c are connected into a plurality of regions. Is preferable. Although it is possible to grasp the amount of the electrolytic solution discharged from each of the outlets 3A, 3B, and 3C without arranging the dividing wall 37, each of the divided walls 37 is arranged in the drainage box 32. The amount of electrolytic solution discharged from each of the outlets 3A, 3B, and 3C can be easily grasped visually.
  • the electrolytic apparatus is provided with a circulation mechanism of an electrolytic solution (not shown) shown in FIGS. 2 to 5.
  • the recirculation mechanism adds additives such as nikawa and thiourea to the electrolytic solution discharged from the drainage unit 30 of the electrolytic cell 1, adjusts necessary components and temperature, and supplies the adjusted electrolytic solution. It recirculates from the pipe 2 into the electrolytic cell 1.
  • the electrolyzer is provided with a power feeding mechanism (not shown).
  • the power feeding mechanism includes a power supply device and wiring for applying a direct current between electrodes including anode plates and cathode plates that are alternately arranged along the longitudinal direction in the electrolytic cell 1.
  • the electrolytic solution is supplied from the width (Y) direction of the electrolytic cell 1, that is, from the first side wall 11 side to the second side wall 12 side of the electrolytic cell 1.
  • the installation positions of the liquid supply ports 21a, 21b ... 23x of the liquid supply pipe 2 are relatively larger than those of the drainage ports 31a, 31b ... 31x of the drainage pipes 3a, 3b and 3c.
  • the so-called “horizontal insertion, top-in, bottom-out method” is adopted, which is configured to be upward.
  • the risk of winding up the palace is reduced. Therefore, even if the supply flow rate of the electrolytic solution is increased, the mixed state of the electrolytic solution can be improved while suppressing the hoisting of the palace, and the electrodeposition efficiency of the electrodeposited object can be improved as compared with the conventional case. Further, since additives such as Nikawa, which affect the surface texture of the electrodeposited material, can be uniformly distributed throughout the electrolytic cell, an electrodeposited material having uniform quality can be obtained in the entire electrolytic cell 1.
  • a metal such as copper can be electrodeposited on a plurality of cathode plates.
  • a blister copper plate having a purity of about 99 mass% is used as an anode plate
  • a copper plate having a purity of about 99.99 mass% or a stainless steel plate is used as a cathode plate
  • a plurality of anode plates and a plurality of cathode plates are alternately arranged in the plate thickness direction.
  • the lower end of the electrode plate is arranged in the electrolytic cell 1 so as to have a predetermined distance from the bottom surface of the electrolytic cell 1 and the side surface of the electrode plate does not come into contact with the trough portion 4.
  • Nikawa and thiourea are added to a mixed aqueous solution of copper sulfate and sulfuric acid from a plurality of liquid supply ports 21a, 21b ... 23x provided in the liquid supply pipe 2 connected to the liquid supply main pipe arranged in the liquid supply unit 20 of FIG.
  • An electrolytic solution to which an additive such as is added is supplied. Further, the electrolytic solution is supplied from the auxiliary pipe 5 and the auxiliary pipe 6 to the central portion and the tip portion in the longitudinal direction of the liquid supply pipe 2.
  • the electrolytic solution supplied by the liquid supply pipe 2 and the auxiliary pipes 5 and 6 is stored in the gutter portion 4. Then, the electrolytic solution stored in the gutter portion 4 overflows from the openings 41a, 41b ...
  • the electrolytic solution in the electrolytic cell 1 is drained from the plurality of drainage ports 31a, 31b ... 31x of the drainage pipes 3a, 3b, 3c connected to the drainage box 32 and the drainage unit 30, and the electrolyte is not discharged.
  • the electrolytic solution is circulated by the shown circulation mechanism.
  • a direct current is applied between the anode plate and the cathode plate using the power feeding mechanism, and the copper of the anode plate is eluted as ions in the electrolytic solution and electrodeposited on the cathode plate.
  • the electrolytic solution is supplied into the electrolytic cell 1 from above the gutter 4 on the first side wall 11 of the electrolytic cell 1, and the second side of the electrolytic cell 1 facing the first side wall 11 is supplied.
  • a liquid flow is generated by draining the electrolytic solution into the drainage pipes 3a, 3b, and 3c below the side wall 12.
  • the electrolytic solution drained into the drainage pipes 3a, 3b, and 3c is pumped up by the drainage box 32 by the head pressure and drained through the drainage section 30.
  • Foreign matter such as dust floating in the upper layer of the electrolytic cell in the electrolytic cell 1 is accommodated in the drainage box 32 by overflow from the notch 33 provided in the drainage box 32 and discharged to the outside of the electrolytic cell 1. ..
  • the electrolysis method according to the second embodiment from one end of the short direction Y of the electrolytic cell 1 to the other end side of the short direction Y, and from the upper side to the lower side in the longitudinal direction X of the electrolytic cell 1.
  • the mixed state of the electrolytic cell in the electrolytic cell 1 is changed. Can be better.
  • an increase in the concentration of metal ions such as copper ions in the lower part of the electrolytic cell 1 can be suppressed, and the metal ions can be more uniformly dispersed in the liquid, so that the current density is high or It is possible to more efficiently suppress the immobilization phenomenon when electrolytic purification is performed using a material having a high impurity concentration for the anode plate.
  • the positions of the liquid supply ports 21a, 21b ... 21x and the liquid drainage ports 31a, 31b ... 31x provided in the liquid supply pipe 2 and the liquid drainage pipes 3a, 3b, 3c, respectively, are the anodes immersed in the electrolytic cell 1. It can be adjusted in relation to the position where the plate and the cathode plate are arranged. For example, a plurality of liquid supply ports 21a, 21b ... 23x provided in the liquid supply pipe 2 and a plurality of liquid drainage ports 31a, 31b ... 31x provided in the liquid drainage pipes 3a, 3b, 3c, respectively.
  • the electrolytic solution can be supplied to the space between the anode plate and the cathode plate.
  • one liquid supply port 21a, 21b ... 23x and one drainage port 31a, 31b ... 31x are arranged.
  • a plurality of liquid supply ports 21a, 21b ... 23x and drainage ports 31a, 31b ... 31x are arranged in the space according to the size of the space between the anode plate and the cathode plate. You may do so.
  • the liquid supply ports 21a, 21b ... 23x and the drainage ports 31a, 31b ... 31x from the central side in the longitudinal direction to the drainage side of the electrolytic cell 1 in which the mixed state of the electrolytic solution, particularly the additive, tends to deteriorate.
  • the number may be larger than the number on the liquid supply side from the center side in the longitudinal direction of the electrolytic cell 1.
  • the opening areas of the liquid supply ports 21a, 21b ... 21x and the liquid drainage ports 31a, 31b ... 31x provided in the liquid supply pipe 2 and the liquid drainage pipes 3a, 3b, 3c, respectively, are basically X in the longitudinal direction. Although the examples showing the same size along the above, different opening areas may be provided in the longitudinal direction X upstream side and the downstream side of the electrolytic cell 1.
  • a plurality of pipes or a pipe in which one pipe is branched in a branch shape along the longitudinal direction can be used.
  • the drainage pipes 3a, 3b, and 3c can be configured by one pipe instead of a plurality of pipes. Further, it goes without saying that the liquid supply pipe 2 may be composed of a plurality of pipes.
  • the electrolyzer according to the embodiment of the present invention contains an electrolytic solution and electrolyzes electrodes arranged at intervals along the longitudinal direction.
  • An electrolytic tank 1 that is immersed in a liquid for electrolysis treatment, and a second side wall 12 of the electrolytic tank 1 that extends along a first side wall 11 extending in the longitudinal direction X of the electrolytic tank 1 and faces the first side wall 11.
  • the liquid supply pipe 2 provided with a plurality of liquid supply ports 21a, 21b ...
  • a drainage pipe 3 extending along the side wall 12 of 2 and having a plurality of drainage ports 31a, 31b ... 31x for draining the electrolytic solution, and an electrolytic solution provided at one end of the electrolytic tank 1 are provided outside the electrolytic tank.
  • the electrolytic cell 1 is located at a liquid level of the electrolytic cell housed in the electrolytic cell 1 or at a height close to the liquid level.
  • a liquid supply pipe 2 extending along the longitudinal direction X is arranged.
  • the liquid supply pipe 2 is connected to a liquid supply unit 20 arranged above the third side wall 13 of the electrolytic cell 1.
  • the liquid supply pipe 2 is preferably provided with a plurality of liquid supply ports 21a, 21b ... 21x along the longitudinal direction X at equal intervals.
  • the plurality of liquid supply ports 21a, 21b ... 21x have a height within 400 mm, more preferably a height within 200 mm, and further preferably within 50 mm from the electrolytic solution surface. It is preferably arranged at the height of.
  • the liquid supply pipe 2 preferably supplies the electrolytic solution into the electrolytic cell 1 so that the supply flow rate of the electrolytic solution is 20 to 100 L / min. If the supply flow rate of the electrolytic solution is less than 20 L / min, the additive may be decomposed before being distributed in the electrolytic cell 1, and the smoothness of the electrodeposited metal may be impaired or passivation may occur.
  • the supply flow rate of the electrolytic solution is preferably high from the viewpoint of electrolytic efficiency, but if the supply flow rate of the electrolytic solution exceeds 100 L / min, the ridges in the electrolytic cell 1 may be rolled up and adhere to the surface of the cathode plate. ..
  • the electrolytic solution is supplied from the upper side of the first side wall 11 and discharged from the lower side of the second side wall 12, and the supply flow rate is 20 to 100 L / L. Minutes.
  • the supply flow rate of the electrolytic solution is preferably 30 to 90 L / min, more preferably 30 to 70 L / min, and even more preferably 50 to 70 L / min.
  • a drainage pipe 3 extending along the longitudinal direction X is arranged on the lower side of the second side wall 12 of the electrolytic cell 1.
  • the drainage pipe 3 can be composed of a pipe or the like.
  • the drainage pipe 3 is provided with a plurality of drainage ports 31a, 31b ... 31x at predetermined intervals along the longitudinal direction X.
  • the plurality of drainage ports 31a, 31b ... 31x are preferably arranged at equal intervals so as to be relatively lower than the plurality of liquid supply ports 21a, 21b ... 21x.
  • the liquid supply pipe 2 and the liquid drainage pipe 3 are arranged so that the electrolytic solution flows from the upper side to the lower side from the first side wall 11 side to the second side wall 12 side, so that the electrolytic solution is released.
  • the drainage ports 31a, 31b ... 31x are preferably arranged in a range of 100 mm upward and 300 mm downward, starting from the lower end of the electrode housed in the electrolytic cell 1, for example, and more preferably upward. It is arranged in a range of 100 mm in and 100 mm below.
  • the opening areas of the drainage ports 31a, 31b, ... are larger than the opening areas of the liquid supply ports 21a, 21b, 21c ...
  • the opening areas of the drainage ports 31a, 31b, ... are more typically 1 to 400 times the opening areas of the liquid supply ports 21a, 21b, 21c ... Can be 100 to 200 times larger.
  • the electrolytic solution in the electrolytic cell 1 can be efficiently drained from the drainage ports 31a, 31b, ....
  • the pipe diameter of the drainage pipe 3 is formed larger than the pipe diameter of the liquid supply pipe 2.
  • the pipe diameter on the drainage pipe 3 side is utilized.
  • the influence of the pressure loss of the drainage pipe 3 can be further reduced.
  • the electrolytic solution sucked up in the liquid supply pipe 2 can be easily discharged to the outside of the electrolytic cell 1.
  • the pipe diameter of the drainage pipe 3 can be 1.5 times or more, more preferably 2 times or more, still more preferably 4 times or more larger than the pipe diameter of the liquid supply pipe 2.
  • the liquid supply ports 21a, 21b, 21c ... Have a circular shape or an elliptical shape, and are arranged at intervals d1 from each other.
  • the drainage ports 31a, 31b, ... Have an oval shape or a substantially rectangular shape having a slit diameter d2, and are arranged at intervals d3 from each other.
  • a drainage unit 30 for draining the electrolytic solution to the outside of the electrolytic cell 1 is arranged on the fourth side wall 14 of the electrolytic cell 1.
  • the drainage unit 30 is provided with a discharge port 300 for discharging the electrolytic solution in the electrolytic cell 1 above the drainage unit 30.
  • a discharge pipe 301 connected to the discharge port 300 is provided below the drain port 31a in order to discharge the electrolytic solution to the outside of the electrolytic cell 1.
  • the drainage box 32 is connected between the drainage unit 30 and the drainage pipe 3.
  • the drainage box 32 includes a bottom surface 32a that is below the liquid level LS of the electrolytic solution.
  • the outlet 3A of the drainage pipe 3 is connected to the bottom surface 32a.
  • the electrolytic solution discharged from the electrolytic cell 1 into the drainage pipe 3 is pumped up by the head difference due to the height difference H between the liquid level LS of the electrolytic solution and the liquid level ls of the electrolytic solution in the drainage box 32. ..
  • the drainage box 32 is arranged between the drainage unit 30 and the drainage pipe 3, so that the power of a pump or the like is not used and the electrolytic cell 1 is used. It is possible to withdraw the electrolytic solution from below the electrolytic cell 1 to the outside of the electrolytic cell 1 while suppressing the entrainment of the drainage deposits on the bottom of the electrolytic cell 1.
  • the height of the upper end of the side wall 32b on the side of the drainage box 32 in contact with the electrolytic solution is arranged so as to be several mm to several tens of mm above the liquid level LS of the electrolytic solution in the electrolytic cell 1. ..
  • the drainage box 32 is provided with a notch 33 for sending foreign matter in the electrolytic solution in the electrolytic cell 1 to the drainage box 32 on the side wall 32b on the side in contact with the electrolytic cell housed in the electrolytic cell 1. Is preferable.
  • the cutout portion 33 has a shape in which the opening width AW of the electrolytic cell 1 decreases from the upper side to the lower side.
  • the shape of the cutout portion 33 may be various shapes such as a U-shape and a trapezoidal shape in addition to the V-shape as shown in FIG. 10, but the specific shape is not particularly limited.
  • the electrolytic solution containing foreign matter such as dust accumulated near the liquid level LS of the electrolytic cell in the electrolytic cell 1 can be overflowed from the notch 33 and discharged. , It is possible to suppress the retention of dust near the liquid level LS of the electrolytic solution in the electrolytic cell 1.
  • an adjusting plate 35 arranged so as to block the electrolytic solution flowing from the drainage box 32 to the drainage section 30 is arranged between the drainage box 32 and the drainage section 30. ing.
  • the electrolytic solution collected in the draining box 32 via the draining pipe 3 overflows from the upper end of the adjusting plate 35 and flows to the draining portion 30.
  • the adjusting plates 35 having different sizes, it is possible to change the height h of the adjusting plate 35 from the bottom surface 32a of the drainage box 32.
  • the height h of the adjusting plate 35 By changing the height h of the adjusting plate 35, it is possible to adjust the height difference H between the liquid level LS of the electrolytic solution in the electrolytic cell 1 and the liquid level ls of the electrolytic solution in the drainage box 32. ..
  • the head pressure difference due to the height difference H between the liquid level LS of the electrolytic solution and the liquid level ls of the electrolytic solution in the electrolytic cell 1 is adjusted, and the electrolytic cell 1 is supplied regardless of the amount of liquid supplied.
  • the height of the liquid level LS of the electrolytic solution inside can be kept constant.
  • the electrolytic apparatus shown in FIGS. 7 (a) and 7 (b) is provided with a circulation mechanism of an electrolytic solution (not shown).
  • the recirculation mechanism adds additives such as nikawa and thiourea to the electrolytic solution discharged from the drainage unit 30 of the electrolytic cell 1, adjusts necessary components and temperature, and supplies the adjusted electrolytic solution. Circulation flows from the ports 21a, 21b, 21c ... 21x into the electrolytic cell 1.
  • the electrolyzer is provided with a power feeding mechanism (not shown).
  • the power feeding mechanism includes a power supply device and wiring for applying a direct current between electrodes including anode plates and cathode plates that are alternately arranged along the longitudinal direction in the electrolytic cell 1.
  • the configuration of the anode plate and the cathode plate is not particularly limited.
  • the anode plate serves as an anode for electrolytic refining or electrowinning, and is composed of a crude metal plate material.
  • the cathode plate serves as a cathode for electrolytic refining or electrowinning, and is composed of a plate-shaped metal having excellent conductivity.
  • the electrolytic solution is from the width (X) direction of the electrolytic cell 1, that is, from the first side wall 11 side to the second side wall 12 side of the electrolytic cell 1.
  • the installation positions of the liquid supply ports 21a, 21b ... 21x on the first side wall 11 side are relative to those of the drainage ports 31a, 31b ... 31x on the second side wall 12 side.
  • the so-called “horizontal insertion, top insertion, bottom removal method” is adopted, which is configured so as to be upward.
  • the risk of winding up the palace is reduced. Therefore, even if the supply flow rate of the electrolytic solution is increased, the mixed state of the electrolytic solution can be improved while suppressing the hoisting of the palace, and the electrodeposition efficiency of the electrodeposited object can be improved as compared with the conventional case. Further, since additives such as Nikawa, which affect the surface texture of the electrodeposited material, can be uniformly distributed throughout the electrolytic cell, an electrodeposited material having uniform quality can be obtained in the entire electrolytic cell 1.
  • a drainage box 32 is arranged between the drainage pipe 3 arranged below the electrolytic cell 1 and the drainage portion arranged above the electrolytic cell 1.
  • the electrolytic solution in the drainage pipe 3 arranged below the electrolytic cell 1 can be used in the electrolytic cell 1 and the drainage box 32 without the need for power such as a pump. Since it can be pumped up by the head pressure difference of the electrolytic solution and sent to the drainage section 30, the existing electrolytic cell 1 is used, and the liquid is supplied into the electrolytic cell while suppressing the winding up of the ridge. It is possible to improve the mixed state of the electrolytic solution.
  • a metal such as copper can be electrodeposited on a plurality of cathode plates.
  • refining blister copper will be described as an example of electrolysis using the electrolytic device according to the embodiment of the present invention.
  • a blister copper plate having a purity of about 99 mass% is used as an anode plate
  • a copper plate having a purity of about 99.99 mass% or a stainless steel plate is used as a cathode plate
  • a plurality of anode plates and a plurality of cathode plates are alternately arranged.
  • the electrode plates are arranged in the electrolytic cell 1 at a predetermined distance from the bottom surface of the electrolytic cell 1 at intervals in the thickness direction.
  • an electrolytic solution obtained by adding additives such as nikawa and thiourea to a mixed aqueous solution of copper sulfate and sulfuric acid is supplied from a plurality of liquid supply ports 21a, 21b ... 21x of the liquid supply pipe 2.
  • the electrolytic solution is circulated by the recirculation mechanism.
  • a direct current is applied between the anode plate and the cathode plate using the power feeding mechanism, and the copper of the anode plate is eluted as ions in the electrolytic solution and electrodeposited on the cathode plate.
  • the electrolytic solution is supplied into the electrolytic cell 1 from above the first side wall 11 of the electrolytic cell 1 facing the side surfaces of the anode plate and the cathode plate, and the second side wall 1 of the electrolytic cell 1 facing the first side wall 11 is supplied.
  • a liquid flow is generated by draining the electrolytic solution into the drainage pipe 3 below the side wall 12.
  • the electrolytic solution drained into the drainage pipe 3 is pumped up by the drainage box 32 and drained through the drainage section 30.
  • Foreign matter such as dust floating in the upper layer of the electrolytic cell in the electrolytic cell 1 is accommodated in the drainage box 32 by overflow from the notch 33 provided in the drainage box 32 and discharged to the outside of the electrolytic cell 1. ..
  • the length of the electrolytic cell 1 is from one end of the electrolytic cell 1 in the lateral direction Y to the other end side in the lateral direction Y and from the upper side to the lower side.
  • the electrolytic cell in the electrolytic cell 1 The mixed state can be improved.
  • an increase in the concentration of metal ions such as copper ions in the lower part of the electrolytic cell 1 can be suppressed, and the metal ions can be more uniformly dispersed in the liquid, so that the current density is high or It is possible to more efficiently suppress the passivation phenomenon when electrolytic purification is performed using a material having a high impurity concentration for the anode plate.
  • the positions of the liquid supply ports 21a, 21b ... 21x and the liquid drainage ports 31a, 31b ... 31x provided in the liquid supply pipe 2 and the liquid drainage pipe 3 are the anode plate and the cathode plate immersed in the electrolytic cell 1. Can be adjusted in relation to the position where is placed.
  • the plurality of liquid supply ports 21a, 21b ... 21x provided in the liquid supply pipe 2 and the plurality of drainage ports 31a, 31b ... 31x provided in the liquid drainage pipe 3 are provided with an anode plate and a cathode, respectively. It can be provided so as to face the gap provided between the plates and the electrolytic solution can be supplied to the space between the anode plate and the cathode plate.
  • the passivation phenomenon when electrolytic refining is performed using a material having a high current density or a high impurity concentration for the anode plate is more efficient. Can be suppressed.
  • one liquid supply port 21a, 21b ... 21x and one drainage port 31a, 31b ... 31x are arranged.
  • a plurality of liquid supply ports 21a, 21b ... 21x and drainage ports 31a, 31b ... 31x are arranged in the space according to the size of the space between the anode plate and the cathode plate. You may do so.
  • the liquid supply ports 21a, 21b ... 21x and the drainage ports 31a, 31b ... 31x from the central side in the longitudinal direction to the drainage side of the electrolytic cell 1 in which the mixed state of the electrolytic solution, particularly the additive, tends to deteriorate.
  • the number may be larger than the number on the liquid supply side from the center side in the longitudinal direction of the electrolytic cell 1.
  • the opening areas of the liquid supply ports 21a, 21b ... 21x and the liquid drainage ports 31a, 31b ... 31x provided in the liquid supply pipe 2 and the liquid drainage pipe 3, respectively, are basically along the longitudinal direction X, respectively. Although an example in which the sizes are the same is shown, different opening areas may be provided in the longitudinal direction X upstream side and the downstream side of the electrolytic cell 1.
  • each of the outlets of the drainage pipes 3 can be independently connected to the drainage box 32.
  • the electrolyzers according to the fourth embodiment of the present invention are spaced apart from each other along the longitudinal direction X of the electrolytic tank 1 containing the electrolytic solution.
  • This is an electrolyzer that immerses the electrodes arranged in the electrolyzer in an electrolytic solution and electrolyzes the electrolytic solution while circulating the electrolytic solution. It extends along the first side wall 11 of the electrolytic tank 1 extending in the longitudinal direction X, and is spaced from each other.
  • a drainage pipe that is arranged below the liquid pipe 2 extends along the second side wall 12, and drains the electrolytic solution from a plurality of drainage ports 31a, 31b ... 31x arranged at intervals from each other.
  • 3 and a drainage section 30 for draining the electrolytic solution drained by the drainage pipe 3 to the outside of the electrolytic tank 1 are provided, and the liquid supply pipe 2 electrolyzes at least the upstream side and the downstream side of the electrolytic tank. It is provided with two or more piping portions 21, 21, 23 (see FIG. 13) capable of supplying liquid independently.
  • the liquid supply pipe 2 is preferably provided with a plurality of liquid supply ports 21a, 21b ... 21x along the longitudinal direction X at equal intervals.
  • the plurality of liquid supply ports 21a, 21b ... 21x have a height within 400 mm, more preferably a height within 200 mm, and further preferably within 50 mm from the electrolytic solution surface. It is preferably arranged at the height of.
  • the liquid supply pipe 2 preferably supplies the electrolytic solution into the electrolytic cell 1 so that the supply flow rate of the electrolytic solution is 20 to 100 L / min. If the supply flow rate of the electrolytic solution is less than 20 L / min, the additive may be decomposed before being distributed in the electrolytic cell 1, and the smoothness of the electrodeposited metal may be impaired or passivation may occur.
  • the supply flow rate of the electrolytic solution is preferably high from the viewpoint of electrolytic efficiency, but if the supply flow rate of the electrolytic solution exceeds 100 L / min, the ridges in the electrolytic cell 1 may be rolled up and adhere to the surface of the cathode plate. ..
  • the electrolytic solution is supplied from the upper side of the first side wall 11 and discharged from the lower side of the second side wall 12, and the supply flow rate is 20 to 100 L / L.
  • the supply flow rate of the electrolytic solution is preferably 30 to 90 L / min, more preferably 30 to 70 L / min, and even more preferably 50 to 70 L / min.
  • the liquid supply pipe 2 may be composed of one pipe having liquid supply ports 21a, 21b ... 21x arranged at equal intervals throughout the longitudinal direction. It is possible. However, when the length of the liquid supply pipe 2 becomes long, a large amount of electrolytic solution is supplied from the upstream side of the liquid supply pipe 2, and the tip portion on the downstream side (near the liquid supply port 21x in FIG. 11B) is sufficient. The electrolyte may not be supplied to the machine.
  • FIG. 12 shows an example of the simulation result of the concentration distribution of the additive such as Nikawa added to the electrolytic solution when the liquid supply pipe 2 is composed of one along the longitudinal direction of the electrolytic cell 1.
  • the concentration of the additive decreases from the upstream side to the downstream side in the longitudinal direction of the electrolytic cell 1, and the additive is almost added to the end of the electrolytic cell 1 on the fourth side wall 14 side. There will be areas where the agent is not supplied.
  • the liquid supply pipe 2 can independently supply the electrolytic solution to at least the upstream side and the downstream side of the electrolytic cell 1 2 It is provided with two or more piping portions 21, 22, and 23.
  • the "upstream side” is a position that is relatively upstream when the fourth side wall 14 side for draining the electrolytic solution is the "downstream side", and is typically the third side wall 13. Means the side.
  • a plurality of piping portions 21, 22 and 23 are arranged along the longitudinal direction, and the electrolytic solution is drained independently from the plurality of piping portions 21, 22 and 23, respectively.
  • the liquid supply pipe 2 as shown in (b) is composed of one, the mixed state of the electrolytic solution can be improved, and the concentration uniformity of the additive added to the electrolytic solution in the entire tank is further improved. It becomes possible to make it.
  • the piping portion 21 has a root portion (not shown) extending downward from the upper side of the third side wall 13, and the height or vicinity of the liquid level of the electrolytic solution contained in the electrolytic cell 1 from the root portion.
  • a tip portion 221 extending at a height along the longitudinal direction X of the electrolytic cell 1 (left-right direction on the paper surface in FIG. 13) is provided.
  • liquid supply ports 21a, 21b ... 21x are arranged along the longitudinal direction X.
  • the piping portion 22 extends from the upper side to the lower side of the third side wall 13, and further extends to the downstream side of the electrolytic cell 1 along the longitudinal direction X of the electrolytic cell 1, that is, to the vicinity of the fourth side wall, the root portion 222, the electrolytic cell.
  • An intermediate portion 223 extending from the lower side to the upper portion of 1 and a tip portion 221 extending along the longitudinal direction X from the intermediate portion 223 at a height close to or near the liquid level of the electrolytic solution are provided.
  • Liquid supply ports 22a, 22b ... 22x are arranged at the tip portion 221 along the longitudinal direction X.
  • the piping portion 23 extends along the longitudinal direction X between the piping portion 21 and the piping portion 22.
  • the piping portion 23 is arranged at a height such that the root portion 232 extending from the upper side to the lower side of the third side wall 13 and further extending along the longitudinal direction X of the electrolytic cell 1 and the liquid level of the electrolytic solution or near the liquid level. It is provided with a tip portion 231 and an intermediate portion 233 connecting between the root portion 232 and the tip portion 231.
  • Liquid supply ports 23a, 23b ... 23x are arranged at the tip portion 231 along the longitudinal direction X.
  • the piping portions 21, 22 and 23 have regions 200 and 201 whose ends are partially overlapped vertically in the electrolytic cell 1.
  • each of them is more than the case where one liquid supply pipe 2 as shown in FIG. 7A is formed.
  • the amount of the electrolytic solution supplied in the region can be made more uniform.
  • the state of supplying the electrolytic solution becomes uneven even in the piping portions 21, 22, and 23.
  • the tip portion of each of the piping portions 21, 22 and 23 tends to have a smaller supply amount of the electrolytic solution than the root portion.
  • the ends of the piping portions 21, 22, and 23 are arranged so as to partially overlap each other in the electrolytic cell 1.
  • the problem of insufficient supply of the electrolytic solution at the ends of the piping portions 21, 22 and 23 can be compensated by the supply by the plurality of piping portions 21, 22 and 23, and a predetermined liquid supply amount can be achieved.
  • the size of the areas 200 and 201 varies depending on the size of the electrolytic cell 1 and how many pipes 21, 22 and 23 are divided, but the liquid supply port provided in one pipe 21, 22 and 23. 21a, 21b ... 23x
  • the first side wall 11 has a length of 1/4 or more, further 1/3, or even 1/2 or more of the length of each of the piping portions 21, 22, and 23 where the electrolytic solution is discharged.
  • the piping portions 21, 22, and 23 By superimposing the piping portions 21, 22, and 23 on the upper and lower sides of the above and forming the regions 200 and 201, the liquid supply is more uniform over the entire electrolytic cell 1 as compared with the case where the liquid supply pipe 2 is one. Can be done.
  • the lengths of the regions 200 and 201 in the longitudinal direction X may be different from each other.
  • a drainage pipe 3 extending along the longitudinal direction X is arranged on the lower side of the second side wall 12 of the electrolytic cell 1.
  • the drainage pipe 3 can be composed of a pipe or the like.
  • the drainage pipe 3 is provided with a plurality of drainage ports 31a, 31b ... 31x at predetermined intervals along the longitudinal direction X.
  • the plurality of drainage ports 31a, 31b ... 31x are preferably arranged at equal intervals so as to be relatively lower than the plurality of liquid supply ports 21a, 21b ... 23x.
  • the liquid supply pipe 2 and the liquid drainage pipe 3 are arranged so that the electrolytic solution flows from the upper side to the lower side from the first side wall 11 side to the second side wall 12 side, so that the electrolytic solution is released. Since it flows from the upper side to the lower side, it is necessary to improve the mixed state of the electrolytic solution, particularly the mixed state of the metal ions and additives in the electrolytic cell, while suppressing the hoisting of the deposits on the bottom of the electrolytic cell 1. Can be done.
  • the drainage ports 31a, 31b ... 31x are preferably arranged in a range of 100 mm upward and 300 mm downward, starting from the lower end of the electrode housed in the electrolytic cell 1, for example, more preferably. It is arranged in a range of 100 mm above and 100 mm below.
  • the opening areas of the drainage ports 31a, 31b, ... are larger than the opening areas of the liquid supply ports 21a, 21b, 21c ...
  • the opening areas of the drainage ports 31a, 31b, ... are more typically 1 to 400 times the opening areas of the liquid supply ports 21a, 21b, 21c ... Can be 100 to 200 times larger.
  • the electrolytic solution in the electrolytic cell 1 can be efficiently drained from the drainage ports 31a, 31b, ....
  • the pipe diameter of the drainage pipe 3 is formed larger than the pipe diameter of the liquid supply pipe 2.
  • the pipe diameter of the drainage pipe 3 can be 1.5 times or more, more preferably 2 times or more, still more preferably 4 times or more larger than the pipe diameter of the liquid supply pipe 2.
  • the liquid supply ports 21a, 21b, 21c ... Have a circular shape or an elliptical shape, and are arranged at intervals d1 from each other.
  • the drainage ports 31a, 31b, ... Have an oval shape or a substantially rectangular shape having a slit diameter d2, and are arranged at intervals d3 from each other.
  • a drainage unit 30 for draining the electrolytic solution to the outside of the electrolytic cell 1 is arranged on the fourth side wall 14 of the electrolytic cell 1.
  • the drainage unit 30 is provided with a discharge port 300 for discharging the electrolytic solution in the electrolytic cell 1 above the drainage unit 30.
  • a discharge pipe 301 connected to the discharge port 300 is provided below the drain port 31a in order to discharge the electrolytic solution to the outside of the electrolytic cell 1.
  • the drainage box 32 is connected between the drainage unit 30 and the drainage pipe 3.
  • the drainage box 32 includes a bottom surface 32a that is below the liquid level LS of the electrolytic solution.
  • the outlet 3A of the drainage pipe 3 is connected to the bottom surface 32a.
  • the electrolytic solution discharged from the electrolytic cell 1 into the drainage pipe 3 is pumped up by the head pressure difference due to the height difference H between the liquid level LS of the electrolytic solution and the liquid level ls of the electrolytic solution in the drainage box 32. ..
  • the drainage box 32 By arranging the drainage box 32 between the drainage portion 30 and the drainage pipe 3, the power of a pump or the like is not used, and the entrainment of the deposits on the bottom of the electrolytic cell 1 is suppressed. , The electrolytic solution can be drawn out of the electrolytic cell 1 from below the electrolytic cell 1.
  • the height of the upper end of the side wall 32b on the side of the drainage box 32 in contact with the electrolytic solution is arranged so as to be several mm to several tens of mm above the liquid level LS of the electrolytic solution in the electrolytic cell 1. ..
  • the drainage box 32 is provided with a notch 33 for sending foreign matter in the electrolytic solution in the electrolytic cell 1 to the drainage box 32 on the side wall 32b on the side in contact with the electrolytic cell housed in the electrolytic cell 1. Is preferable.
  • the cutout portion 33 has a shape in which the opening width AW of the electrolytic cell 1 decreases from the upper side to the lower side.
  • the shape of the cutout portion 33 may be various shapes such as a U-shape and a trapezoidal shape in addition to the V-shape as shown in FIG. 4, but the specific shape is not particularly limited.
  • the electrolytic solution containing foreign matter such as dust accumulated in the vicinity of the electrolytic cell surface LS of the electrolytic cell 1 can be overflowed from the notch 33 and discharged. It is possible to suppress the retention of dust near the liquid level LS of the electrolytic solution in the tank 1.
  • an adjusting plate 35 is arranged between the drainage box 32 and the drainage portion 30 so as to block the electrolytic solution flowing from the drainage box 32 to the drainage portion 30. Is placed. By arranging the adjusting plate 35, the electrolytic solution collected in the draining box 32 via the draining pipe 3 overflows from the upper end of the adjusting plate 35 and flows to the draining portion 30.
  • the adjusting plates 35 having different sizes, it is possible to change the height h of the adjusting plate 35 from the bottom surface 32a of the drainage box 32.
  • the height h of the adjusting plate 35 By changing the height h of the adjusting plate 35, it is possible to adjust the height difference H between the liquid level LS of the electrolytic solution in the electrolytic cell 1 and the liquid level ls of the electrolytic solution in the drainage box 32. ..
  • the head pressure difference due to the height difference H between the liquid level LS of the electrolytic solution and the liquid level ls of the electrolytic solution in the electrolytic cell 1 is adjusted, and the electrolytic cell 1 is supplied regardless of the amount of liquid supplied.
  • the height of the liquid level LS of the electrolytic solution inside can be kept constant.
  • the electrolytic apparatus shown in FIGS. 11A and 11B is provided with a circulation mechanism of an electrolytic solution (not shown).
  • the recirculation mechanism adds additives such as nikawa and thiourea to the electrolytic solution discharged from the drainage unit 30 of the electrolytic cell 1, adjusts necessary components and temperature, and supplies the adjusted electrolytic solution. Circulation flows from the ports 21a, 21b, 21c ... 21x into the electrolytic cell 1.
  • the electrolyzer is provided with a power feeding mechanism (not shown).
  • the power feeding mechanism includes a power supply device and wiring for applying a direct current between electrodes including anode plates and cathode plates that are alternately arranged along the longitudinal direction in the electrolytic cell 1.
  • the electrolytic solution is supplied from the width (X) direction of the electrolytic cell 1, that is, from the first side wall 11 side to the second side wall 12 side of the electrolytic cell 1.
  • the installation positions of the liquid supply ports 21a, 21b ... 23x on the first side wall 11 side are relatively higher than the drainage ports 31a, 31b ... 31x on the second side wall 12 side.
  • the so-called "horizontal insertion, top insertion, bottom removal method” is adopted.
  • the risk of winding up the palace is reduced. Therefore, even if the supply flow rate of the electrolytic solution is increased, the mixed state of the electrolytic solution can be improved while suppressing the hoisting of the palace, and the electrodeposition efficiency of the electrodeposited object can be improved as compared with the conventional case. Further, since additives such as Nikawa, which affect the surface texture of the electrodeposited material, can be uniformly distributed throughout the electrolytic cell, an electrodeposited material having uniform quality can be obtained in the entire electrolytic cell 1.
  • the liquid supply pipe 2 is divided into a plurality of pipe parts 21, 22 and 23, and the section where the liquid can be supplied by the respective pipe parts 21, 22 and 23 is shorter than the case where the liquid supply pipe 2 is configured by one. Therefore, the electrolytic solution can be supplied more uniformly over the entire longitudinal direction of the electrolytic cell 1. In particular, since the additive added to the electrolytic solution can be supplied to the entire longitudinal direction of the electrolytic cell 1, a higher quality electrodeposited product with less surface roughness can be obtained.
  • the ends of the piping portions 21, 22, and 23 are arranged so as to partially overlap each other in the electrolytic cell 1, so that the portion of the tip portion of the piping where the amount of liquid supplied is small can be divided into a plurality of piping portions 21. , 22 and 23 can be complemented, and the liquid can be supplied almost uniformly over the entire tank.
  • a metal such as copper can be electrodeposited on a plurality of cathode plates.
  • refining blister copper will be described as an example of electrolysis using the electrolytic device according to the embodiment of the present invention.
  • a blister copper plate having a purity of about 99 mass% is used as an anode plate
  • a copper plate having a purity of about 99.99 mass% or a stainless steel plate is used as a cathode plate
  • a plurality of anode plates and a plurality of cathode plates are alternately arranged.
  • the electrode plates are arranged in the electrolytic cell 1 at a predetermined distance from the bottom surface of the electrolytic cell 1 at intervals in the thickness direction.
  • a piping portion 21 for supplying the electrolytic solution to the upstream side in the longitudinal direction of the electrolytic cell 1 and a piping portion for supplying the electrolytic solution to the downstream side in the longitudinal direction are provided on the first side wall 11 of the electrolytic cell 1.
  • a liquid supply pipe 2 including a pipe portion 23 for supplying the electrolytic solution is arranged in the intermediate portion, and copper sulfate and copper sulfate are provided from a plurality of liquid supply ports 21a, 21b ... 23x provided in the respective piping portions 21, 22, 23.
  • An electrolytic solution prepared by adding additives such as Nikawa and thiourea to a mixed aqueous solution of sulfuric acid is supplied, and the electrolytic solution is circulated by a circulation mechanism.
  • a direct current is applied between the anode plate and the cathode plate using the power feeding mechanism, and the copper of the anode plate is eluted as ions in the electrolytic solution and electrodeposited on the cathode plate.
  • the electrolytic solution is supplied into the electrolytic cell 1 from above the first side wall 11 of the electrolytic cell 1 facing the side surfaces of the anode plate and the cathode plate, and the second side wall 1 of the electrolytic cell 1 facing the first side wall 11 is supplied.
  • a liquid flow is generated by draining the electrolytic solution into the drainage pipe 3 below the side wall 12.
  • the electrolytic solution drained into the drainage pipe 3 is pumped up by the drainage box 32 and drained through the drainage section 30.
  • Foreign matter such as dust floating in the upper layer of the electrolytic cell in the electrolytic cell 1 is accommodated in the drainage box 32 by overflow from the notch 33 provided in the drainage box 32 and discharged to the outside of the electrolytic cell 1. ..
  • the length of the electrolytic cell 1 is from one end of the electrolytic cell 1 in the lateral direction Y to the other end of the lateral direction Y and from the upper side to the lower side.
  • the electrolysis method according to the fourth embodiment of the present invention it is possible to suppress an increase in the concentration of metal ions such as copper ions in the lower part of the electrolytic cell 1 and disperse the metal ions more uniformly in the liquid, which is high. It is possible to more efficiently suppress the immobilization phenomenon when electrolytic purification is performed using a material having a high current density or an impurity concentration for the anode plate.
  • the positions of the liquid supply ports 21a, 21b ... 23x and the liquid drainage ports 31a, 31b ... 31x provided in the liquid supply pipe 2 and the liquid drainage pipe 3 are the anode plate and the cathode plate immersed in the electrolytic cell 1. Can be adjusted in relation to the position where is placed.
  • a plurality of liquid supply ports 21a, 21b ... 23x provided in the liquid supply pipe 2 and a plurality of drainage ports 31a, 31b ... 31x provided in the liquid drainage pipe 3 are provided with an anode plate and a cathode, respectively.
  • the electrolytic solution can be supplied to the space between the anode plate and the cathode plate.
  • one liquid supply port 21a, 21b ... 23x and one drainage port 31a, 31b ... 31x are arranged.
  • a plurality of liquid supply ports 21a, 21b ... 23x and drainage ports 31a, 31b ... 31x are arranged in the space according to the size of the space between the anode plate and the cathode plate. You may do so.
  • the liquid supply ports 21a, 21b ... 23x and the drainage ports 31a, 31b ... 31x from the central side in the longitudinal direction to the drainage side of the electrolytic cell 1 in which the mixed state of the electrolytic solution, particularly the additive, tends to deteriorate.
  • the number may be larger than the number on the liquid supply side from the center side in the longitudinal direction of the electrolytic cell 1.
  • the opening areas of the liquid supply ports 21a, 21b ... 23x and the liquid drainage ports 31a, 31b ... 31x provided in the liquid supply pipe 2 and the liquid drainage pipe 3, respectively, are basically along the longitudinal direction X, respectively. Although an example in which the sizes are the same is shown, different opening areas may be provided on the upstream side and the downstream side in the longitudinal direction X of the electrolytic cell 1.
  • each of the outlets of the drainage pipes 3 can be independently connected to the drainage box 32.
  • the electrolyzer according to the fifth embodiment of the present invention has electrodes arranged at intervals along the longitudinal direction X of the electrolysis tank 1 containing the electrolytic solution.
  • a plurality of electrolyzers that are immersed in an electrolytic solution and electrolyze while circulating the electrolytic solution, which extend along the first side wall 11 of the electrolytic tank 1 extending in the longitudinal direction X and are arranged at intervals from each other. From the liquid supply pipes 2 and the liquid supply pipes 2 that supply the electrolytic solution from the liquid supply ports 21a, 21b ... 21x to the second side wall 12 side of the electrolytic tank 1 facing the first side wall 11.
  • a drainage section 30 for draining the electrolytic solution drained by the liquid pipe 3 to the outside of the electrolytic tank 1 is provided, and the drainage pipe 3 has at least two or more pipes 3a, 3b, and 3c along the longitudinal direction. Be prepared.
  • the liquid supply pipe 2 is preferably provided with a plurality of liquid supply ports 21a, 21b ... 21x along the longitudinal direction X at equal intervals.
  • the plurality of liquid supply ports 21a, 21b ... 21x have a height within 400 mm, more preferably a height within 200 mm, and further preferably within 200 mm from the liquid level of the electrolytic solution. It is preferably arranged at a height of 50 mm or less.
  • the liquid supply pipe 2 preferably supplies the electrolytic solution into the electrolytic cell 1 so that the supply flow rate of the electrolytic solution is 20 to 100 L / min. If the supply flow rate of the electrolytic solution is less than 20 L / min, the additive may be decomposed before being distributed in the electrolytic cell 1, and the smoothness of the electrodeposited metal may be impaired or passivation may occur.
  • the supply flow rate of the electrolytic solution is preferably high from the viewpoint of electrolytic efficiency, but if the supply flow rate of the electrolytic solution exceeds 100 L / min, the ridges in the electrolytic cell 1 may be rolled up and adhere to the surface of the cathode plate. ..
  • the electrolytic device by setting the supply flow rate to 20 to 100 L / min, the mixed state of the electrolytic solution supplied into the electrolytic cell 1 is further improved while suppressing the hoisting of the ridge. It is possible to carry out more efficient electrolytic purification.
  • the supply flow rate of the electrolytic solution is preferably 30 to 90 L / min, more preferably 30 to 70 L / min, and even more preferably 50 to 70 L / min.
  • a drainage section 30 for discharging the electrolytic solution in the electrolytic cell 1 to the outside of the electrolytic cell 1 and a drainage box 32 connected to the drainage section 30 are provided above the fourth side wall 14 side of the electrolytic cell 1.
  • a plurality of drainage pipes 3a, 3b, and 3c are connected to the drainage box 32, respectively.
  • the drainage pipes 3a, 3b, and 3c are arranged below the liquid supply pipe 2, extend along the second side wall 12, and are spaced apart from each other in the longitudinal direction of the electrolytic cell 1.
  • a plurality of drainage ports 31a, 31b ... 31f, 31g, 31h ... 31l, 31m, 31o ... 31x arranged along the line are provided.
  • An example is described in which three pipes of the drainage pipe 3c provided with ⁇ 31x are arranged vertically apart from each other, but it is needless to say that the arrangement is not limited to this.
  • the drainage pipe 3a having the longest pipe length is arranged at a position closest to the bottom of the electrolytic cell 1, and the drainage pipe 3c having the shortest pipe length is arranged into three drainage pipes 3a and 3b.
  • the drainage pipes 3a, 3b, and 3c are each provided with drainage ports 31a to 31x at the tip portions on the opposite side to the one end side connected to the drainage box 32, respectively.
  • the drainage ports 31a to 31x are provided only at the tips of the drainage pipes 3a, 3b, and 3c as shown in FIG. 15, so that the drainage ports are uniformly provided over the entire one drainage pipe. Since the length of the electrolytic tank 1 in the region where the drainage ports 31a to 31x are formed can be shortened in the longitudinal direction, the pressure loss can be reduced and the drainage ports 31a to 31x are arranged. It becomes easier to drain the electrolytic solution in each region more efficiently. As a result, uneven drainage in the longitudinal direction of the electrolytic cell 1 is less likely to occur.
  • the drainage ports 31a, 31g, 31m and the like at the most tip portions of the drainage pipes 3a, 3b and 3c are located farthest from the drainage box 32, they flow in the drainage pipes 3a, 3b and 3c. Due to the resistance of the electrolytic solution, pressure loss, etc., the drainage box 32 may not be sufficiently drained. As shown in FIG. 15, the ends of the drainage ports 31a to 31x of the drainage pipes 3a, 3b, and 3c, that is, the drainage port 31f and the drainage port 31g, and the drainage port 31l and the drainage port 31m are mutually connected.
  • the drainage pipes 3a, 3b, and 3c By arranging the drainage pipes 3a, 3b, and 3c so as to overlap each other, the drainage can be sufficiently performed even at the tip portions of the drainage pipes 3a, 3b, and 3c. As a result, uneven drainage in the longitudinal direction of the electrolytic cell 1 can be prevented from occurring.
  • the pipe diameters of the drainage pipes 3a, 3b, and 3c are configured to be larger than the pipe diameter of the liquid supply pipe 2.
  • the electrolytic solution is discharged from the drainage box 32 to the outside of the electrolytic solution tank 1 by utilizing the head pressure difference of the electrolytic solution.
  • the influence of the pressure loss of the drainage pipes 3a, 3b, and 3c can be made smaller. As a result, the electrolytic solution sucked up in the liquid supply pipe 2 can be easily discharged to the outside of the electrolytic cell 1.
  • the pipe diameter of the drainage pipes 3a, 3b, and 3c can be 1.5 times or more, more preferably 2 times or more, still more preferably 4 times or more larger than the pipe diameter of the liquid supply pipe 2.
  • the drainage ports 31a to 31x are preferably arranged in a range of 100 mm upward and 300 mm downward, more preferably 100 mm upward, starting from the lower end of the electrode housed in the electrolytic cell 1. It is arranged in a range of 100 mm below.
  • the drainage ports 31a, 31b ... 31x provided in the liquid drainage pipes 3a, 3b, 3c are larger than the opening areas of the liquid supply ports 21a, 21a, 21c ... 21x provided in the liquid supply pipe 2. It is preferable that the opening area is large. By increasing the opening area of the drainage ports 31a, 31b ... 31x, the influence of pressure loss when the electrolytic solution in the drainage pipes 3a, 3b, 3c is discharged to the outside of the electrolytic cell 1 is further reduced. Can be done.
  • each opening area of the drainage ports 31a to 31x is increased by 1 to 400 times, more typically 100 to 200 times, with respect to each opening area of the liquid supply ports 21a to 21x. be able to. As a result, the electrolytic solution in the electrolytic cell 1 can be efficiently drained from the drainage ports 31a to 31x.
  • the shapes, hole diameters (slit diameters), and intervals of the liquid supply ports 21a to 21x and the liquid drainage ports 31a to 31x can be appropriately adjusted according to the size of the electrolytic cell 1.
  • the liquid supply ports 21a, 21b, 21 ... 21x have a circular shape, an elliptical shape, or a rectangular shape, and are arranged at a distance d1 from each other.
  • the drainage ports 31a, 31b ... 31x have an oval shape or a substantially rectangular shape having a slit diameter d2, and are arranged at intervals d3 from each other.
  • the electrolytic cell spacing d1 is 50 mm and the hole diameter is 5 ⁇ , which is a circular or elliptical liquid supply port 21a, 21b, 21 ... 21x is formed.
  • the drainage ports 31a, 31b, ... With a width of 10 mm and a slit diameter (d2) of 400 mm, which are oval or substantially rectangular, have an interval d3 of 200 mm. And each is arranged.
  • a drainage unit 30 for draining the electrolytic solution to the outside of the electrolytic cell 1 is arranged on the fourth side wall 14 side of the electrolytic cell 1.
  • a drainage box 32 is connected to the drainage unit 30.
  • the drainage unit 30 is provided with a discharge port 300 for discharging the electrolytic solution in the electrolytic cell 1.
  • a discharge pipe 301 connected to the discharge port 300 is provided below the discharge port 300 in order to discharge the electrolytic solution to the outside of the electrolytic cell 1.
  • the drainage box 32 includes a bottom surface 32a that is below the liquid level LS of the electrolytic solution.
  • outlets 3A, 3B, and 3C of the drainage pipes 3a, 3b, and 3c are connected to the bottom surface 32a, respectively.
  • the electrolytic solution discharged from the electrolytic cell 1 into the drainage pipes 3a, 3b, and 3c has a head pressure difference due to the height difference H between the liquid level LS of the electrolytic solution and the liquid level ls of the electrolytic solution in the drainage box 32. Is pumped up by.
  • the drainage box 32 By arranging the drainage box 32 between the drainage portion 30 and the drainage pipes 3a, 3b, and 3c, the power of a pump or the like is not used, and the ridges deposited on the bottom of the electrolytic cell 1 are involved.
  • the electrolytic solution can be drawn out of the electrolytic cell 1 from below the electrolytic cell 1 while suppressing the above.
  • the height of the upper end of the side wall 32b on the side of the drainage box 32 in contact with the electrolytic solution is arranged so as to be several mm to several tens of mm above the liquid level LS of the electrolytic solution in the electrolytic cell 1. ..
  • the drainage box 32 is provided with a notch 33 for sending foreign matter in the electrolytic solution in the electrolytic cell 1 to the drainage box 32 on the side wall 32b on the side in contact with the electrolytic cell housed in the electrolytic cell 1. Is preferable.
  • the cutout portion 33 has a shape in which the opening width AW of the electrolytic cell 1 decreases from the upper side to the lower side.
  • the cutout portion 33 may have various shapes such as a V-shape, a U-shape, and a trapezoidal shape, but the specific shape is not particularly limited.
  • the electrolytic solution containing foreign matter such as dust accumulated near the liquid level LS of the electrolytic cell in the electrolytic cell 1 can be overflowed from the notch 33 and discharged. , It is possible to suppress the retention of dust near the liquid level LS of the electrolytic solution in the electrolytic cell 1.
  • an adjusting plate 35 arranged so as to block the electrolytic solution flowing from the drainage box 32 to the drainage section 30 is arranged between the drainage box 32 and the drainage section 30. ing.
  • the electrolytic solution collected in the draining box 32 via the draining pipe 3 (3a, 3b, 3c) overflows from the upper end of the adjusting plate 35 and drains the liquid portion 30. Flow to.
  • the electrolytic apparatus of FIGS. 14 and 15 is provided with a circulation mechanism of an electrolytic solution (not shown).
  • the recirculation mechanism adds additives such as nikawa and thiourea to the electrolytic solution discharged from the drainage unit 30 of the electrolytic cell 1, adjusts necessary components and temperature, and supplies the adjusted electrolytic solution. It recirculates from the pipe 2 into the electrolytic cell 1.
  • the electrolyzer is provided with a power feeding mechanism (not shown).
  • the power feeding mechanism includes a power supply device and wiring for applying a direct current between electrodes including anode plates and cathode plates that are alternately arranged along the longitudinal direction in the electrolytic cell 1.
  • the electrolytic solution is supplied from the width (Y) direction of the electrolytic cell 1, that is, from the first side wall 11 side to the second side wall 12 side of the electrolytic cell 1.
  • the installation positions of the liquid supply ports 21a, 21b ... 23x of the liquid supply pipe 2 are relatively larger than those of the drainage ports 31a, 31b ... 31x of the drainage pipes 3a, 3b and 3c.
  • the so-called “horizontal insertion, top-in, bottom-out method” is adopted, which is configured to be upward.
  • the risk of winding up the palace is reduced. Therefore, even if the supply flow rate of the electrolytic solution is increased, the mixed state of the electrolytic solution can be improved while suppressing the hoisting of the palace, and the electrodeposition efficiency of the electrodeposited object can be improved as compared with the conventional case. Further, since additives such as Nikawa, which affect the surface texture of the electrodeposited material, can be uniformly distributed throughout the electrolytic cell, an electrodeposited material having uniform quality can be obtained in the entire electrolytic cell 1.
  • a metal such as copper can be electrodeposited on a plurality of cathode plates.
  • refining blister copper will be described as an example of electrolysis using the electrolytic device according to the embodiment of the present invention.
  • a blister copper plate having a purity of about 99 mass% is used as an anode plate
  • a copper plate having a purity of about 99.99 mass% or a stainless steel plate is used as a cathode plate
  • a plurality of anode plates and a plurality of cathode plates are alternately arranged.
  • the electrode plates are arranged in the electrolytic cell 1 at a predetermined distance from the bottom surface of the electrolytic cell 1 at intervals in the thickness direction.
  • An electrolytic solution prepared by adding additives such as nikawa and thiourea to a mixed aqueous solution of copper sulfate and sulfuric acid is supplied from a plurality of liquid supply ports 21a, 21b ... 23x of the liquid supply pipe 2 connected to the liquid supply unit 20.
  • the electrolytic solution in the electrolytic tank 1 is drained from the plurality of drainage ports 31a, 31b ... 31x of the drainage pipes 3a, 3b, 3c connected to the drainage box 32 and the drainage unit 30, and is not shown.
  • the electrolytic solution is circulated by the recirculation mechanism of.
  • a direct current is applied between the anode plate and the cathode plate using the power feeding mechanism, and the copper of the anode plate is eluted as ions in the electrolytic solution and electrodeposited on the cathode plate.
  • the electrolytic solution is supplied into the electrolytic cell 1 from above the first side wall 11 of the electrolytic cell 1 facing the side surfaces of the anode plate and the cathode plate, and the second side wall 1 of the electrolytic cell 1 facing the first side wall 11 is supplied.
  • a liquid flow is generated so as to drain the electrolytic solution into the drain pipes 3a, 3b, and 3c below the side wall 12.
  • the electrolytic solution drained into the drainage pipes 3a, 3b, and 3c is pumped up by the drainage box 32 and drained through the drainage section 30.
  • Foreign matter such as dust floating in the upper layer of the electrolytic cell in the electrolytic cell 1 is accommodated in the drainage box 32 by overflow from the notch 33 provided in the drainage box 32 and discharged to the outside of the electrolytic cell 1. ..
  • the length of the electrolytic cell 1 is from one end of the electrolytic cell 1 in the lateral direction Y to the other end side in the lateral direction Y and from the upper side to the lower side.
  • the electrolytic cell in the electrolytic cell 1 The mixed state can be improved.
  • the electrolysis method according to the fifth embodiment of the present invention it is possible to suppress an increase in the concentration of metal ions such as copper ions in the lower part of the electrolytic cell 1 and disperse the metal ions more uniformly in the liquid, which is high. It is possible to more efficiently suppress the immobilization phenomenon when electrolytic purification is performed using a material having a high current density or an impurity concentration for the anode plate.
  • the positions of the liquid supply ports 21a, 21b ... 23x and the liquid drainage ports 31a, 31b ... 31x provided in the liquid supply pipe 2 and the liquid drainage pipes 3a, 3b, 3c, respectively, are the anodes immersed in the electrolytic cell 1. It can be adjusted in relation to the position where the plate and the cathode plate are arranged. For example, a plurality of liquid supply ports 21a, 21b ... 23x provided in the liquid supply pipe 2 and a plurality of liquid drainage ports 31a, 31b ... 31x provided in the liquid drainage pipes 3a, 3b, 3c, respectively.
  • the electrolytic solution can be supplied to the space between the anode plate and the cathode plate.
  • one liquid supply port 21a, 21b ... 23x and one drainage port 31a, 31b ... 31x are arranged.
  • a plurality of liquid supply ports 21a, 21b ... 23x and drainage ports 31a, 31b ... 31x are arranged in the space according to the size of the space between the anode plate and the cathode plate. You may do so.
  • the liquid supply ports 21a, 21b ... 23x and the drainage ports 31a, 31b ... 31x from the central side in the longitudinal direction to the drainage side of the electrolytic cell 1 in which the mixed state of the electrolytic solution, particularly the additive, tends to deteriorate.
  • the number may be larger than the number on the liquid supply side from the center side in the longitudinal direction of the electrolytic cell 1.
  • the opening areas of the liquid supply ports 21a, 21b ... 23x and the liquid drainage ports 31a, 31b ... 31x provided in the liquid supply pipe 2 and the liquid drainage pipes 3a, 3b, 3c, respectively, are basically X in the longitudinal direction. Although the examples showing the same size along the above, different opening areas may be provided in the longitudinal direction X upstream side and the downstream side of the electrolytic cell 1.
  • a plurality of pipes or a pipe in which one pipe is branched in a branch shape along the longitudinal direction can be used as the liquid supply pipe 2 and the liquid drainage pipe 3a, 3b, 3c.
  • Example 1 When an electrolyzer having the configuration shown in FIG. 1 is used (Example 1), as shown in FIG. 16A, the electrolytic solution is supplied from two locations below one end in the longitudinal direction of the electrolytic tank, and the electrolytic solution is supplied in the longitudinal direction.
  • Example 1 When an electrolyzer is used in which the electrolytic solution is drawn out from above the other end (Comparative Example 1), and as shown in FIG. 16B, the electrolytic solution is supplied from one location below one end in the longitudinal direction of the electrolytic tank.
  • sampling is performed 50 mm (upper) from the liquid level of the electrolytic solution at the liquid supply side end, the center, and the drainage side end, respectively. It is carried out at a total of 9 points of 525 mm (middle) and 1050 mm (bottom), and represents the relative concentration ratio of each sampling point when the supply Cu concentration and the supply liquid Nikawa concentration are 1.00.
  • the “liquid supply” in FIGS. 17 (a) and 17 (b) corresponds to the third side wall 13 side of the electrolytic device of FIG. 1, and the “drainage” of FIGS. 17 (a) and 17 (b).
  • the “liquid” corresponds to the fourth side wall 14 side of the electrolytic device of FIG.
  • the “liquid supply” of FIGS. 17 (c) to 17 (f) corresponds to one end of the electrolytic cell on the side where the electrolytic solution supply unit of FIGS. 16 (A) and 16 (B) is arranged, and is “drainage”. Corresponds to the other end of the electrolytic cell on the side where the electrolytic solution discharge port of FIGS. 16A and 16B is arranged.
  • the nikawa concentration as shown in FIG. 17 (f), in the conventional liquid supply method shown in Comparative Example 2, the nikawa concentration was almost 0 on the drain side from the vicinity of the center of the electrolytic cell, but FIG. 17 ( As shown in b), in Example 1, the Nikawa concentration could be maintained above a predetermined value in the entire electrolytic cell in any region.
  • the Cu concentration and the Nikawa concentration at the above 9 locations in each electrolytic cell are relative to each other when the feed Cu concentration and the feed Nikawa concentration are 1.00.
  • Tables showing the concentration ratios are shown in FIGS. 18 (a) to 18 (f).
  • Example 1 the Cu concentration ratio was substantially uniform over the entire electrolytic cell, the mixed state of the electrolytic cells was good, and the Cu concentration at the bottom of the electrolytic cell increased with respect to the Cu concentration of the supplied liquid. Was hardly seen.
  • FIG. 18B in Comparative Example 1, the concentration of the electrolytic solution was almost uniform over the entire electrolytic cell, but the Cu concentration was higher than the Cu concentration of the feed solution at the bottom of the electrolytic cell. A high area has occurred.
  • FIG. 18C in Comparative Example 2, a region having a Cu concentration higher than the Cu concentration of the feed solution was generated toward the lower part of the electrolytic cell.
  • the concentration of Nikawa was almost uniform over the entire electrolytic cell in Example 1, and the mixed state was good.
  • the concentration of shavings on the draining side was lower than that on the liquid supply side, and the concentration of shavings on the lower part of the draining side was the lowest.
  • the concentration of Nikawa on the liquid supply side was higher than that of Comparative Example 1
  • the concentration of Nikawa on the drain side was lower than that of Comparative Example 1
  • the concentration of Nikawa on the drain side was lower than that of Comparative Example 1.
  • the concentration was the lowest than that of Comparative Example 1.
  • 19 (a) and 19 (b) show the distribution of Cu concentration and Nikawa concentration in the electrode parallel direction (Y direction in FIG. 1) when the electrolytic device having the configuration shown in FIG. 1 is used (Example 1). It is a graph which evaluated the situation. Sampling represents the average value of the measurement results measured on the surfaces of the first, 25th, and 49th electrodes out of the 50 electrodes immersed in the electrolytic cell. Regarding the surface of each of the 1st, 25th, and 49th electrodes, the liquid supply of the electrolytic cell is performed at the center of the electrode and at 3 locations 470 mm apart from the center of the electrode to the left and right (Y direction of the electrolytic cell).
  • the Cu concentration ratio is almost uniform over the entire electrolytic cell, and it can be seen that the mixed state of the electrolytic solution is good even on the electrode parallel plane.
  • FIG. 19B even when looking at the graph of the concentration distribution of Nikawa, there is no part where the concentration of Nikawa is extremely low, and a relatively uniform concentration distribution of Nikawa in the tank can be obtained even on the electrode parallel plane. You can see that there is.
  • FIG. 20A shows a table showing the average values of the relative concentration ratios of the Cu concentration and the Nikawa concentration in the parallel direction of the electrodes when the Cu concentration of the feed liquid and the Nikawa concentration of the feed liquid are 1.00. And shown in FIG. 20 (b). As shown in FIGS. 20 (a) and 20 (b), both the Cu concentration ratio and the Nikawa concentration ratio were substantially uniform over the entire electrolytic tank even on the electrode parallel plane, and the mixed state of the electrolytic solution was good.
  • FIG. 22 shows the total points of 50 mm (top), 525 mm (middle), and 1050 mm (bottom) from the liquid levels on the liquid supply side, the center, and the drainage side of the electrolytic cell, respectively, and the liquid supply nikawa concentration was 1.00. Represents the relative concentration ratio of each sampling point.
  • “Liquid supply” in FIG. 22 corresponds to the third side wall 13 side of the electrolytic device of FIG. 1, and “drainage” corresponds to the fourth side wall 14 side of the electrolytic device of FIG.
  • the second embodiment there is no region where the squid does not reach the lower part of the electrolytic cell, and the mixed state of the squid added to the electrolytic solution in the electrolytic cell can be improved. It was.
  • Electrolytic cell 2 Liquid supply piping (electrolyzate supply unit) 3, 3a, 3b, 3c ... Drainage piping (electrolyte discharge part) 3A ... Outlet 3A ... Outlet 4 ... Gutter 5 ... Auxiliary pipe 6 ... Auxiliary pipe 11 ... First side wall 12 ... Second side wall 13 ... Third side wall 14 ... Fourth side wall 20 ... Liquid supply parts 21, 22 , 23 ... Piping section 21a, 21b ... 21x ... Liquid supply port (supply port) 22a, 22b ... 22x ... Liquid supply port 23a, 23b ... 23x ... Liquid supply port 30 ... Drainage section 31a, 31b ...

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention concerne un appareil d'électrolyse et un procédé d'électrolyse capables d'inhiber l'entraînement de boue tout en améliorant l'état de mélange d'un électrolyte fourni à un réservoir d'électrolyse. Cet appareil d'électrolyse est un appareil dans lequel des électrodes, qui comprennent de multiples plaques d'anode et de multiples plaques de cathode qui sont espacées l'une de l'autre et disposées en alternance le long de la direction longitudinale d'un réservoir d'électrolyse 1 contenant un électrolyte, sont immergées dans une électrolyse et une électrolyse est effectuée tout en faisant circuler l'électrolyte, ledit appareil d'électrolyse étant pourvu : d'un tuyau d'alimentation en liquide 2 pour fournir l'électrolyte à partir de multiples orifices d'alimentation en liquide 21a, 21b... 21x disposés sur une première paroi latérale 11 du réservoir d'électrolyse 1 qui fait face aux surfaces latérales des plaques d'anode et des plaques de cathode vers un second côté de paroi latérale 12 qui fait face à la première paroi latérale 11; et un tuyau d'évacuation de liquide 3 pour décharger l'électrolyte à partir de multiples orifices de décharge de liquide 31a, 31b... 31x disposés sur le second côté de paroi latérale 12 et disposés de manière à être inférieurs aux orifices d'alimentation en liquide 21a, 21b... 21x.
PCT/JP2020/014682 2019-03-29 2020-03-30 Appareil d'électrolyse et procédé d'électrolyse WO2020204003A1 (fr)

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JP2001014036A (ja) * 1999-07-01 2001-01-19 Sumitomo Metal Mining Co Ltd 電解槽の液面調整装置
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CN104404575A (zh) * 2014-11-28 2015-03-11 阳谷祥光铜业有限公司 金属电解槽及金属电解工艺
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JP6065706B2 (ja) * 2013-03-27 2017-01-25 三菱マテリアル株式会社 金属の電解精製方法、電解精製装置
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JP2000144476A (ja) * 1998-11-02 2000-05-26 Sumitomo Metal Mining Co Ltd 電解槽用液面自動制御装置
JP2001014036A (ja) * 1999-07-01 2001-01-19 Sumitomo Metal Mining Co Ltd 電解槽の液面調整装置
JP2002105684A (ja) * 2000-09-29 2002-04-10 Dowa Mining Co Ltd 電解方法及びこれに使用する電解槽
JP2015209550A (ja) * 2014-04-23 2015-11-24 三菱マテリアル株式会社 電解精錬方法
CN104404575A (zh) * 2014-11-28 2015-03-11 阳谷祥光铜业有限公司 金属电解槽及金属电解工艺

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