JP6929320B2 - Electrolyzer and electrolysis method - Google Patents

Description

The present invention relates to an electrolyzer and an electrolyzer.

In the conventional electrolyzer, the electrolyte is supplied from the lower part on one end side in the longitudinal direction of the electrolytic cell, and the electrolyte is discharged from the upper part on the other end side. 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 solution, 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 the electrolytic solution is supplied toward the side surface from the upper part of one end in the longitudinal direction of the 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 Japanese Unexamined Patent Publication No. 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. The liquid supplied from the liquid supply port has a lighter specific gravity than the liquid at the bottom of the electrolytic cell. 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 the additive is not 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. be.

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 the problem of cathode contamination due to the hoisting of the ridge and the like may occur.

In view of the above problems, the present disclosure provides an electrolyzer and an electrolysis method capable of improving the mixed state of the electrolytic solution supplied into the electrolytic cell while suppressing the hoisting of the ridge.

In one embodiment, the electrolytic device according to the embodiment of the present invention circulates the electrolytic cell by immersing the electrodes arranged at intervals along the longitudinal direction of the electrolytic cell accommodating the electrolytic cell in the electrolytic cell. A liquid supply pipe that extends along a first side wall extending in the longitudinal direction of the electrolytic cell and has a plurality of liquid supply ports arranged at intervals from each other, and a liquid supply pipe. A gutter that extends along the first side wall so as to house the electrolyte, stores the electrolytes supplied from the plurality of liquid supply ports, overflows the electrolytes from the upper part, and supplies the electrolytes into the electrolytic cell. It has a plurality of drainage ports extending along the second side wall facing the first side wall, arranged below the gutter portion, and arranged at intervals from each other, and from the drainage port into the electrolytic cell. It is an electrolytic device provided with a drainage pipe for draining the electrolytic solution.

In one embodiment of the electrolytic method according to the embodiment of the present invention, electrodes arranged at intervals along the longitudinal direction of an electrolytic cell accommodating the electrolytic cell are immersed in the electrolytic solution, and the electrolytic solution is circulated. This is an electrolytic method for performing electrolytic treatment while performing electrolytic treatment, in which the electrolytic solution is supplied to a liquid supply pipe provided with a plurality of liquid supply ports extending along a first side wall extending in the longitudinal direction of the electrolytic cell and supplying the electrolytic solution into the electrolytic cell. The electrolytic solution supplied from the liquid supply pipe is housed in a gutter extending along the first side wall so as to supply and house the liquid supply pipe inside, and the stored electrolyte solution overflows from the upper part of the gutter. A drainage pipe that supplies into the electrolytic cell, extends along the second side wall facing the first side wall, is arranged below the gutter, and has a plurality of drainage ports arranged at intervals from each other. It is an electrolytic method including draining the electrolytic solution in the electrolytic cell.

According to the present disclosure, it is possible to provide an electrolyzer and an electrolyzing method capable of improving the mixed state of the electrolytic solution supplied into the electrolytic cell while suppressing the hoisting of the tongue.

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 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 in 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 a liquid level of the electrolytic cell housed in the electrolytic cell 1 or at a height close to the liquid level. 2 is arranged. The liquid supply pipe 2 is connected to a liquid supply unit 20 arranged above the third side wall 13 of the electrolytic cell 1. The liquid supply unit 20 can supply the electrolytic solution to other electrolytic cells other than the electrolytic cell 1 in addition to the electrolytic cell 1 shown in FIGS. 1 (a) and 1 (b). A 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 it is needless to say that the present invention is not limited to this example.

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.

A plurality of liquid supply ports 21a, 21b ... 21x are preferably provided at equal intervals on the upper portion of the liquid supply pipe 2 along the longitudinal direction X. The number of the plurality of liquid supply ports 21a, 21b ... 21x is not particularly limited. As shown in FIG. 2, the gutter portion 4 is arranged above the first side wall 11 of the electrolytic cell 1, accommodates the liquid supply pipe 2 inside, and extends along the longitudinal direction of the first side wall 11. There is.

The gutter portion 4 has a concave shape for storing the electrolytic solution supplied from the plurality of liquid supply ports 21a, 21b ... 21x of the liquid supply pipe 2. As shown in FIG. 1, the gutter portion 4 is fixed on the first side wall portion 11 and is constant with the first wall portion 42 extending along the longitudinal direction of the first side wall portion 11 and the first wall portion 42. A second wall portion 43 facing each other at intervals, a plurality of beam portions 44 supporting the first wall portion 42 and the second wall portion 43, and a bottom surface invisible from FIG. 1 can be provided.

The beam portion 44 has a certain distance between the first wall portion 42 and the second wall portion 42 so as to support the first wall portion 42 and the second wall portion 43. The number of the beam portions 44 is not particularly limited as long as they are provided and a plurality of the beam portions 44 are arranged. The distance between the first wall portion 42 and the second wall portion 43 is not particularly limited as long as it has a distance that does not collide with the electrode inserted into the electrolytic cell 1. The gutter portion 4 can be formed of a material having corrosion resistance to an electrolytic solution, for example, stainless steel (SUS), vinyl chloride, fiber reinforced plastic (FRP), or the like.

A plurality of openings 41a, 41b, 41x are formed above the gutter portion 4. The electrolytic solution is supplied from the plurality of liquid supply ports 21a, 21b ... 21x of the liquid supply pipe 2 and temporarily stored inside the gutter portion 4. A part of the electrolytic solution stored inside the gutter portion 4 overflows from the openings 41a, 41b, 41x and flows into the electrolytic cell 1.

As described above, the difference generated in the elongated liquid supply pipe 2 is caused by the electrolytic solution supplied from the liquid supply pipe 2 being temporarily stored inside the trough 4 and then supplied into the electrolytic cell 1. Since the pressure is made uniform in the trough portion 4, the electrolytic solution can be supplied evenly over the entire electrolytic cell 1. Further, since the electrolytic solution is once stored in the trough 4, the components of the electrolytic solution and the additive can be made uniform along the longitudinal direction of the electrolytic cell 1, so that the liquid is supplied into the electrolytic cell. It is possible to improve the mixed state of the electrolytic solution as a whole. Further, since the electrolytic solution is supplied into the electrolytic cell 1 by overflow, the power of a pump or the like for extracting and discharging the electrolytic solution from the inside of the gutter portion 4 to the outside of the gutter portion 4 becomes unnecessary, and the device can be simplified. It can be planned.

If the height of the openings 41a, 41b, ... 41x of the gutter portion 4 is too high with respect to the liquid level of the electrolytic solution, the electrolytic solution overflowing from the gutter portion 4 collides with the liquid level of the electrolytic solution and bubbles are generated. It may occur and affect electrolysis. On the other hand, when the heights of the openings 41a, 41b, ... 41x of the gutter portion 4 are lower than the liquid level of the electrolytic solution, the electrolytic solution in the electrolytic cell 1 flows into the gutter portion 4 side, and the liquid supply is smooth. It may not proceed to. The heights of the openings 41a, 41b, ... 41x of the gutter portion 4 are arranged at a height within 400 mm, more preferably within 200 mm, and further preferably within 50 mm from the liquid level of the electrolytic solution. It is preferable to be done.

The width of the gutter portion 4 along the depth direction of the electrolytic cell 1 can be appropriately changed according to the pipe diameter of the liquid supply pipe 2 and the device scale of the electrolytic cell 1. In the example of FIG. 1, an example in which the width of the gutter portion 4 along the depth direction is 50 to 100 mm is shown, but in order to make the pressure bias of the electrolytic solution supplied to the gutter portion 4 more uniform. In addition, the width of the gutter portion 4 along the depth direction of the gutter portion 4 may be made larger than 100 mm.

As shown in FIG. 2, below the liquid supply pipe 2, the electrolytic solution fixed on the first side wall 11 and supplied from the liquid supply unit 20 is supplied from the upstream side along the longitudinal direction of the electrolytic cell 1. An auxiliary pipe 5 for supplying to the downstream side is provided. The auxiliary pipe 5 is connected to the central portion in the longitudinal direction of the liquid supply pipe 2 via the supply portions 51 and 52 arranged in the central portion in the longitudinal direction of the electrolytic cell 1. The electrolytic solution supplied from the liquid supply unit 20 flows into the liquid supply pipe 2 via the supply units 51 and 52 of the auxiliary pipe 5.

A large amount of the electrolytic solution supplied to the liquid supply pipe 2 flows out from the drainage port 31a side on the third side wall 13 side of the electrolytic cell 1 near the liquid supply unit 20, and the drainage liquid on the fourth side wall 14 side. The electrolyte may not flow out sufficiently as it progresses to the mouth 31x. As shown in FIG. 2, the electrolytic solution is also supplied from the longitudinal central portion of the liquid supply pipe 2 via the auxiliary pipe 5, so that the electrolytic solution is sufficiently supplied to the longitudinal central portion of the liquid supply pipe 2. Therefore, the electrolytic solution can be supplied more uniformly over the entire electrolytic cell 1.

Further, at the tip of the liquid supply pipe 2 provided with the liquid supply port 21x that minimizes the supply amount of the electrolytic solution on the downstream side in the longitudinal direction, the liquid supply pipe 2 is fixed on the first side wall 11 further below the auxiliary pipe 5. , An auxiliary pipe 6 extending in the longitudinal direction of the first side wall 11 and having a tip connected to the tip of the liquid supply pipe 2 is arranged. A supply unit 61 is provided at the tip of the auxiliary pipe 6, and the electrolytic solution supplied from the liquid supply unit 20 via the supply unit 61 is supplied to the tip of the auxiliary pipe 6. As a result, the electrolytic solution is also supplied from the distal end portion of the liquid supply pipe 2 in the longitudinal direction via the auxiliary pipe 6, so that the electrolytic solution can be supplied more uniformly over the entire electrolytic cell 1.

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. 3, 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, are fixed on the second side wall 12, extend along the second side wall 12, and are spaced from each other. A plurality of drainage ports 31a to 31x arranged along the longitudinal direction of the electrolytic cell 1 are provided.

In the example of FIG. 2, the drainage pipe 3a provided with the drainage ports 31a, 31b, 31c capable of draining the electrolytic solution in the electrolytic solution tank 1 on the upstream side of the electrolytic tank 1, that is, the side close to the liquid supply unit 20. , The drainage pipe 3b provided with the drainage ports 31d, 31e, 31f capable of draining the electrolytic solution near the center of the electrolytic tank 1 and the electrolytic solution on the side close to the drainage box 32 of the electrolytic tank 1 can be drained. Three drainage pipes 3c having drainage ports 31g and 31x are arranged vertically separated from each other. However, it goes without saying that the arrangement of the drainage pipes 3a, 3b, and 3c is not limited to the arrangement shown in FIG.

For example, the drainage pipe 3a having the longest pipe length is arranged at a position closest to the bottom of the electrolytic tank 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. As shown in FIG. 2, by selectively providing the drainage ports 31a to 31x at the tips of the drainage pipes 3a, 3b, and 3c, the drainage ports are uniformly provided over the entire one drainage pipe. Compared with the case where the drainage ports 31a to 31x are formed, the lengths of the electrolytic tanks 1 along the longitudinal direction can be shortened, so that the pressure loss can be reduced and the drainage ports 31a to 31x can be reduced. It becomes easier to drain the electrolytic solution in each region where the is arranged more efficiently. As a result, uneven drainage of the electrolytic cell 1 in the longitudinal direction is less likely to occur.

Since the drainage ports 31a, 31d, and 31g at the most advanced portions of the drainage pipes 3a, 3b, and 3c are located farthest from the drainage box 32, they flow in the drainage pipes 3a, 3b, and 3c. Due to the resistance of the electrolytic solution, pressure loss, etc., the solution may not be sufficiently drained. As shown in FIG. 2, the tips of the drainage ports 31a to 31x of the drainage pipes 3a, 3b, and 3c, that is, the drainage port 31c and the drainage port 31d, and the drainage port 31f and the drainage port 31g are mutually connected. By arranging 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. This makes it possible to prevent uneven drainage of the electrolytic cell 1 in the longitudinal direction.

The pipe diameters of the drainage pipes 3a, 3b, and 3c are preferably configured to be larger than the pipe diameters of the liquid supply pipes 2 and the auxiliary pipes 5 and 6. The pipe diameters of the liquid supply pipe 2 and the auxiliary pipes 5 and 6 may be the same or different. 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 diameters of the drainage pipes 3a, 3b, and 3c should be 1.5 times or more, more preferably 2 times or more, still more preferably 4 times or more larger than the pipe diameters of the liquid supply pipes 2 and the auxiliary pipes 5 and 6. Can be done.

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.

The opening area of the drainage ports 31a, 31b ... 31x provided in the drainage pipes 3a, 3b, 3c is larger than the opening area of the liquid supply ports 21a, 21a, 21c ... 21x provided in the liquid supply pipe 2. It is preferably formed in. By increasing the opening area of the drainage ports 31a, 31b ... 31x, the influence of pressure loss when discharging the electrolytic solution in the drainage pipes 3a, 3b, 3c 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.

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. 4, 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. 5, a discharge pipe 301 connected to the discharge port 300 is provided below the discharge port 300 in order to discharge the electrolytic solution to the outside of the electrolytic cell 1.

The drainage box 32 includes a bottom surface 32a below the liquid level LS of the electrolytic solution shown in FIG. As shown in FIG. 4, the bottom 32a is connected to the outlets 3A, 3B, and 3C of the drainage pipes 3a, 3b, and 3c, respectively. The electrolytic solution discharged from the electrolytic cell 1 into the drainage pipes 3a, 3b, and 3c is pumped up by 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. NS.

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 electrolyte solution in the electrolytic cell 1 to the drainage box 32 on the side wall 32b on the side in contact with the electrolytic solution 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 decreases from the upper side to the lower side of the electrolytic cell 1. The shape of the cutout portion 33 may be various shapes such as a V-shape, a U-shape, and a trapezoidal shape, 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 FIGS. 4 and 5, an adjusting plate 35 is arranged between the drainage box 32 and the drainage section 30 so as to block the electrolytic solution flowing from the drainage box 32 to the drainage section 30. Is placed. 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.

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. Is preferable. Although it is possible to grasp the amount of the electrolytic solution discharged from each of the outlets 3A, 3B, and 3C without arranging the dividing wall 37, each of the divided walls 37 is arranged in the drainage box 32. The amount of electrolytic solution discharged from each of the outlets 3A, 3B, and 3C can be easily visually grasped.

The electrolytic apparatus is provided with a circulation mechanism of an electrolytic solution (not shown) shown in FIGS. 1 to 5. The recirculation mechanism adds additives such as nikawa and thiourea to the electrolytic solution discharged from the drainage unit 30 of the electrolytic cell 1, adjusts necessary components and adjusts the 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 the electrodes including the anode plate and the cathode plate which 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 electrorefining 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 cell in the electrolytic cell 1, but the conventional method of flowing the electrolytic cell from one end side in the longitudinal direction to the other end side in the longitudinal direction in the electrolytic cell 1. 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 cell 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 liquid 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 metal ion concentration such as 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 ridge 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 ridge, and the electrodeposition efficiency of the electrodeposited object can be improved as compared with the conventional case. Further, since additives such as glue that affect the surface properties 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 or a stainless steel plate having a purity of about 99.99 mass% 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 at intervals in the thickness direction so that the lower ends of the electrode plates are spaced apart from the bottom surface of the electrolytic cell 1 by a predetermined distance and the side surfaces of the electrode plates do not come into contact with the trough portion 4.

Addition of nikawa, thiourea, etc. to a mixed aqueous solution of copper sulfate and sulfuric acid from a plurality of liquid supply ports 21a, 21b ... 23x provided in the liquid supply pipe 2 connected to the liquid supply main pipe arranged in the liquid supply unit 20. The electrolytic solution to which the agent is added is supplied. Further, the electrolytic solution is supplied from the auxiliary pipe 5 and the auxiliary pipe 6 to the central portion and the tip portion in the longitudinal direction of the liquid supply pipe 2. The electrolytic solution supplied by the liquid supply pipe 2 and the auxiliary pipes 5 and 6 is stored in the gutter portion 4. Then, the electrolytic solution stored in the gutter portion 4 overflows from the openings 41a, 41b ... 41x at the upper part of the gutter portion 4 and is supplied into the electrolytic cell 1. On the other hand, the electrolytic solution in the electrolytic cell 1 is drained from the plurality of drainage ports 31a, 31b ... 31x of the drainage pipes 3a, 3b, 3c connected to the drainage box 32 and the drainage unit 30, and the electrolyte is not discharged. The electrolytic solution is circulated by the shown circulation mechanism.

A direct current is applied between the anode plate and the cathode plate using 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. As described above, the electrolytic solution is supplied into the electrolytic cell 1 from above the gutter 4 on the first side wall 11 of the electrolytic cell 1, and the second side of the electrolytic cell 1 facing the first side wall 11 is supplied. A liquid flow is generated by draining the electrolytic solution into the 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 in which the electrolytic cell is flown 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 immobilization 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. This disclosure will reveal to those skilled in the art various alternative embodiments and operational techniques.

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 pipes 3a, 3b, and 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. The drainage pipes 3a, 3b, and 3c can be configured by one pipe instead of a plurality of pipes. Further, it goes without saying that the liquid supply pipe 2 may be composed of a plurality of pipes.

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 ... Electrolyte tank 2 ... Liquid supply pipe 3 (3a, 3b, 3c) ... Drainage pipe 4 ... Hidden part 5 ... Auxiliary pipe 6 ... Auxiliary pipe 11 ... First side wall 12 ... Second side wall 13 ... Third side wall Side wall 14 ... Fourth side wall 20 ... Liquid supply section 21a to 21x ... Liquid supply port 30 ... Drainage section 31a to 31x ... Drainage port 32 ... Drainage box 32 ... Wall section 32a ... Bottom surface 32b ... Side wall 33 ... Notch Part 35 ... Adjusting plate 37 ... Dividing wall 41a to 41x ... Opening 42 ... First wall part 43 ... Second wall part 44 ... Beam part 51, 52, 61 ... Supply part 300 ... Discharge port 301 ... Discharge pipe

Claims (9)

An electrolytic device in which electrodes arranged at intervals along the longitudinal direction of an electrolytic cell accommodating an electrolytic solution are immersed in the electrolytic solution and electrolyzed while circulating the electrolytic solution.
A liquid supply pipe extending along a first side wall extending in the longitudinal direction of the electrolytic cell and having a plurality of liquid supply ports arranged at intervals from each other.
It extends along the first side wall so as to accommodate the liquid supply pipe, stores the electrolytic solution supplied from the plurality of liquid supply ports, overflows the electrolytic solution, and supplies the electrolytic solution into the electrolytic cell. Hibe and
A plurality of drainage ports extending along a second side wall facing the first side wall, arranged below the gutter portion, and arranged at intervals from each other are provided, and the electrolysis is performed from the drainage port. An electrolytic device characterized by being provided with a drainage pipe for draining the electrolytic solution in the tank. The electrolyzer according to claim 1, further comprising an auxiliary pipe connected to a central portion in the longitudinal direction of the liquid supply pipe and supplying an electrolytic solution to the liquid supply pipe. The electrolyzer according to claim 1 or 2, further comprising an auxiliary pipe connected to a tip on the downstream side in the longitudinal direction of the liquid supply pipe and supplying an electrolytic solution to the drainage pipe. Any of claims 1 to 3, wherein the gutter portion is provided with an opening for overflowing the electrolytic solution, and the opening is arranged at a height within 50 mm from the liquid surface of the electrolytic solution. The electrolyzer according to item 1. It is provided with a bottom surface below the liquid level of the electrolytic solution, an outlet of the drainage pipe is connected to the bottom surface, and a drainage box capable of pumping the electrolytic solution in the drainage pipe is further provided. The electrolyzer according to any one of claims 1 to 4. The claim is characterized in that the drainage box is provided with a notch for sending foreign matter in the electrolytic solution in the electrolytic cell to the drainage box on a side wall on the side of the electrolytic cell in contact with the electrolytic solution. Item 5. The electrolyzer according to Item 5. A drainage unit for discharging the electrolytic solution in the drainage box to the outside of the electrolytic cell is provided.
An adjusting plate that is arranged between the drainage box and the drainage portion and adjusts the difference between the height of the electrolyte level in the drainage box and the height of the electrolyte level in the electrolytic cell. The electrolyzer according to claim 5 or 6, further comprising. The electrolyzer according to any one of claims 1 to 7, wherein the drainage pipe includes at least two or more pipes. 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 for electrolytic treatment.
The electrolytic solution is supplied to a liquid supply pipe provided with a plurality of liquid supply ports extending along a first side wall extending in the longitudinal direction of the electrolytic cell and supplying the electrolytic cell into the electrolytic cell.
The liquid supply pipe is housed inside, the electrolytic solution supplied from the liquid supply pipe is stored in a gutter extending along the first side wall, and the stored electrolytic solution is overflowed from the upper part of the gutter. Supply into the electrolytic cell
Inside the electrolytic cell from a drainage pipe having a plurality of drainage ports extending along a second side wall facing the first side wall, arranged below the gutter portion, and arranged at intervals from each other. An electrolysis method that involves draining the electrolyte.

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