JP7150768B2 - Electrolysis apparatus and electrolysis method - Google Patents

Description

TECHNICAL FIELD The present invention relates to an electrolysis device and an electrolysis method.

In a conventional electrolytic device, the electrolyte is supplied and drained from the bottom of one end in the longitudinal direction of the electrolytic cell, and the electrolyte is drained from the top of the other end. has been done. Keeping the liquid composition and additive concentration in the electrolytic cell uniform is one of the important techniques for improving, for example, the quality of electrolytic copper and the electrolysis results, 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 and lower layers of the electrolytic solution, and the liquid on the opposite end side A method of draining from the surface upper layer has been proposed. Japanese Patent Application Laid-Open No. 2015-209550 (Patent Document 2) proposes a method in which an electrolytic solution is supplied from the upper part of one end in the longitudinal direction of the electrolytic cell toward the side surface and drained from the lower part of the other end. there is In addition, as a completely different method, Japanese Patent Application Laid-Open No. 2014-189851 (Patent Document 3) and Japanese Patent No. 5227404 (Patent Document 4) disclose a method of supplying the electrolytic solution from the bottom of the electrolytic cell or the side of the electrolytic cell. is proposed.

Japanese Patent Application Laid-Open No. 2007-204779 JP 2015-209550 A JP 2014-189851 A Japanese Patent No. 5227404

However, as electrolysis progresses, a difference in the concentration of the liquid is created in the electrolytic cell, and the liquid with a higher specific gravity accumulates toward the bottom of the electrolytic cell. Since the liquid supplied from the liquid supply port has a lighter specific gravity than the liquid at the bottom of the electrolytic cell, when the electrolyte solution is supplied and drained by the bottom-up, top-out method as described in Patent Documents 1 and 2, , there is a dead space below the liquid supply position where the electrolyte and additive are not supplied. If there is a region in the electrolytic bath where the additive is not supplied, the surface of the electrodeposit may become rough, and when the electrolytic solution is not supplied, the copper concentration in the solution may partially increase and passivation may easily occur. be.

In the invention described in Patent Document 3, the electrolytic solution is supplied from the lower side of the electrolytic cell and the side of the cathode, and the electrolytic solution is drained from the electrolytic solution discharge port at the top of the electrolytic cell, thereby performing electrolysis on the drain side. It is possible to prevent the increase in copper concentration at the bottom of the tank. However, since the liquid supply side is supplied from above as in the conventional case, there is a dead space below the electrolytic cell on the liquid supply side where the electrolyte is not supplied, and the mixing state in the electrolytic cell cannot be sufficiently improved. I can't say there is.

In the invention described in Patent Document 4, the mixing state of the electrolyte in the electrolytic cell can be improved by supplying the electrolytic solution from the bottom of the electrolytic cell and the side of the electrolytic cell. However, in Patent Document 4, the forced convection of the electrolytic solution from the bottom to the top may cause a problem of contamination of the cathode due to sediments being lifted up.

In view of the above problems, the present disclosure provides an electrolysis apparatus and an electrolysis method capable of more uniformly supplying an electrolytic solution into an electrolytic cell while suppressing the winding up of precipitates.

In one embodiment of the electrolytic device according to the embodiment of the present invention, electrodes arranged at intervals in the longitudinal direction of an electrolytic bath containing an electrolytic solution are immersed in the electrolytic solution, and while the electrolytic solution is circulated An electrolytic device for electrolytic treatment, comprising: a plurality of liquid supply ports for supplying an electrolytic solution spaced apart from each other along a first side wall extending in the longitudinal direction of the electrolytic cell; a gutter portion for accommodating the electrolytic solution, overflowing the electrolytic solution and supplying it into the electrolytic cell; The rectifying plate described above and a plurality of drain ports for draining the electrolytic solution are arranged along the second side wall facing the first side wall below the gutter portion at intervals. It is an electrolytic device.

In one embodiment of the electrolysis method according to the embodiment of the present invention, electrodes arranged at intervals in the longitudinal direction of an electrolytic bath containing an electrolytic solution are immersed in the electrolytic solution, and while the electrolytic solution is circulated An electrolysis method for electrolytic treatment, wherein the electrolytic solution is supplied from a plurality of liquid supply ports spaced apart from each other along a first side wall extending in the longitudinal direction of the electrolytic cell, and is supplied from the liquid supply port One or more rectifying plates arranged in the gutter for containing the electrolytic solution make the flow velocity distribution of the electrolytic solution uniform in the longitudinal direction of the electrolytic cell, causing the electrolytic solution to overflow from the gutter and flow into the electrolytic cell. supplying and draining the electrolytic solution through a plurality of spaced drain ports along a second side wall opposite the first side wall below the gutter. is.

Advantageous Effects of Invention According to the present disclosure, it is possible to provide an electrolysis device and an electrolysis method that can more uniformly supply an electrolytic solution into an electrolytic cell while suppressing the winding up of precipitates.

1 is a schematic top view of an electrolytic device according to an embodiment of the present invention; FIG. It is a schematic diagram showing a positional relationship between a liquid supply pipe and a liquid discharge pipe when the electrolytic device according to the embodiment of the present invention is viewed from the side. FIG. 3(a) is a schematic diagram showing a configuration example of a gutter provided with a rectifying plate according to an embodiment of the present invention, and FIG. 4 is a schematic diagram showing a configuration example of a mechanism; FIG. 4(a), 4(c), and 4(e) are plan views showing examples of arrangement of rectifying ports provided in the rectifying plate according to the embodiment of the present invention. 4(d) and 4(f) are cross-sectional views showing examples of arrangement of rectifying ports provided in the rectifying plate according to the embodiment of the present invention. FIG. 4 is an explanatory diagram showing the arrangement positions of the drainage box and the drainage pipe in the electrolytic cell. FIG. 4 is a schematic top view showing a liquid supply section and a liquid drainage box; FIG. 4 is a schematic cross-sectional view showing how an electrolytic solution flows from a drainage box to a liquid supply section; FIG. 5 is an explanatory diagram showing an example of simulation results when an electrolytic solution is supplied using the electrolytic device according to the embodiment of the present invention; FIG. 4 is a graph showing an example of flow velocity distribution when an electrolytic solution is overflowed from the longitudinal direction of the electrolytic cell using the electrolyzer according to the embodiment of the present invention. FIG.

Hereinafter, an electrolysis device and an electrolysis method according to embodiments of the present invention will be described with reference to the drawings. The embodiments shown below are examples of devices and methods for embodying the technical idea of this invention. are not specific to the following:

(Electrolyzer)
An electrolysis apparatus according to an embodiment of the present invention, as shown in FIG. 1, includes a rectangular parallelepiped electrolytic cell 1 for containing an electrolytic solution. The size of the electrolytic cell 1 is, for example, 5200 to 5900 mm in length (inner diameter in the longitudinal direction X), 1095 to 1110 mm in width (inner diameter in the lateral direction Y), and 1275 to 1510 mm in depth. can be formed as

The electrolytic cell 1 has 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 at one end of the longitudinal direction X the first side wall 11 and the second side wall 12. and a fourth sidewall 14 extending perpendicularly to the first sidewall 11 and the second sidewall 12 at the other end in the longitudinal direction X and facing the third sidewall 13 . and

As shown in FIG. 2 , above the first side wall 11 of the electrolytic cell 1 , the liquid level of the electrolytic solution contained in the electrolytic cell 1 or a height close to the liquid level is provided in the longitudinal direction of the electrolytic cell 1 . Liquid supply pipes 2a, 2b, and 2c are arranged extending along. The liquid supply pipes 2 a , 2 b , 2 c are connected to a liquid supply section 20 arranged above the third side wall 13 of the electrolytic cell 1 for supplying the electrolytic solution.

Although illustration is omitted here, the liquid supply unit 20 can supply the electrolytic solution not only to the electrolytic cell 1 in FIG. 2 but also to other electrolytic cells other than the electrolytic cell 1 in FIG. It is possible to provide a main supply pipe and branch pipes branching the electrolytic solution from the main supply pipe to the supply pipes 2a, 2b, 2c.

The liquid supply pipes 2a, 2b, and 2c preferably supply the electrolytic solution into the electrolytic cell 1 so that the flow rate of the electrolytic solution supplied to 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 is decomposed before it spreads throughout the electrolytic cell 1, which may impair the smoothness of the electrodeposited metal or cause passivation. Although the supply flow rate of the electrolytic solution is preferably high in terms of electrolysis efficiency, if the supply flow rate of the electrolytic solution exceeds 100 L/min, precipitates 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 of the electrolytic solution to the electrolytic cell 1 to be 20 to 100 L/min, the electrolytic solution supplied into the electrolytic cell 1 is suppressed while the precipitation is suppressed. The mixed state can be further improved, and more efficient electrorefining can be carried out. 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.

Liquid supply ports 21 are provided at the tip portions of the liquid supply pipes 2a, 2b, and 2c. The liquid supply ports 21 are preferably provided at regular intervals so as to be spaced apart from each other in the longitudinal direction of the electrolytic cell 1 . As shown in FIG. 2, the liquid supply ports 21 are connected to the bottoms of the gutter portions 4, respectively, and allow the electrolytic solution to flow upward from below the gutter portion 4. As shown in FIG.

The gutter portion 4 is configured to accommodate the electrolytic solution supplied from the plurality of liquid supply ports 21 therein, temporarily store the electrolytic solution, and then overflow the electrolytic solution to supply it into the electrolytic cell 1 . It is As shown in FIG. 1, the gutter portion 4 includes a wall portion 42 extending substantially parallel to the first side wall 11 along the longitudinal direction X of the electrolytic cell 1, and a A plurality of beams 44 are provided to support between the wall 42 and the first side wall 11 so as to leave a constant interval W therebetween. The interval W can be about 10 to 30 mm, more specifically about 15 mm.

As shown in FIG. 1, the wall portion 42 is attached to the gutter portion 4 by inserting and fixing fasteners 47 such as screws into the beam portion 44 from the wall portion 42 side toward the first side wall 11 side. can be removably placed on the Since the wall portion 42 is detachably arranged with respect to the gutter portion 4, it is possible to easily perform the work of removing scale generated due to antimony, which is an impurity in the electrolytic solution, generated inside the gutter portion 4. and simplifies maintenance work.

As shown in FIG. 3( a ), in the gutter portion 4 , one or more rectifying plates 46 a are provided to make the flow velocity of the electrolytic solution supplied into the gutter portion 4 uniform in the longitudinal direction X of the electrolytic cell 1 . , 46b and 46c are provided. Although the number of rectifying plates 46a, 46b, and 46c is not limited, it is more preferable to provide two or more.

As shown in FIG. 2, the rectifying plates 46a, 46b, 46c preferably have a plurality of rectifying ports 45 through which the electrolytic solution flows. Further, it is preferable that the rectifying ports 45 of the upper and lower rectifying plates 46a and 46b are arranged alternately so that the rectifying ports 45 are arranged at different positions in the vertical direction (perpendicular to the paper surface of FIG. 2).

As a result, the electrolytic solution supplied from the liquid supply port 21 toward the top of the gutter portion 4 first collides with the current plate 46 a at the lowest end of the gutter portion 4 and flows in the longitudinal direction of the electrolytic cell 1 . After that, the electrolytic solution passes through the straightening port 45 provided in the straightening plate 46a, collides with the straightening plate 46b above it, and flows in the longitudinal direction of the electrolytic cell 1 between the straightening plates 46a and 46b. The electrolytic solution further passes through the rectifying port 45 provided in the rectifying plate 46b, collides with the rectifying plate 46c located above it, and flows above the gutter portion 4 through the rectifying port 45 provided in the rectifying plate 46c.

In this manner, the electrolytic solution supplied from the liquid supply port 21 is passed through the rectifying ports 45 of the plurality of rectifying plates 46a, 46b, and 46c that are alternately arranged at different positions in the vertical direction. can be expanded in the longitudinal direction of the electrolytic cell 1. As a result, when the electrolytic solution overflows from the opening 41 of the gutter portion 4 , the flow velocity distribution of the overflowing electrolytic solution can be made uniform in the longitudinal direction of the electrolytic cell 1 .

The flow velocity of the electrolytic solution supplied to the gutter portion 4 is the fastest in the vicinity of the liquid supply port 21 . Therefore, if the rectifying port 45 for passing the electrolytic solution is formed directly above the liquid supply port 21, the electrolytic solution flows upward through the rectifying port 45, causing the rectifying plates 46a, 46b, and 46c to flow upward. This makes it difficult to diffuse the electrolytic solution in the longitudinal direction of the electrolytic cell 1 .

In this embodiment, the opening area of the straightening port 45 arranged directly above the liquid supply port 21 is formed smaller than the opening area of the straightening port 45 other than the straightening port 45 located directly above the liquid supply port 21, or the liquid supply port 21 , or the position of the rectifying port 45 is displaced from directly above the liquid supply port 21 . As a result, the electrolytic solution flowing upward from the liquid supply port 21 can be brought into contact with the rectifying plate 46a located directly above the liquid supply port 21, and the electrolytic solution can flow in the longitudinal direction. It can be expanded in the longitudinal direction of the tank 1 . As a result, the flow velocity distribution of the electrolytic solution overflowing from the opening 41 of the gutter 4 can be made uniform in the longitudinal direction of the electrolytic cell 1 .

As shown in FIG. 3, the distance d1 between the rectifying plate 46a arranged directly above the liquid supply port 21 and the bottom surface 48 of the gutter portion 4 for storing the electrolytic solution is equal to the rectifying plate arranged directly above the liquid supply port 21. It is preferable that the heights of the straightening vanes 46a, 46b and 46c are adjusted so as to be narrowest compared to the intervals d2 and d3 between the other straightening vanes 46b and 46 above 46a.

The gap d1 between the rectifying plate 46a arranged directly above the liquid supply port 21 and the bottom surface 48 of the gutter portion 4 is arranged so as to be the narrowest compared to the gaps d2 and d3. The electrolytic solution can be spread in the longitudinal direction of the electrolytic cell 1 while effectively utilizing the flow velocity of the electrolytic solution flowing upward from the opening.

If the straightening plates 46a, 46b, and 46c are arranged too far above the gutter portion 4, the straightening effect may not be obtained. The rectifying plates 46a, 46b, 46c are preferably arranged at a height of 1/2 or less, more preferably 1/3 or less of the height of the gutter portion 4. As shown in FIG.

Although not limited to the following, for example, the height h of the gutter portion 4 is about 150 to 300 mm, the thickness of the rectifying plates 46a, 46b, and 46c is about 2 to 8 mm, the interval d1 is about 5 to 15 mm, and the interval d2 and d3 can be about 20 to 40 mm.

If the opening area of the rectifying port 45 is too small, the resistance of the electrolytic solution flowing through the rectifying port 45 increases, and the flow velocity may decrease too much. For example, as shown in FIGS. 4(a) and 4(b), the rectifying ports 45 of the rectifying plates 46a and 46b are circular in the longitudinal direction of the electrolytic cell 1 at regular intervals and have a constant diameter. When the rectifying ports 45 are arranged at equal intervals, the diameter of the rectifying ports 45 is preferably 8 mm or more, typically about 10 mm, and the interval between adjacent rectifying ports 45 is about 20 to 40 mm, typically is preferably about 30 mm.

In such a configuration, in order to spread the electrolytic solution having a high flow velocity from the liquid supply port 21 more effectively in the longitudinal direction of the electrolytic cell 1, the liquid supply to the first rectifying plate 46a, which is the lowest stage, is required. For example, about 6 to 10 rectifying ports 45 in the vicinity of the port 21 are closed, and 1 to 3 rectifying ports 45 in the vicinity of the liquid supply port 21 of the second stage rectifying plate 46b are preferably closed.

The specific configuration of the rectifying port 45 suppresses the flow of the electrolytic solution directly above the liquid supply port 21, spreads the electrolytic solution in the longitudinal direction of the electrolytic cell 1, and reduces the flow rate of the electrolytic solution overflowing from the gutter portion 4. There is no particular limitation as long as the configuration can be made uniform.

For example, as shown in FIGS. 4(c) and 4(d), rectangular rectifying ports 45 are arranged at different positions in the vertical direction between upper and lower rectifying plates 46a and 46b. good too. As shown in FIGS. 4(e) and 4(f), polygonal (here, triangular) rectifying ports 45 are arranged at different positions in the vertical direction between the upper and lower rectifying plates 46a and 46b. may have been

Further, in order to facilitate the diffusion of the flow of the electrolytic solution supplied from the liquid supply port 21 in the longitudinal direction of the electrolytic cell 1, the opening areas of the plurality of rectifying ports 45 are made larger as the distance from the liquid supply port 21 increases. may be formed.

In this way, the electrolytic solution supplied from the liquid supply pipes 2a, 2b, and 2c is temporarily stored inside the gutter portion 4, and after the flow velocity of the electrolytic solution is adjusted by the rectifying plates 46a, 46b, and 46c, By being supplied into the electrolytic cell 1, the flow velocity distribution of the electrolytic solution overflowing from the opening 41 of the gutter portion 4 is made uniform within the gutter portion 4, so that the electrolytic solution is unevenly distributed throughout the electrolytic cell 1. can be supplied without

In addition, once the electrolytic solution is stored in the gutter portion 4, the components of the electrolytic solution and the additive can be made uniform along the longitudinal direction of the electrolytic cell 1. It is possible to improve the mixed state of the electrolytic solution that is used as a whole. In addition, since the electrolytic solution is supplied into the electrolytic cell 1 by the overflow, the fluctuation of the liquid surface of the electrolytic solution due to the supply of the electrolytic solution can be reduced.

If the height of the opening 41 of the gutter 4 is too high with respect to the liquid surface of the electrolyte, the electrolyte overflowing from the gutter 4 collides with the liquid surface of the electrolyte to generate air bubbles, which affects electrolysis. may affect On the other hand, if the height of the opening 41 of the gutter 4 is lower than the liquid surface of the electrolytic solution, the additive is not supplied to the vicinity of the liquid surface in the electrolytic bath 1, and there is a possibility that the electrodeposition on the upper portion of the electrolytic copper will be rough. .

The height of the opening 41 of the gutter 4 is preferably within 400 mm, more preferably within 200 mm, and even more preferably within 50 mm from the liquid surface of the electrolytic solution. The height h of the gutter portion 4 can be appropriately changed according to the pipe diameters of the liquid supply pipes 2a, 2b, and 2c and the scale of the electrolytic cell 1.

As shown in FIGS. 1 and 2, above the fourth side wall 14 side of the electrolytic cell 1, a draining portion 30 for discharging the electrolytic solution in the electrolytic cell 1 to the outside of the electrolytic cell 1 and a draining portion 30 are provided. There is a drain box 32 connected to. As shown in FIG. 5, a plurality of drainage pipes 3a, 3b, and 3c are connected to the drainage box 32, respectively. The drainage pipes 3a, 3b, 3c are arranged below the liquid supply pipes 2a, 2b, 2c, are fixed on the second side wall 12, extend along the second side wall 12, and are spaced apart from each other. A plurality of drain ports 31 are arranged along the longitudinal direction of the electrolytic cell 1 .

In the example of FIG. 2, the upstream side of the electrolytic cell 1, that is, the electrolytic cell 1 on the side close to the liquid supply unit 20, a drain pipe 3a having a drain port 31 capable of draining the electrolytic solution in the electrolytic cell 1, and the electrolytic cell 1 A drainage pipe 3b provided with a drainage port 31 capable of draining the electrolyte near the center of the electrolyzer 1 The three pipes of the pipe 3c are vertically spaced apart from each other. However, the arrangement of the drainage pipes 3a, 3b, and 3c is of course not limited to the arrangement shown in FIG.

For example, the drain pipe 3a with the longest pipe length is arranged closest to the bottom of the electrolytic cell 1, and the drain pipe 3c with the shortest pipe length is arranged between the three drain pipes 3a and 3b. , 3c can be arranged at the top.

The drain pipes 3 a , 3 b , 3 c are each provided with a drain port 31 on the tip end side opposite to the one end side connected to the drain box 32 . As shown in FIG. 2, when a drainage port 31 is selectively provided at the tip of each of the drainage pipes 3a, 3b, and 3c, and the drainage ports are provided uniformly over the entire one drainage pipe. Compared to, the length along the longitudinal direction of the electrolytic cell 1 in the region where the drain port 31 is formed can be shortened, so the pressure loss can be reduced, and each region where the drain port 31 is arranged It becomes easier to drain the electrolyte solution of the As a result, uneven drainage in the longitudinal direction of the electrolytic cell 1 is less likely to occur.

For example, the liquid discharge port 31 located at the most distal end of each of the liquid discharge pipes 3a, 3b, and 3c is located farthest from the liquid discharge box 32, so the resistance of the electrolyte flowing through the liquid discharge pipes 3a, 3b, and 3c is or pressure loss, etc., the liquid may not be drained sufficiently. As shown in FIG. 2, by arranging the tip portions of the drain ports 31 of the drain pipes 3a, 3b, and 3c so as to overlap each other, the tip portions of the drain pipes 3a, 3b, and 3c are sufficiently can be configured to drain to As a result, it is possible to make it difficult for uneven drainage in the longitudinal direction of the electrolytic cell 1 to occur.

It is preferable that the pipe diameters of the drain pipes 3a, 3b, 3c are larger than the pipe diameters of the liquid supply pipes 2a, 2b, 2c. The pipe diameters of the liquid supply pipes 2a, 2b, and 2c may be the same or different. By making the pipe diameters of the drain pipes 3a, 3b, and 3c larger than the pipe diameters of the liquid supply pipes 2a, 2b, and 2c, the electrolyte is discharged from the drain box 32 to the electrolytic cell by utilizing the head pressure difference of the electrolyte. 1, the influence of pressure loss in the drainage pipes 3a, 3b, and 3c can be reduced. As a result, the electrolytic solution supplied to the liquid supply pipes 2a, 2b, and 2c can be more smoothly discharged to the outside of the electrolytic cell 1. FIG.

The pipe diameters of the drainage pipes 3a, 3b, and 3c can be 1.5 times or more, more preferably 2 times or more, and still more preferably 4 times or more than the pipe diameters of the liquid supply pipes 2a, 2b, and 2c. .

If the height of the drainage pipes 3a, 3b, and 3c is too close to the bottom of the electrolytic cell 1, sediment or the like at the bottom of the electrolytic cell 1 may be caught in the drainage port 31, causing clogging or malfunction. For example, the drain port 31 is preferably arranged in a range of 100 mm upward and 300 mm downward, more preferably 100 mm upward and 300 mm downward, starting from the lower end of the electrode housed in the electrolytic cell 1. They are arranged in a range of 100 mm.

It is preferable that the opening area of the drain port 31 of the liquid drain pipes 3a, 3b, and 3c is larger than the opening area of the liquid supply port 21 of the liquid supply pipes 2a, 2b, and 2c. By increasing the opening area of the drain port 31, the influence of the pressure loss when the electrolyte in the drain pipes 3a, 3b, and 3c is discharged to the outside of the electrolytic cell 1 can be reduced.

Although not limited to the following, the opening area of each drain port 31 can be 1 to 400 times larger than the opening area of each liquid supply port 21, more typically 100 to 200 times larger. As a result, the electrolytic solution in the electrolytic cell 1 can be efficiently drained from the drain port 31 . The shape, hole diameter (slit diameter) and spacing of the liquid supply port 21 and the liquid drain port 31 can be appropriately adjusted according to the size of the electrolytic cell 1 and the like.

As shown in FIG. 6 , the drainage part 30 is provided with a discharge port 300 for discharging the electrolytic solution in the electrolytic cell 1 . As shown in FIG. 7 , a discharge pipe 301 connected to the discharge port 300 is provided below the discharge port 300 to discharge the electrolytic solution to the outside of the electrolytic cell 1 .

The drainage box 32 has a bottom surface 32a below the liquid surface LS of the electrolytic solution shown in FIG. As shown in FIG. 6, the outlets 3A, 3B and 3C of the drainage pipes 3a, 3b and 3c are connected to the bottom surface 32a, respectively. The electrolyte discharged from the electrolytic cell 1 into the drain pipes 3a, 3b, and 3c is pumped up by the height difference H between the liquid level LS of the electrolyte and the liquid level ls of the electrolyte in the drain box 32. be.

By arranging the drainage box 32 between the drainage part 30 and the drainage pipes 3a, 3b, and 3c, the power of a pump or the like is not used, and sediments deposited on the bottom of the electrolytic cell 1 are not involved. The electrolytic solution can be extracted from the bottom of the electrolytic cell 1 to the outside of the electrolytic cell 1 while suppressing the

The height of the upper end of the side wall 32b of the drainage box 32 on the side in contact with the electrolytic solution is arranged to be several mm to several tens of mm above the liquid surface LS of the electrolytic solution in the electrolytic cell 1. . The drainage box 32 is provided with a notch 33 on a side wall 32b on the side that contacts the electrolyte contained in the electrolytic bath 1 for sending foreign matter in the electrolyte in the electrolytic bath 1 to the drainage box 32. is preferred. As shown in FIG. 6, the notch 33 has a shape such that the opening width AW of the electrolytic cell 1 decreases from the upper side to the lower side of the electrolytic cell 1 . The shape of the notch portion 33 may take various shapes such as a V shape, a U shape, and a trapezoidal shape, but the specific shape is not particularly limited.

In the electrolytic cell 1, foreign matter such as dust may accumulate on the liquid surface LS of the electrolytic solution as electrolysis is performed. If this foreign matter stays in the electrolytic cell 1, it may adversely affect electrolysis. According to the electrolytic device according to the embodiment of the present invention, the electrolytic solution containing foreign matter such as dust accumulated in the vicinity of the liquid surface LS of the electrolytic solution in the electrolytic cell 1 can be overflowed from the notch portion 33 and discharged. , stagnation of dust near the liquid surface LS of the electrolytic solution in the electrolytic bath 1 can be suppressed.

As shown in FIG. 6, an adjustment plate 35 is arranged between the drainage box 32 and the drainage section 30 so as to block the electrolyte flowing from the drainage box 32 to the drainage section 30 . ing. By arranging the adjustment plate 35 , the electrolytic solution recovered in the drainage box 32 through the drainage pipe 3 overflows from the upper end of the adjustment plate 35 and flows to the drainage section 30 .

For example, by arranging adjusting plates 35 of different sizes, it is possible to change the height of the adjusting plate 35 from the bottom surface 32 a of the drainage box 32 . By changing the height of the adjustment plate 35, the height difference H between the liquid level LS of the electrolytic solution in the electrolytic bath 1 and the liquid level ls of the electrolytic solution in the drainage box 32 can be adjusted. As a result, the head pressure difference due to 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 is adjusted, and the electrolytic cell 1 The height of the liquid level LS of the internal electrolyte can be kept constant.

Further, 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. preferably. Although it is possible to grasp the amount of electrolyte discharged from each of the outlets 3A, 3B, and 3C without arranging the dividing wall 37, by arranging the dividing wall 37 in the drainage box 32, each The amount of electrolyte discharged from the outlets 3A, 3B, and 3C can be easily grasped by visual observation.

The electrolytic device is provided with an electrolytic solution circulation mechanism (not shown in FIGS. 1 to 7). The circulation mechanism adds additives such as glue and thiourea to the electrolytic solution discharged from the drainage part 30 of the electrolytic cell 1, performs necessary component adjustment and temperature adjustment, and supplies the adjusted electrolytic solution. It is circulated into the electrolytic cell 1 through the pipes 2a, 2b, and 2c. The electrolytic device is provided with a power supply mechanism (not shown). The power supply mechanism includes a power supply device and wiring for applying a direct current between electrodes including anode plates and cathode plates alternately arranged along the longitudinal direction in the electrolytic cell 1 .

The configurations of the anode plate and the cathode plate are not particularly limited. The anode plate serves as an anode for electrorefining or electrowinning, and is composed of a crude metal plate. The cathode plate serves as a cathode for electrorefining or electrowinning, and is made of a highly conductive plate-shaped metal.

Various investigations have been made to improve the mixing state of the electrolyte in the electrolytic cell 1. However, the conventional method of flowing the electrolyte from one longitudinal end of the electrolytic cell 1 to the other longitudinal end has been proposed. In the bottom-up, top-out method electrolysis apparatus, the concentration of metal ions such as copper and the concentration of additives in the electrolyte are uneven between the upstream side and the downstream side in the electrolyte supply direction, and as the electrolysis progresses, The concentration of metal ions tended to increase toward the bottom.

According to the electrolytic device according to the embodiment of the present invention, the electrolytic solution is supplied in the width (Y) direction of the electrolytic cell 1, that is, from the first side wall 11 side of the electrolytic cell 1 to the second side wall 12 side. In addition, the electrolytic solution is allowed to flow out from the opening 41 of the gutter portion 4, and electrolysis is performed through the drainage ports 31 of the drainage pipes 3a, 3b, and 3c relatively below the opening 41. A so-called "horizontal top-loading bottom-loading method" is adopted, which is configured to drain the liquid. As a result, it is possible to effectively suppress an increase in the concentration of metal ions such as the concentration of copper ions at the bottom of the electrolytic cell 1, and to make the concentration distribution of various additives contained in the electrolytic solution more uniform throughout the electrolytic cell 1. can do.

Furthermore, by flowing the electrolytic solution from the upper side to the lower side in the electrolytic cell 1, the risk of sediments being lifted up is reduced. Therefore, even if the supply flow rate of the electrolyte solution is increased, it is possible to improve the mixed state of the electrolyte solution while suppressing the winding up of sediments, and the electrodeposition efficiency of the electrodeposit can also be improved as compared with the conventional method. Furthermore, since the additive such as glue that affects the surface properties of the electrodeposit can be spread evenly over the entire electrolytic cell, electrodeposits of uniform quality can be obtained in the entire electrolytic cell 1 .

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

First, for example, a crude copper plate material with a purity of about 99 mass% is used as an anode plate, a copper plate material with 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 plated. The electrode plates are arranged in the electrolytic cell 1 with a space in the thickness direction so that the lower end of the electrode plate is spaced from the bottom of the electrolytic cell 1 by a predetermined distance and the side surface of the electrode plate does not come into contact with the gutter portion 4 .

Additives such as glue and thiourea are added to the mixed aqueous solution of copper sulfate and sulfuric acid from a plurality of liquid supply ports 21 provided in the liquid supply pipes 2a, 2b, and 2c connected to the liquid supply main pipe arranged in the liquid supply unit 20. Supply the added electrolyte. The electrolytic solution is supplied into the gutter portion 4 from the liquid supply ports 21 of the liquid supply pipes 2a, 2b, and 2c.

Next, the flow of the electrolytic solution supplied from the liquid supply port 21 is adjusted so as to be uniform in the longitudinal direction of the electrolytic cell 1 by one or more rectifying plates 46a, 46b, and 46c. Then, the electrolytic solution is overflowed from the opening 41 of the gutter portion 4 and supplied into the electrolytic bath. On the other hand, the electrolytic solution in the electrolytic cell 1 is drained from the plurality of drain ports 31 of the drain pipes 3 a , 3 b , and 3 c connected to the drain box 32 and the drain section 30 .

A direct current is applied between the anode plate and the cathode plate using a power feeding mechanism, and the copper on the anode plate is eluted into the electrolytic solution as ions and electrodeposited on the cathode plate. The electrolytic solution is supplied into the electrolytic cell 1 through the opening 41 of the gutter portion 4 on the first side wall 11 of the electrolytic cell 1 as described above, and the electrolytic cell 1 opposite to the first side wall 11 is supplied. Below the second side wall 12, the electrolyte is drained into the drain pipes 3a, 3b, 3c to generate a liquid flow.

The electrolytic solution drained into the drain pipes 3 a , 3 b , 3 c is pumped up by the drain box 32 and drained through the drain section 30 . Foreign matter such as dust floating in the upper layer of the electrolytic solution in the electrolytic cell 1 is accommodated in the drainage box 32 by overflow from the notch 33 provided in the drainage box 32, and discharged to the outside of the electrolytic cell 1, The electrolytic solution is circulated by a circulation mechanism (not shown).

According to the electrolysis method according to the embodiment of the present invention, the By flowing the electrolyte solution from a plurality of locations, the mixed state of the electrolyte solution in the electrolytic bath 1 is improved compared to the conventional method of flowing the electrolyte solution from one end side to the other end side in the longitudinal direction X of the electrolytic bath 1. can be

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, resulting in a high current density or It is possible to more efficiently suppress the passivation phenomenon when electrolytic refining is performed using a material with a high impurity concentration for the anode plate.

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

As shown in FIG. 3B, an outflow adjustment mechanism 49 for adjusting the outflow of the electrolyte may be provided at the upper end of the opening 41 of the gutter 4 through which the electrolyte overflows. The outflow rate adjusting mechanism 49 can have, for example, an uneven shape. By arranging the concave portion of the unevenness so as to face the gap between the electrodes, it is possible to make it easier for the electrolytic solution to flow into the gap between the electrodes.

As described above, the present invention is represented by the matters specifying the invention in the scope of claims that are valid from the above disclosure, and can be modified and embodied at the stage of implementation without departing from the gist of the invention.

FIG. 8 shows an example of the configuration of the gutter 4 and an example of simulation results of the flow velocity distribution of the electrolytic solution when three rectifying plates are arranged in the gutter 4 . In this example, the height h of the gutter portion (see FIG. 3A) is 200 mm, and the distance from the wall portion 42 of the gutter portion 4 to the first side wall, that is, the inner diameter of the gutter portion 4 (see FIG. 1) is 15 mm. , the length of the gutter portion 4 in the longitudinal direction of the electrolytic cell 1 was set to 5400 mm. Three straightening plates with a thickness of 5 mm are used, and straightening ports with a diameter of 10mm are arranged at equal intervals of 30mm on each straightening plate. placed in Furthermore, 7 rectifying ports located directly above the liquid supply ports of the lowermost rectifying plate were closed, and 2 rectifying ports located directly above the liquid supply ports of the middle rectifying plate were closed. The distance d1 (see FIG. 3(a)) between the bottom rectifying plate and the bottom surface of the gutter portion is 10 mm, and the distances d2 and d3 (see FIG. 3(a)) between the bottom and middle rectifying plates and between the middle and upper rectifying plates. was set to 30 mm, and the electrolytic solution was supplied from the liquid supply port 21 at a flow rate of 1.35 m/s.

As shown in FIG. 8, according to the present embodiment, a region where the flow rate of the electrolytic solution is high is not formed around the liquid supply port 21, and the lowermost rectifying plate 46a and the bottom surface of the gutter portion 4 are not formed. It can be observed that the electrolytic solution spreads well in the longitudinal direction in the region between them. Further, it was found that the electrolytic solution can be discharged from the rectifying port 45 at substantially the same flow rate as the rectifying plates 46b and 46c on the upper stage are approached.

FIG. 9 is an example of a graph showing the flow velocity distribution of the electrolytic solution overflowing from the gutter portion 4 by simulation . Numbers 1 to 3 in FIG. 9 correspond to the positions of the liquid supply port 21 . As shown in FIG. 9, the flow velocity of the electrolytic solution flowing out from the vicinity of the liquid supply port 21 is suppressed in the range of 2.7 to 3.5 cm/s in the longitudinal direction, and the overflow from the gutter portion 4 It can be seen that the flow velocity of the supplied electrolytic solution can be averaged within a certain range in the longitudinal direction.

REFERENCE SIGNS LIST 1 electrolytic baths 2a, 2b, 2c liquid supply pipes 3a, 3b, 3c drainage pipes 4 gutter 11 first side wall 12 second side wall 13 third side wall 14 fourth side wall 20... Liquid supply part 21... Liquid supply port 30... Liquid drain part 31... Liquid drain port 32b... Side wall 32a... Bottom surface 32... Liquid drain box 33... Notch 35... Adjusting plate 37... Divided wall 41... Opening 42... Wall portion 44 Beam portion 45 Straightening ports 46a, 46b, 46c Straightening plate 47 Fixing tool 48 Bottom surface 49 Outflow adjusting mechanism 300 Discharge port 301 Discharge pipe

Claims (8)

An electrolysis device that performs electrolysis while circulating the electrolyte by immersing electrodes arranged at intervals in the longitudinal direction of an electrolytic bath containing the electrolyte in the electrolyte,
a plurality of liquid supply ports spaced apart from each other along a first longitudinally extending side wall of the electrolytic cell for supplying an electrolytic solution;
a gutter containing the electrolytic solution supplied from the liquid supply port, overflowing the electrolytic solution and supplying it into the electrolytic cell;
one or more rectifying plates provided in the gutter portion for uniformizing the flow velocity distribution of the electrolytic solution in the longitudinal direction of the electrolytic cell;
an electrolytic device comprising a plurality of drain ports for draining the electrolytic solution, which are spaced apart from each other along a second side wall facing the first side wall below the gutter. 2. The electrolysis according to claim 1, wherein said one or more rectifying plates are provided with a plurality of rectifying ports for passing said electrolytic solution, and said rectifying ports of said upper and lower rectifying plates are arranged at mutually different positions in the vertical direction. Device. The one or more rectifying plates are provided with a plurality of rectifying ports for passing the electrolytic solution,
The opening area of the straightening port arranged immediately above the liquid supply port is formed to be smaller than the opening area of the straightening port other than the straightening port located directly above the liquid supply port, or the straightening port directly above the liquid supply port 2. The electrolysis device according to claim 1, wherein the rectifying port is arranged to be shifted from directly above the liquid supply port. The distance between the rectifying plate arranged directly above the liquid supply port and the bottom surface of the gutter portion is compared with the distance between the other rectifying plates located above the rectifying plate arranged directly above the liquid supply port. 2. The electrolytic device of claim 1, including being arranged to be narrowest at the The electrolysis apparatus according to any one of claims 1 to 4, wherein the rectifying plate is arranged at a height equal to or less than 1/2 of the height of the gutter portion. The electrolytic device according to any one of claims 2 to 5, wherein the opening area of the rectifying port is formed so as to increase with increasing distance from the liquid supply port. 7. Any one of claims 1 to 6, wherein the gutter includes an opening for overflowing the electrolytic solution, and the opening is arranged at a height within 50 mm from the liquid surface of the electrolytic solution. 2. The electrolytic device according to item 1. An electrolysis method in which electrodes arranged at intervals in the longitudinal direction of an electrolytic bath containing an electrolytic solution are immersed in the electrolytic solution, and electrolytic treatment is performed while the electrolytic solution is circulated,
supplying an electrolytic solution from a plurality of liquid supply ports spaced apart from each other along a first side wall extending in the longitudinal direction of the electrolytic cell;
The flow velocity distribution of the electrolytic solution is made uniform in the longitudinal direction of the electrolytic cell by one or more rectifying plates arranged in a gutter portion for containing the electrolytic solution supplied from the liquid supply port, thereby distributing the electrolytic solution. Overflow from the gutter and supply into the electrolytic cell,
Draining the electrolytic solution through a plurality of drain ports spaced apart from each other along a second side wall facing the first side wall below the gutter. .

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