JP2020164962A - Electrolyzer and electrolysis method - Google Patents

Abstract

To provide an electrolyzer and an electrolysis method, in which an electrolytic solution may be more uniformly supplied over the entire chamber so as to improve a mixed state of the electrolytic solution.SOLUTION: There is provided an electrolyzer in which electrodes arranged at intervals along the longitudinal direction of an electrolytic chamber 1 storing an electrolytic solution are immersed in the electrolytic solution so as to an execute electrolytic treatment while circulating the electrolytic solution. The electrolyzer comprises: a liquid supply pipe 2 that extends along a first side wall 11 of the electrolytic chamber 1 extending in a direction X and supplies the electrolytic solution from a plurality of liquid supply ports 21a to 23x arranged at intervals from each other toward a second side wall 12 facing the first side wall 11; a drainage pipe 3 that is arranged below the liquid supply pipe 2, extends along the second side wall 12 and drains the electrolytic solution from a plurality of liquid discharge ports 31a to 31x arranged at intervals from each other; and a drainage unit 30 that drains the electrolytic solution drained by the drainage pipe 3 to the outside of the electrolytic chamber 1. The liquid supply pipe 2 comprises two or more pipes 21, 22 and 23 that may independently supply the electrolytic solution to at least the upstream side and the downstream side of the electrolytic chamber 1.SELECTED DRAWING: Figure 3

Description

The present invention relates to an electrolyzer and an electrolyzer.

In the conventional electrolytic cell, 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. It has been 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.

For example, in Japanese Patent Application Laid-Open No. 2007-204779 (Patent Document 1), 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. Japanese Unexamined Patent Publication No. 2015-209550 (Patent Document 2) proposes a method in which an electrolytic solution is supplied toward a side surface from the upper part of one end in the longitudinal direction of an electrolytic cell and drained from the lower part of the other end. There is. Further, as a completely different method, Japanese Patent Application Laid-Open No. 2014-189851 (Patent Document 3) and Japanese Patent No. 5227404 (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.

JP-A-2007-204779 JP-A-2015-209550 Japanese Unexamined Patent Publication No. 2014-189851 Japanese Patent No. 5227404

However, as the electrolysis progresses, a difference in the concentration of the liquid is generated in the electrolytic cell, and the liquid having a heavier specific gravity accumulates toward the bottom of the electrolytic cell. Since the liquid supplied from the liquid supply port has a lower specific gravity than the liquid at the bottom of the electrolytic cell, when the electrolyte liquid of the bottom-in / top-draining method as described in Patent Documents 1 and 2 is supplied / discharged. There is a dead space below the liquid supply position where the electrolyte and additives are not supplied. If there is a region in the electrolytic cell where no additive is supplied, the surface of the electrodeposited material may become rough, or the copper concentration in the liquid may partially increase due to the absence of the electrolyte, and passivation may easily occur. is there.

In the invention described in Patent Document 3, 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. However, since 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.

In the invention described in Patent Document 4, 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. However, in 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 inventors have arranged a supply pipe in the upper part of the side wall in the longitudinal direction of the electrolytic cell as an effective method for improving the mixed state of the electrolytic cell supplied into the electrolytic cell while suppressing the hoisting of the drainage. It was considered that the drainage pipe was arranged at the lower part of the side wall facing the opposite side in the longitudinal direction, and the liquid was supplied from a plurality of liquid supply ports provided at equal intervals along the longitudinal direction. However, as the length of the liquid supply pipe becomes longer, more electrolytic solution is supplied toward the base of the liquid supply pipe, and the amount of liquid supply decreases toward the tip of the pipe, making it impossible to supply liquid uniformly throughout the tank. It turned out that there is. As a result, in particular, the concentration uniformity of the additive added to the electrolytic solution may not be sufficiently obtained.

In view of the above problems, the present disclosure provides an electrolyzer and an electrolyzing method capable of more uniformly supplying the electrolytic solution over the entire tank and improving the mixed state of the electrolytic solution.

In one embodiment, the electrolytic apparatus according to the embodiment of the present invention circulates the electrolytic solution by immersing electrodes arranged at intervals along the longitudinal direction of the electrolytic solution containing the electrolytic solution in the electrolytic solution. It is an electrolyzer that performs electrolysis treatment while being electrolyzed, and is an electrolyzer that extends along the first side wall of the electrolytic tank that extends in the longitudinal direction and faces the first side wall from a plurality of liquid supply ports that are arranged at intervals from each other. A liquid supply pipe that supplies the electrolytic solution toward the second side wall, and a plurality of drainage pipes that are arranged below the liquid supply pipe, extend along the second side wall, and are arranged at intervals from each other. It is provided with a drainage pipe for draining the electrolytic solution from the mouth 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 and The electrolytic apparatus is provided with two or more piping portions capable of independently supplying an electrolytic solution to the downstream side.

In one embodiment, the electrolysis method according to the embodiment of the present invention is an electrolysis method in which an electrolyzer is immersed in an electrolytic solution and electrolyzed while circulating the electrolytic solution, and is formed on a first side wall of an electrolytic tank extending in the longitudinal direction. First from a plurality of liquid supply ports provided in a liquid supply pipe having two or more piping portions extending along the line and capable of independently supplying the electrolytic solution to at least the upstream side and the downstream side of the electrolytic tank. The electrolytic solution was supplied toward the second side wall side of the electrolytic tank facing the side wall of the electrolytic solution, and was arranged below the liquid supply pipe, extended along the second side wall, and arranged at a distance from each other. This is an electrolysis method including draining an electrolytic solution into a drainage pipe provided with a plurality of drainage ports and draining the electrolytic solution drained into the drainage pipe to the outside of the electrolytic tank.

According to the present disclosure, it is possible to provide an electrolyzer and an electrolyzing method capable of supplying an electrolytic solution more uniformly over the entire tank and improving a mixed state of the electrolytic solution.

FIG. 1A is a schematic top view of the electrolyzer according to the embodiment of the present invention, and FIG. 1B is a schematic cross-sectional view of the electrolyzer according to the embodiment of the present invention. It is explanatory drawing which shows the example of the simulation result of the concentration distribution along the electrolytic cell 1 longitudinal direction of the additive such as Nikawa added to the electrolytic solution when the liquid supply pipe is composed of one. It is a top view which shows the arrangement example of the liquid supply pipe which concerns on embodiment of this invention. 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 sectional drawing which shows the liquid supply part and the drainage box. 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. 8 (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 present embodiment, and FIG. 8 (b) shows the simulation result of the central portion of the electrolytic cell according to the present embodiment. The cross-electrode Cu concentration distribution is shown, FIG. 8 (c) shows the simulation result of the central cross-section Nikawa concentration distribution along the longitudinal direction of the electrolytic cell according to the present embodiment, and FIG. 8 (d) shows the present implementation. It is explanatory drawing which shows the cross-electrode Nikawa concentration distribution of the central part of the electrolytic cell which concerns on an example. It is an image figure which shows the density distribution of the Nikawa concentration in the electrolytic cell of the electrolytic cell which concerns on this Example.

Hereinafter, the electrolysis apparatus and the electrolysis method according to the embodiment of the present invention will be described with reference to the drawings. The embodiments shown below exemplify devices and methods for embodying the technical idea of the present invention, and the technical idea of the present invention includes the structure, arrangement, procedure, etc. of each component. Is not specified as the following.

(Electrolyzer)
As shown in FIGS. 1 (a) and 1 (b), the electrolyzer according to the embodiment of the present invention includes a rectangular parallelepiped electrolytic cell 1 for accommodating the electrolytic solution. The size of the electrolytic cell 1 is, for example, a length (inner diameter in the longitudinal direction X) of 5200 to 5900 mm, a width (inner diameter in the lateral direction Y) of 1095 to 1110 mm, and a depth of 1275 to 1510 mm. Can be formed as follows.

The electrolytic cell 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 in the longitudinal direction X and facing the third side wall 13. Have.

As shown in FIG. 1 (b), above the first side wall 11 of the electrolytic cell 1, the electrolytic cell 1 is located at a height close to or near the liquid level of the electrolytic cell housed in the electrolytic cell 1. A liquid supply pipe 2 extending along the longitudinal direction X is arranged. The liquid supply pipe 2 is connected to a supply unit 20 arranged above the third side wall 13 of the electrolytic cell 1. The supply unit 20 can supply the electrolytic solution to other electrolytic cells other than the electrolytic cell 1 in addition to the electrolytic cell 1 shown in FIGS. 1 (a) and 1 (b). A main pipe and a branch pipe for branching the electrolytic solution from the supply main pipe to the liquid supply pipe 2 can be provided, but of course, the present invention is not limited to this example.

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. In order to improve the mixed state of the electrolytic solution, 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. ..

In the electrolytic apparatus according to the present embodiment, a method is adopted in which 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 / min. As a result, it is possible to further improve the mixed state of the electrolytic solution supplied into the electrolytic cell 1 while suppressing the hoisting of the palace, and it is possible to carry out more efficient electrolytic refining. 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.

As shown in FIG. 1 (b), the liquid supply pipe 2 may be composed of one pipe having liquid supply ports 21a, 21b ... 21x arranged at equal intervals as a whole along 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. 1B) is sufficient. The electrolyte may not be supplied to the machine.

FIG. 2 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. As shown in FIG. 2, 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.

In the electrolytic apparatus according to the embodiment of the present invention, as shown in FIG. 3, 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.

As shown in FIG. 3, 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. Compared with the case where 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. 3) is provided. In the piping portion 21, 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.

It is preferable that the piping portions 21, 22 and 23 have regions 200 and 201 in which the ends thereof partially overlap each other in the electrolytic cell 1. By distributing the electrolytic solution supply area at least on the upstream side and the downstream side by the piping portions 21, 22, and 23, each of them is more than the case where one liquid supply pipe 2 as shown in FIG. 1A is formed. The amount of the electrolytic solution supplied in the region can be made more uniform. On the other hand, the state of supplying the electrolytic solution becomes uneven even in the piping portions 21, 22, and 23. In particular, 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.

According to the electrolyzer according to the embodiment of the present invention, as shown in FIG. 3, 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 liquid supply ports 21a, 21b ... In the regions 200, 201 where one piping portion 21, 22, 23 overlaps with the other piping portions 21, 22, 23 with respect to the total opening area. It can be arranged so that the ratio of the total opening area of 23x is 1/4 or more, more preferably 1/3 or more, still more preferably 1/2 or more.

Alternatively, 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. 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.

As shown in FIG. 1B, 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. In this way, 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.

When the plurality of drainage ports 31a, 31b ... 31x are too close to the bottom, the drainage ports 31a, 31b ... 31x may be clogged or malfunction due to the involvement of the bottom ridge of the electrolytic cell 1. There is. 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.

As shown in FIG. 4, it is preferable that the opening areas of the drainage ports 31a, 31b, ... Are larger than the opening areas of the liquid supply ports 21a, 21b, 21c ... By increasing the opening area of the drainage ports 31a, 31b, ..., The influence of pressure loss when the electrolytic solution in the drainage pipe 3 is discharged to the outside of the electrolytic cell 1 can be further reduced. Although not limited to the following, 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. As a result, the electrolytic solution in the electrolytic cell 1 can be efficiently drained from the drainage ports 31a, 31b, ....

The pipe diameter of the liquid drainage pipe 3 is preferably formed larger than the pipe diameter of the liquid supply pipe 2. By making the pipe diameter on the drainage pipe 3 side larger than the pipe diameter of the liquid supply pipe 2, when the electrolytic solution is discharged from the drainage box 32 to the outside of the electrolytic tank 1 by utilizing the head pressure difference of the electrolytic solution. The influence of the pressure loss of the drainage pipe 3 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 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 pipe diameters of the liquid supply pipe 2 and the liquid drainage pipe 3, the shapes, hole diameters (slit diameters), and intervals of the liquid supply ports 21a, 21b, 21c ... And the liquid drainage ports 31a, 31b, ... It can be appropriately adjusted according to the size of 1. In the example shown in FIG. 4, 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.

Although not limited to the following, in the example of FIG. 4, in the liquid supply pipe 2, circular or elliptical liquid supply ports 21a, 21b, 21c, ... With an interval d1 of 50 mm and a hole diameter of 5φ are formed. There is. In the drainage pipe 3, elliptical or substantially rectangular drainage ports 31a, 31b, ... With a width of 10 mm and a slit diameter (d2) of 400 mm are arranged with an interval d3 of 200 mm.

As shown in FIGS. 1A and 1B, 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. As shown in FIG. 1A, 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. As shown in FIG. 5, 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.

As shown in FIG. 1 (b), the drainage box 32 is connected between the drainage unit 30 and the drainage pipe 3. As shown in FIG. 5, 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. ..

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. As shown in FIG. 5, the cutout portion 33 has a shape in which the opening width AW decreases from the upper side to the lower side of the electrolytic cell 1. The shape of the cutout portion 33 may be various shapes such as a V-shape, a U-shape, and a trapezoidal shape as shown in FIG. 7, but the specific shape is not particularly limited.

In the electrolytic cell 1, foreign matter such as dust may accumulate on the electrolytic solution surface LS as the electrolysis is performed. If this foreign matter stays in the electrolytic cell 1, it may adversely affect the electrolysis. According to the electrolyzer according to the embodiment of the present invention, 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.

As shown in FIG. 5, 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. 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.

For example, by arranging 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. 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. .. As a result, 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 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 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.

Various studies have been conducted to improve the mixed state of the electrolytic solution in the electrolytic tank 1, but the conventional method of flowing the electrolytic solution from one end side in the longitudinal direction to the other end side in the longitudinal direction in the electrolytic tank 1 has been carried out. In the bottom-in top-pull type electrolyzer, the concentration of metal ions such as copper and the concentration of additives in the electrolytic solution are biased on the upstream side and the downstream side in the electrolytic solution supply direction, and as the electrolysis progresses, the electrolytic tank 1 The metal ion concentration tended to increase from the top to the bottom.

According to the electrolyzer according to the embodiment of the present invention, 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 above 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. As a result, an increase in the metal ion concentration such as the copper ion concentration at the bottom of the electrolytic cell 1 can be effectively suppressed, and the concentration distribution of various additives contained in the electrolytic cell is made more uniform throughout the electrolytic cell 1. can do.

Further, by flowing the electrolytic solution from the upper side to the lower side in the electrolytic cell 1, 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.

Further, 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.

Further, 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.

(Electrolysis method)
By electrolyzing the electrolytic solution using the electrolytic device according to the embodiment of the present invention, a metal such as copper can be electrodeposited on a plurality of cathode plates. In the following, a case of refining blister copper will be described as an example of electrolysis using the electrolytic device according to the embodiment of the present invention.

First, for example, 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, and a plurality of anode plates and a plurality of cathode plates are alternately arranged. The electrode plates are arranged in the electrolytic cell 1 so as to have a predetermined distance from the bottom surface of the electrolytic cell 1 at intervals in the thickness direction. As shown in FIG. 4, on the first side wall 11 of the electrolytic cell 1, 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. 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 a power feeding mechanism, and the copper of the anode plate is eluted as ions in the electrolytic solution and electrodeposited on the cathode plate. At this time, 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. ..

According to the electrolysis method according to the embodiment of the present invention, 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. Compared with the conventional method of flowing the electrolytic solution from one end side to the other end side in the longitudinal direction X of the electrolytic cell 1 by flowing the electrolytic solution from a plurality of locations along the line, the mixed state of the electrolytic cell in the electrolytic cell 1 is changed. Can be better.

In particular, according to the electrolysis method according to the embodiment of the present invention, 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.

(Other embodiments)
Although the present invention has been described in accordance with the above embodiments, the statements and drawings that form part of this disclosure should not be understood to limit the invention. Various alternative embodiments and operational techniques will be apparent to those skilled in the art from this disclosure.

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. For example, 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. 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. By generating a liquid flow on the surfaces of the anode plate and the cathode plate in this way, 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.

In the space between the anode plate and the cathode plate housed in the electrolytic cell 1, one liquid supply port 21a, 21b ... 23x and one drainage port 31a, 31b ... 31x are arranged. Not only that, 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. Further, 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 in the longitudinal direction X upstream side and the downstream side of the electrolytic cell 1.

As the liquid supply pipe 2 and the liquid drainage pipe 3, a plurality of pipes or a pipe in which one pipe is branched in a branch shape along the longitudinal direction can be used. When a plurality of drainage pipes 3 are arranged, each of the outlets of the drainage pipes 3 can be independently connected to the drainage box 32.

As described above, the present invention is represented by the matters specifying the invention within the scope of claims reasonable from the above disclosure, and at the implementation stage, it can be modified and embodied without departing from the gist thereof.

Examples of the present invention are shown below together with comparative examples, but these examples are provided for a better understanding of the present invention and its advantages, and are not intended to limit the present invention. Absent.

For an electrolytic cell in which a liquid supply pipe having three piping portions having the configuration shown in FIG. 4 is installed, a plurality of anode plates and cathode plates are alternately provided in each electrolytic cell along the longitudinal direction of the electrolytic cell. Immerse in the electrolytic cell at intervals, perform electrolysis at a current density of 350 A / m ² and a supply amount of 43 L / min (residence time in the electrolytic cell 2.5 hours), and distribute the Cu concentration in the cross section in the central part of the electrolytic cell. And the Nikawa concentration distribution was evaluated.

As shown in FIGS. 8 (a) and 8 (b), according to the examples, a relatively uniform Cu concentration distribution could be obtained in the tank. As shown in FIGS. 8 (c) and 8 (d), the nikawa concentration distribution was uniform over the entire longitudinal direction of the tank, and no dead space to which nikawa was added was observed.

FIG. 9 was carried out at a total of 9 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. It represents the relative concentration ratio of each sampling point when it is set to 00.

The “liquid supply” in FIG. 9 corresponds to the third side wall 13 side of the electrolytic device of FIG. 1, and the “drainage” corresponds to the fourth side wall 14 side of the electrolytic device of FIG. As can be seen from FIG. 9, in the example, there was no region where the nikawa did not reach the lower part of the electrolytic cell, and the mixed state of the nikawa added to the electrolytic solution in the electrolytic cell could be improved.

1 ... Electrolytic cell 2 ... Liquid supply pipe 3 ... Drainage pipe 3A ... Outlet 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 to 23x ... Liquid supply port 24 ... Main pipe 30 ... Drainage section 31a to 31x ... Drainage port 32a ... Bottom surface 32b ... Side wall 32 ... Drainage box 33 ... Notch 35 ... Adjustment plate 200, 201 ... Areas 221 and 231 ... Tip portion 222, 232 ... Root portion 223, 233 ... Intermediate portion 300 ... Discharge port 301 ... Discharge pipe

Claims (6)

An electrolytic device in which electrodes arranged at intervals along the longitudinal direction of an electrolytic cell containing an electrolytic solution are immersed in the electrolytic solution, and the electrolytic solution is circulated for electrolytic treatment.
A plurality of liquid supply ports extending along the first side wall of the electrolytic cell extending in the longitudinal direction and arranged at intervals from each other toward the second side wall of the electrolytic cell facing the first side wall. And the liquid supply pipe that supplies the electrolytic solution
A drainage pipe arranged below the liquid supply pipe, extending along the second side wall, and draining the electrolytic solution from a plurality of drainage ports arranged at intervals from each other.
It is provided with a drainage unit for draining the electrolytic solution discharged by the drainage pipe to the outside of the electrolytic cell.
An electrolyzer characterized in that the liquid supply pipe includes two or more pipe portions capable of independently supplying the electrolytic liquid to at least the upstream side and the downstream side of the electrolytic cell. The electrolyzer according to claim 1, wherein 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 region where the 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. The electrolyzer according to claim 1 or 2, which comprises being arranged in such a manner. The electrolyzer according to any one of claims 1 to 3, wherein the diameter of the drainage pipe is larger than the diameter of the liquid supply pipe. The drainage portion is connected to the drainage pipe and has 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 electrolysis in the drainage pipe is provided. The electrolyzer according to any one of claims 1 to 4, further comprising a drainage box capable of pumping liquid. This is an electrolytic method in which electrodes arranged at intervals along the longitudinal direction of an electrolytic cell containing an electrolytic solution are immersed in the electrolytic solution, and the electrolytic solution is circulated and electrolyzed.
Two or more piping portions extending along the first side wall of the electrolytic cell extending in the longitudinal direction and capable of independently supplying the electrolytic cell to at least the upstream side and the downstream side of the electrolytic cell. The electrolytic solution is supplied from a plurality of liquid supply ports provided in the liquid supply pipes provided toward the second side wall side of the electrolytic cell facing the first side wall.
The electrolytic solution is drained into a drainage pipe having a plurality of drainage ports arranged below the liquid supply pipe, extending along the second side wall, and arranged at intervals from each other.
An electrolysis method comprising draining the electrolytic solution discharged into the drainage pipe to the outside of the electrolytic cell.