JP2020164963A - 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 an 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 execute an 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 the longitudinal direction and supplies the electrolytic solution from a plurality of liquid supply ports 21a to 21x arranged at intervals from each other toward a second side wall 12 of the electrolytic chamber 1 facing the first side wall 11; drainage pipes 3a, 3b, 3c that are arranged below the liquid supply pipe 2, extend along the second side wall 12 and drain 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 pipes 3a, 3b, 3c to the outside of the electrolytic chamber 1. The drainage pipes 3a, 3b, 3c comprise two or more pipes along the longitudinal direction.SELECTED DRAWING: Figure 2

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.

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 extending in the longitudinal direction and faces the first side wall from a plurality of liquid supply ports arranged at intervals from each other. A liquid supply pipe that supplies the electrolytic solution toward the second side wall side, and a plurality of discharges 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 liquid port 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 is at least along the longitudinal direction. It is an electrolyzer equipped with two or more pipes.

In one embodiment, the electrolysis method according to the embodiment of the present invention circulates the electrolytic solution by immersing the electrodes arranged at intervals along the longitudinal direction of the electrolytic solution containing the electrolytic solution in the electrolytic solution. A method of electrolyzing while electrolyzing, which is a method of electrolyzing an electrolytic tank that faces the first side wall from a plurality of liquid supply ports provided in a liquid supply pipe extending along the first side wall of the electrolytic tank extending in the longitudinal direction. The electrolytic solution is supplied toward the side wall side of 2, and electrolyzed through a plurality of drainage ports of a plurality of drainage pipes which are arranged below the liquid supply pipe and extend in the longitudinal direction along the second side wall. This is an electrolysis method including draining a liquid and draining the electrolytic liquid drained by the drain 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.

It is a top view of the electrolysis apparatus which concerns on 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 embodiment of this invention is seen from the side. 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 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.

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 FIG. 1, the electrolyzer according to the 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, 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 of the longitudinal direction X and facing the third side wall 13. And have.

Above the first side wall 11 of the electrolytic cell 1, 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. In addition to the electrolytic cell 1 shown in FIGS. 1 (a) and 1 (b), the liquid supply unit 20 can supply the electrolytic solution to other electrolytic cells other than the electrolytic cell 1. A liquid 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 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. ..

In the electrolytic device according to the present embodiment, by setting the supply flow rate to 20 to 100 L / min, 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 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.

Above the fourth side wall 14 side of the 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. Has been done. As shown in FIG. 4, a plurality of drainage pipes 3a, 3b, and 3c are connected to the drainage box 32, respectively. As shown in FIG. 2, 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.

In the example of FIG. 2, the drainage pipe 3a provided with the drainage ports 31a to 31f 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, and the electrolytic solution A drainage pipe 3b having a drainage port 31g to 31l capable of draining the electrolytic solution near the center of the tank 1 and a drainage port 31m capable of draining the electrolytic solution on the side close to the drainage box 32 of the electrolytic tank 1 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.

For example, 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. Of course, it is also possible to arrange it so that it is the uppermost part of 3c.

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. When the drainage ports 31a to 31x are provided only at the tips of the drainage pipes 3a, 3b, and 3c as shown in FIG. 2, 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.

Since 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. 2, 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. 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 preferably configured to be larger than the pipe diameter of the liquid supply pipe 2. By making the pipe diameters on the drainage pipes 3a, 3b, and 3c sides 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.

If the heights of the drainage pipes 3a, 3b, and 3c are too close to the bottom portion, the bottom portion of the electrolytic cell 1 may be caught in the heights of the drainage pipes 3a, 3b, and 3c, which may cause clogging or malfunction of the drainage ports 31a to 31x. 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.

As shown in FIG. 3, 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.

Although not limited to the following, 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. In the example shown in FIG. 3, 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.

Although not limited to the following, as shown in the example of FIG. 3, in the liquid supply pipe 2, the electrolytic cell spacing d1 is 50 mm and the hole diameter is 5φ, which is a circular or elliptical liquid supply port 21a, 21b, 21 ... 21x is formed. At the tips of the drainage pipes 3a, 3b, and 3c, 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.

As shown in FIG. 2, 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. As shown in FIG. 5, the drainage unit 30 is provided with a discharge port 300 for discharging the electrolytic solution in the electrolytic cell 1. As shown in FIG. 6, 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.

As shown in FIG. 6, 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. 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.

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. As shown in FIG. 4, 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.

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

As shown in FIG. 6, 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 (3a, 3b, 3c) overflows from the upper end of the adjusting plate 35 and drains the liquid portion 30. Flow to.

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.

As shown in FIG. 5, 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. It is preferably provided in the box 32. 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 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. 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 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 between the upstream side and the downstream side in the electrolytic solution supply direction, and as the electrolysis progresses, from the upper part of the electrolytic tank 1 The metal ion concentration tended to increase toward the bottom.

According to the electrolyzer according to the embodiment of the present invention, 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 insertion, bottom removal method" is adopted, which is configured to be upward. 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.

(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.

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 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 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. ..

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 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. It can be provided so as to face the gap provided between the anode plate and the cathode plate, 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 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. As the liquid supply pipe 2 and the liquid drainage pipe 3a, 3b, 3c, 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 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.

1 ... Electrolytic cell 2 ... Liquid supply pipe 3 (3a, 3b, 3c) ... Drainage pipe 3A, 3B, 3C ... Outlet 11 ... First side wall 12 ... Second side wall 13 ... Third side wall 14 ... Fourth Side wall 20 ... Liquid supply part 21a to 21x ... Liquid supply port 30 ... Drainage part 31a to 31x ... Drainage port 32 ... Drainage box 32a ... Bottom surface 32b ... Side wall 33 ... Notch 35 ... Adjustment plate 37 ... Divided wall 300 ... Discharge port 301 ... Discharge piping

Claims (9)

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.
From 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, to the second side wall side of the electrolytic cell facing the first side wall. A liquid supply pipe that supplies the electrolytic solution toward the liquid
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 drained by the drainage pipe to the outside of the electrolytic cell.
An electrolyzer characterized in that the drainage pipe includes at least two or more pipes along the longitudinal direction. It is characterized by having a bottom surface below the liquid level of the electrolytic solution, the outlet of the drainage pipe being connected to the bottom surface, and a drainage box capable of pumping the electrolytic solution in the drainage pipe. The electrolytic apparatus according to claim 1. The drainage pipe is characterized by including at least two or more pipes, a first pipe capable of recovering 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. The electrolyzer according to claim 1. 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 electrolyzer according to claim 1, wherein the opening area of the drainage port is larger than the opening area of the liquid supply port. 2. The second aspect of the present invention, wherein the drainage box is provided with a notch on a 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. Electrolyzer. An adjusting plate that is arranged between the drainage box and the drainage portion and adjusts the difference between the height of the electrolytic solution in the drainage box and the height of the electrolytic solution in the electrolytic cell. The electrolyzer according to claim 2 or 6, further comprising. Any one of claims 2, 6 and 7, wherein a dividing wall for dividing the bottom surface to which the outlet of the drainage pipe is connected into a plurality of regions is provided in the drainage box. The electrolyzer according to. 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.
From a plurality of liquid supply ports provided in the liquid supply pipe extending along the first side wall of the electrolytic cell extending in the longitudinal direction toward the second side wall side of the electrolytic cell facing the first side wall. Supply the electrolytic solution and
The electrolytic solution is drained through a plurality of drainage ports of a plurality of drainage pipes arranged below the liquid supply pipe and extending in the longitudinal direction along the second side wall.
An electrolysis method comprising draining the electrolytic solution discharged by the drainage pipe to the outside of the electrolytic cell.