Electrolytic cell and method for manufacturing a metal material using the electrolytic cell

Abstract

To provide means for improving uniformity of an electrolyte to be supplied.SOLUTION: In one aspect, the present disclosure provides the following invention. An electrolytic cell comprises a drain port and a feed tube for an electrolyte solution, wherein the electrolytic cell comprises a bottom surface, a first side located on a side closer to the feed tube, a second side facing the first side and provided with the drain port, a third side and a fourth side connecting the first side and the second side, the feed tube extends along the first side that abuts a short side of the bottom surface of the electrolytic cell, the extended portion of the feed tube includes a nozzle, a side closer to a top of the extended portion includes a plate-like member, and a direction of a discharge hole is provided on a side closer to the first side.SELECTED DRAWING: Figure 10

Description

Technical Field

[0001] The present disclosure relates to an electrolytic cell and a method for manufacturing a metal material using the electrolytic cell.

Background Art

[0002] An electrolysis apparatus is used to immerse a cathode and an anode in an electrolytic cell and deposit a desired metal on the cathode. Many electrolytic cells have a rectangular parallelepiped shape or a shape close to it, and the cathode and the anode are alternately arranged along the longitudinal direction of the rectangular parallelepiped. And, on two side surfaces perpendicular to the longitudinal direction, a liquid supply port and a liquid discharge port are provided respectively.

[0003] The quality of the deposited metal is affected by various factors. One of such factors is the method of supplying the electrolytic solution. Patent Document 1 discloses supplying the electrolytic solution from the lower side of one side wall of the electrolytic cell and discharging it from the upper part of the other side wall. Patent Document 2 discloses a configuration in which a plurality of liquid supply ports are provided along the side wall parallel to the longitudinal direction of the electrolytic cell.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] The approaches in the above patent documents rely on enhancing the uniformity of the supplied electrolytic solution. However, there is still room for improvement in the uniformity of the electrolytic solution. Therefore, an object of the present disclosure is to provide means for improving the uniformity of the supplied electrolytic solution.

Means for Solving the Problems

[0006] The inventor focused on the uniformity of the electrolytic solution in the width direction. As shown in FIG. 1, the width direction described here is the direction perpendicular to the longitudinal direction of the electrolytic cell and also perpendicular to the height direction. Then, the inventor improved the orientation of the liquid supply port. Specifically, the orientation of the liquid supply port was changed, and the electrolytic solution was supplied toward the side surface on the opposite side instead of the drainage port side. As a result, since the electrolytic solution heads toward the drainage port side after bouncing back from the side wall, the uniformity of the electrolytic solution in the width direction was enhanced.

[0007] Based on the above findings, the invention was completed, and the present disclosure includes the following inventions in one aspect. (Invention 1) An electrolytic cell including a drainage port for an electrolytic solution and a liquid supply pipe, wherein the electrolytic cell includes a bottom surface, a first side surface located on the liquid supply pipe side, a second side surface facing the first side surface and provided with the drainage port, a third side surface and a fourth side surface connecting the first side surface and the second side surface, the liquid supply pipe extends along the first side surface in contact with the short side of the bottom surface of the electrolytic cell, a nozzle is provided in the extending portion of the liquid supply pipe, a plate-like member is provided on the top side of the extending portion, the nozzle is provided such that the electrolytic solution heads toward the first side surface side, Electrolytic cell. (Invention 2) The electrolytic cell according to Invention 1, wherein the nozzle includes a plurality of holes. (Invention 3) The electrolytic cell according to Invention 1, wherein the nozzle includes one or a plurality of slits. (Invention 4) The electrolytic cell according to any one of Inventions 1 to 3, wherein the cross-sectional shape of the liquid supply pipe is circular, when the height direction of the electrolytic cell is set to 0° and the angle in the direction of the first side surface side is set to positive, the orientation of the discharge hole is set such that the discharge angle is in the range of 20° to 160°, Electrolytic cell. (Invention 5) The electrolytic cell according to any one of Inventions 1 to 4, wherein the plate-like member constitutes a housing for accommodating an extending portion of the liquid supply pipe, a plurality of holes are provided on a side surface of the housing located on the drainage port side of the electrolytic cell, and a part of the plurality of holes is configured such that the flow rate is restricted. Electrolytic cell. (Invention 6) A method for manufacturing a metal material by electrolytic refining, the method including using the electrolytic cell according to any one of Inventions 1 to 5.

Advantages of the Invention

[0008] In one aspect of the above invention, the orientation of the nozzle is set such that the electrolytic solution is directed toward the side surface on the liquid supply pipe side. As a result, the distance that the electrolytic solution travels becomes longer, and accordingly, the homogenization due to the diffusion of the electrolytic solution further progresses.

Brief Description of the Drawings

[0009]

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Embodiments for Carrying Out the Invention

[0010] Hereinafter, specific embodiments for carrying out the invention will be described. The following description is for facilitating the understanding of the invention. That is, it is not intended to limit the scope of the present invention.

[0011] 1. Electrolytic cell 1-1. Target metal In one embodiment, the present disclosure relates to an electrolytic cell. The electrolytic cell is a device used for electrolytic smelting. The target metal is not particularly limited. For example, gold, silver, copper, lead, nickel, zinc, cadmium, manganese, etc. are targets. Also, the composition of the electrolytic solution can be appropriately changed according to the type of the target metal.

[0012] 1-2. Shape of the electrolytic cell (100) The shape of the electrolytic cell (100) is typically a rectangular parallelepiped. The upper part of the electrolytic cell (100) is open, and the electrolytic cell (100) has a bottom surface (150) and a plurality of side surfaces. Specifically, as shown in FIG. 1, the electrolytic cell (100) has the following five surfaces: a bottom surface (150), four side surfaces (the first side surface (liquid supply pipe side) (130), the second side surface (drain port side) (140), the third side surface (the first surface parallel to the longitudinal direction) (160), the fourth side surface (the second surface parallel to the longitudinal direction) (170)).

[0013] 1-3. Arrangement of each part inside the electrolytic cell (100) The electrolytic cell (100) holds the electrolytic solution inside. Then, as shown in FIG. 2, by immersing the anode (210) and the cathode (220) in the electrolytic solution and applying an electric current, metal can be deposited on the cathode (220) side. The electrolytic solution can be circulated and used. For this purpose, the electrolytic cell (100) can be provided with a liquid supply pipe (120) and a drain port (110). The positions of the liquid supply port of the liquid supply pipe (120) and the drain port (110) are not particularly limited, but typically, the electrolytic solution is supplied from the lower part. And the electrolytic solution is discharged by overflowing at the upper part. However, as will be described later, if the position of supplying the liquid is too low, there is a possibility of rolling up the sediment at the bottom of the electrolytic cell (100). Therefore, it is preferable that the lower end of the liquid supply port is located at a place where a certain distance is maintained from the bottom.

[0014] The electrolytic solution can be supplied into the electrolytic cell (100) through the liquid supply pipe (120). The liquid supply pipe (120) may be connected to a tank of the electrolytic solution existing outside the electrolytic cell (100). The liquid supply pipe (120) is provided with a nozzle (180), and the electrolytic solution is discharged into the electrolytic cell (100) through the nozzle (180). In this specification, the nozzle means a pipe-shaped mechanical part used to define the flowing direction of a fluid such as gas or liquid.

[0015] 1-4. Liquid supply pipe (120) 1-4-1. Material The material of the liquid supply pipe (120) and the material of the nozzle (180) are not particularly limited and may be materials known in the art. Also, in the nozzle (180), the structure for discharging the electrolytic solution is not particularly limited. For example, as shown in FIG. 3, a plurality of holes (190) may be provided in the nozzle (180). The plurality of holes (190) are preferably provided so as to be linearly arranged in the longitudinal direction so that they can be discharged in a certain direction. The distance between the plurality of holes (190) is not particularly limited. In another example, as shown in FIG. 4, a slit (200) structure may be provided in the nozzle (180). The number, size, shape, etc. of the holes (190) and the slit (200) are not particularly limited. For example, the slit (200) structure may be one or plural. Also, the shape of the hole (190) may be circular, rectangular, or other polygons.

[0016] 1-4-2. Direction of the nozzle (180) As described above, the nozzle (180) is used to define the flow direction of a fluid such as a gas or a liquid. In the present disclosure, the direction in which the electrolytic solution is discharged is important. In a normal concept, the orientation of the nozzle (180) is set so as to be discharged toward the drainage port (110) side of the electrolytic cell (100). However, in one embodiment, the orientation of the nozzle (180) is set so that the electrolytic solution is directed toward the side surface (specifically, the first side surface (130) on the liquid supply pipe side) in contact with the short side of the bottom surface (150) of the electrolytic cell (100). The significance of this is that when the electrolytic solution hits the first side surface (130) on the liquid supply pipe side, the flow in a certain direction is disturbed and the diffusion of the electrolytic solution in the width direction proceeds.

[0017] Another significance can be explained as shown in FIG. 5.

[0018] Figure 5 shows the state when the orientation of the nozzle (180) is set to discharge toward the drain port (110) side of the electrolytic cell (100). Here, at the point where the distance after discharge is X1, there is a bias in the electrolyte in the width direction. Specifically, a portion with a concentrated composition of the newly supplied electrolyte and a relatively thin portion are mixed in the width direction. However, at the point where the distance after discharge is X2 (X2 > X1), the bias of the electrolyte in the width direction is less than in the case of X1.

[0019] The reason for this is that as the moving distance in the longitudinal direction increases, the degree of diffusion of the electrolyte in the width direction increases. From this perspective, a means of increasing the size of the electrolytic cell (100) in the longitudinal direction to secure space for promoting the degree of diffusion of the electrolyte in the width direction can also be adopted. However, when such an approach is adopted, it may be necessary to change the size of the electrolytic cell (100). And when the size of each electrolytic cell (100) increases, it may affect the space of the entire facility.

[0020] In the electrolytic cell (100) according to an embodiment, the orientation of the nozzle (180) is set so that the electrolyte flows toward the side surface (specifically, the first side surface (130) on the liquid supply pipe side) in contact with the short side of the bottom surface (150) of the electrolytic cell (100). As a result, the electrolyte hits the first side surface (130) on the liquid supply pipe side and then moves toward the drain port (110) side, so the moving distance in the longitudinal direction becomes longer. Therefore, the diffusion in the width direction is further promoted. And the space in the longitudinal direction for diffusion in the width direction can be saved.

[0021] Here, the distance between the nozzle (180) and the first side surface (130) on the liquid supply pipe side is not particularly limited, but it is preferably long enough to promote diffusion in the width direction. For example, it is 10 cm or more (preferably, 20 cm to 30 cm).

[0022] The orientation of the nozzle (180) can be set within a certain width range as long as it faces the first side surface (130) on the liquid supply pipe side. For example, referring to FIG. 6, the orientation of the nozzle (180) may be set so that the discharge angle is in the range of 20° to 160° (preferably 60° to 120°, more preferably 80° to 100°). Here, the discharge angle is defined as follows. · The height direction of the electrolytic cell (100) is set to 0°. · The angle of the orientation on the drain port (110) side is negative, and the angle of the orientation on the liquid supply side is positive. · The angle formed by a straight line from the center of the cross-section to the center of the hole (190) (or slit (200)) and a straight line parallel to the height direction is defined as the discharge angle θ.

[0023] 1-4-3. Mounting position of the nozzle (180), etc. The attachment positions of the liquid supply pipe (120) and the nozzle (180) extend along the side surface (the first side surface (130) on the liquid supply pipe side) in contact with the short side of the bottom surface (150) of the electrolytic cell (100) for the purpose of ensuring a certain degree of uniformity at least in the width direction. At this time, the liquid supply pipe (120) extends from the outside to the inside of the electrolytic cell (100), but its position is not particularly limited. Also, the number of liquid supply pipes (120) is not particularly limited.

[0024] For example, any one of several variations shown in FIGS. 7, 8, 9, etc. may be adopted. In FIG. 7, two liquid supply pipes (120) are provided. The two liquid supply pipes (120) extend through the vicinity of the center of the first side surface (130) on the liquid supply pipe side in the height direction, and further bend parallel to the width direction and toward both ends of the first side surface (130) on the liquid supply pipe side near the bottom surface (150).

[0025] In FIG. 8, the two liquid supply pipes (120) extend through both ends of the first side surface (130) on the liquid supply pipe side, and further bend parallel to the width direction and toward the center of the first side surface (130) on the liquid supply pipe side near the bottom surface (150).

[0026] In Fig. 9, there is one liquid supply pipe (120), which extends through one end of the first side surface (130) on the liquid supply pipe side, and further bends near the bottom surface (150) toward the other end.

[0027] Although not shown in Fig. 7, Fig. 8, Fig. 9, etc., the liquid supply pipe (120) does not extend from the upper part of the electrolytic cell (100), and for example, it may be provided to penetrate the first side surface (130) on the liquid supply pipe side of the electrolytic cell (100).

[0028] Also, the position of the nozzle (180) in the height direction is not particularly limited, but it is preferably at the position of the lower end of the electrode (for example, when the positions of the lower ends of the electrodes are different for each electrode, the lower end of the electrode located at the lowest position) or at a position below it. The reason for this is that at such positions, fresh electrolytic solution can be sufficiently supplied to the electrodes.

[0029] 1-5. Plate-like member (230) In one embodiment, for example, as shown in Fig. 10, a plate-like member (230) is provided above the above-described nozzle (180) portion. This is to prevent the electrolytic solution discharged from the nozzle (180) from diffusing to the top side. More specifically, as described above, the electrolytic solution discharged from the nozzle (180) first heads toward the first side surface (130) on the liquid supply pipe side, so there is a possibility that a part of the flow flows upward along the first side surface (130) on the liquid supply pipe side. The presence of the plate-like member (230) can block such a flow and guide the flow toward the drain port (110) side.

[0030] The material and thickness of the plate-shaped member (230) are not particularly limited and may be appropriately determined in consideration of resistance to the electrolytic solution and the like. The width of the plate-shaped member (230) may be sized to fit the inner dimension of the width of the electrolytic cell (100). If the length of the plate-shaped member (230) is too long, it will exceed the positions of the anode (210) and the cathode (220), and fresh electrolytic solution cannot be supplied to these electrodes. Therefore, the length of the plate-shaped member (230) is preferably shorter than the distance from the first side surface (130) on the liquid supply pipe side of the electrolytic cell (100) to the position of the electrode closest to the side surface (FIG. 11).

[0031] In a preferred embodiment, as shown in FIG. 12, the plate-shaped member (230) may form part of the housing (240). And the housing (240) may be configured to house the nozzle (180) portion. In this case, a plurality of holes (250) are provided on a part of the housing (240), that is, the side surface on the drain port (110) side, and the electrolytic solution discharged from the nozzle (180) can be finally discharged. Also, in order to maintain the structural strength of the housing (240), the housing (240) may be provided with a grating structure on the side surface on the drain port (110) side.

[0032] At this time, the sizes of the plurality of holes (250) in the housing (240) may be equal. However, in a preferred embodiment, a part of the plurality of holes (250) in the housing (240) may be configured such that the flow rate is restricted. For example, when viewed in the width direction, the flow rates at both ends may be configured to be restricted. In addition to this, when viewed in the width direction, the flow rate at the central portion may also be configured to be restricted.

[0033] The reason for restricting the flow rates at both ends is that a part of the flow of the discharged electrolytic solution may be accelerated by the repulsion from the wall. In the configuration shown in FIG. 12, in the portions close to both ends, the electrolytic solution discharged from the liquid supply pipe (120) may collide with the wall of the electrolytic cell (100) and be accelerated.

[0034] In addition, in the configuration shown in FIG. 12, the nozzle (180) inside the housing (240) is arranged as shown in FIG. 7. Therefore, at a position closer to the central portion, the pressure from the liquid supply source tends to be stronger compared to both ends. Therefore, the flow rate is restricted not only near both ends but also near the center.

[0035] On the other hand, at a portion that does not correspond to either near both ends or near the center, the size of the holes (250) may be made relatively large. In FIG. 12, there are 14 rectangular holes (250) when counted in the lateral direction. Since the 1st - 2nd and 13th - 14th holes (250) are near both ends, the size of the holes (250) is set relatively small. Also, since the 6th - 9th holes (250) are near the center, the size of the holes (250) is set relatively small. On the other hand, the 3rd - 5th and 10th - 12th holes (250) are set relatively large. Thereby, the uniformity of the liquid supply rate of the electrolytic solution in the width direction can be enhanced.

[0036] When the nozzle (180) of the liquid supply pipe (120) is arranged differently from that in FIG. 7, for example, in the case of the arrangement of the nozzle (180) of the liquid supply pipe (120) as shown in FIG. 9, due to two reasons: the repulsion from the wall and the position close to the liquid supply source, the flow rate on one end side may be the highest. In that case, the flow rate on one end side may be restricted most severely, the flow rate on the other end side may be restricted moderately, and the flow rate in the central portion may not be restricted.

[0037] Also, in the case of the arrangement of the nozzle (180) of the liquid supply pipe (120) as shown in FIG. 8, near both ends, due to the reasons that the distance from the wall is close and the pressure from the liquid supply source is relatively strong, the size of the holes (250) on both end sides may be restricted. And the size of the holes (250) may be set larger as going from both ends toward the vicinity of the center.

[0038] In any case, in order to adjust the flow rate according to the deviation of the flow rate from the nozzle (180), the degree of restricting the flow from the holes (250) of the housing (240) may be adjusted. The same applies when providing slits (200) instead of the holes (250).

[0039] The means for controlling the flow is not particularly limited. For example, the size of the hole (250) itself may be reduced, or a filter may be provided at a portion of the hole (250), or a plate that obstructs the flow may be provided at the outlet of the hole (250).

[0040] By adopting the above configuration, the uniformity of the newly supplied electrolytic solution can be enhanced. Further, by adopting the above configuration, the size required to achieve uniformity can be saved.

[0041] 2. Method for manufacturing a metal material In one embodiment, the present disclosure relates to a method for manufacturing a metal material. In the manufacturing method, the above-described electrolytic cell (100) is used. For example, the metal material can be obtained by the following steps.

[0042] Supplying an electrolytic solution to the above-described electrolytic cell (100). Immersing the anode (210) and the cathode (220) in the electrolytic solution. Applying a voltage to deposit a target metal material on the cathode (220). Appropriately exchanging the electrolytic solution by using the liquid supply pipe (120) and the drain port (110). Peeling the deposited metal material from the cathode (220).

[0043] By the above steps, a metal material of good quality can be manufactured.

[0044] The specific embodiments of the invention have been described above. The above embodiments are merely specific examples, and the present invention is not limited to the above embodiments. For example, the technical features disclosed in one of the above embodiments can be applied to other embodiments. Further, unless otherwise specified, for a specific method, some steps can be interchanged with the order of other steps, and additional steps can be added between two specific steps. The scope of the present invention is defined by the scope of the claims.

Example

[0045] The following shows further specific examples corresponding to some of the embodiments described above. Similar to the embodiments described above, the following description does not limit the scope of the present invention.

[0046] Two liquid supply pipes were passed through the electrolytic cell so as to penetrate the side surface of the electrolytic cell near the center of the side surface where liquid supply is performed. And the two liquid supply pipes were provided so as to extend toward both end sides of the side surface (as shown in FIG. 7). Further, a plurality of holes were provided in the two liquid supply pipes. Note that the plurality of holes are provided on the side surface side so that the discharged electrolytic solution is directed toward the side surface. And the two liquid supply pipes extending inside the electrolytic cell were covered with a housing. The housing is provided with a plurality of holes so that the electrolytic solution inside the housing is directed toward the drain port side. Further, among the plurality of holes provided in the housing, the center and the end portions have smaller hole sizes than the other portions.

[0047] For convenience of the experiment, water was put into the electrolytic cell, and the liquid supplied from the liquid supply pipe was colored so that diffusion could be visually recognized.

[0048] In the structure described above, FIG. 13 shows the state when the colored liquid is supplied from the supply pipe into the electrolytic cell. There was no difference in the shade at any of the holes for the fresh electrolytic solution discharged from the housing. This indicates that the electrolytic solution is supplied relatively uniformly.

Description of reference numerals

[0049] 100 Electrolytic cell 110 Drain port 120 Liquid supply pipe 130 First side surface (liquid supply pipe side) 140 Second side surface (drain port side) 150 Bottom surface 160 Third side surface (longitudinal direction) 170 Fourth side surface (longitudinal direction) 180 Nozzle 190 Hole (hole provided in the nozzle) 200 Slit 210 Anode 220 Cathode 230 Plate-like member 240 Housing 250 Hole (hole provided in the housing)

Claims

1. An electrolytic cell comprising a drain port and a supply pipe for an electrolytic solution, wherein the electrolytic cell includes a bottom surface, a first side surface located on the supply pipe side, a second side surface facing the first side surface and provided with the drain port, a third side surface and a fourth side surface connecting the first side surface and the second side surface, the supply pipe extends along the first side surface in contact with the short side of the bottom surface of the electrolytic cell, a nozzle is provided in the extending portion of the supply pipe, a plate-like member is provided on the top side of the extending portion, the direction of the nozzle is provided such that the electrolytic solution faces the first side surface side, an electrolytic cell.

2. The electrolytic cell according to Claim 1, wherein the nozzle includes a plurality of holes.

3. The electrolytic cell according to Claim 1, wherein the nozzle includes one or more slits.

4. The electrolytic cell according to any one of Claims 1 to 3, wherein the cross-sectional shape of the supply pipe is circular, when the height direction of the electrolytic cell is set to 0° and the angle in the direction of the first side surface side is set to positive, the direction of the discharge holes is set such that the discharge angle is in the range of 20° to 160°, an electrolytic cell.

5. The electrolytic cell according to any one of Claims 1 to 4, wherein the plate-like member constitutes a housing for accommodating the extending portion of the supply pipe, a plurality of holes are provided in the side surface of the housing located on the drain port side of the electrolytic cell, a part of the plurality of holes is configured such that the flow rate is restricted, an electrolytic cell.

6. A method for manufacturing a metal material by electrolytic smelting, the method including using the electrolytic cell according to any one of Claims 1 to 5.

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