KR20210033321A - A supplement device of a copper pellet and an Electrolytic refining Apparatus using the supplement device of a copper - Google Patents

Abstract

The present invention relates to an electrolytic refining aid device of a copper pellet and an electrolytic refining apparatus using the same, which can efficiently obtain ultrapure copper. To this end, the electrolytic refining apparatus of copper comprises: an aid device (100) including a position fixing means installed in an electrolytic refining reaction tank (200) of copper, and an inclined plate (140) which is connected to the position fixing means, accommodates copper pellets (10), and guides the copper pellets (10) to come in contact with polar plates in the reaction tank (200); a reaction tank (200) allowing the aid device (100) to be fixed on an upper portion thereof; an anode plate (210) and a cathode plate (220) separated from each other in the reaction tank (200) to be installed; and an electrolyte (240) filled in the reaction tank (200).

Description

A supplement device of a copper pellet and an Electrolytic refining Apparatus using the supplement device of a copper}

The present invention relates to an electrolytic refining apparatus for copper, and more specifically, an auxiliary apparatus for electrorefining copper pellets capable of recovering high-purity copper from an anode through electrolytic refining by using copper pellets as coarse copper, and using the same. It relates to an electrolytic refining device.

Generally, copper plating, Waste nitric acid is generated in the manufacturing equipment washing process and the like. For example, when manufacturing printed circuit board (PCB), which is a core material in the electronics industry, a large amount of waste acid containing copper is generated, and it is generated in the form of waste copper chloride, waste copper sulfate, and waste copper nitrate.

Waste copper chloride and waste copper sulfate are easy to recycle because iron or aluminum is added to the waste acid and copper is concentrated and recovered through a substitution reaction, so that many recycling technologies have been developed and commercialized.

On the other hand, nitric acid generates a large amount of nitrogen oxide (NOx) fumes, unlike hydrochloric acid and sulfuric acid, and it is difficult to recover copper through a substitution reaction using iron or aluminum. Therefore, it is known that the only method of recovering copper-containing waste nitric acid by neutralizing nitric acid, which is a strong inorganic acid, precipitates copper in the form of hydroxide. In addition, there is no case of commercialization due to excessive cost of chemicals such as sodium hydroxide, calcium hydroxide, and potassium hydroxide used as neutralizing agents.

In addition, the waste liquid generated after neutralization incurs enormous costs during wastewater treatment because of a very high nitrogen concentration (T-N, total nitrogen) caused by nitric acid.

When copper is recovered through copper extraction processes such as organic solvent extraction method, metal hydroxide precipitation method, and electro-collection method, the waste nitrate containing 3 to 8% by weight of copper is high compared to the economic benefits of copper recycling and a large amount of waste liquid. There is a problem in that the cost of wastewater treatment by the amount of generation is significant, and the economic value is remarkably reduced. Accordingly, 3 to 8% by weight of copper-containing waste nitric acid is buried after dilution and neutralization treatment without a copper extraction process.

In particular, among the wet extraction methods of copper, the precipitation method (ion exchange method) and the electrolytic extraction method are representative. Among them, the electrolytic extraction method is widely used because of its high efficiency, and in the process of electrorefining ultra-high purity (99.99%) dml copper, copper of high purity (99% or more) is molded into a plate shape and used in a little speed. However, in order to mold such high-purity copper into a plate shape, there is a disadvantage in that a lot of energy is consumed because it must be melted using a furnace.

Korean Patent Application Publication No. 2008-00730038

An object of the present invention is to provide an electrolytic refining apparatus for copper pellets capable of efficiently obtaining ultra-high-purity copper by directly using high-purity copper in the form of pellets without melt-molding, and an electrolytic refining apparatus using the same.

However, the technical problems to be achieved in the present invention are not limited to the technical problems mentioned above, and other technical problems that are not mentioned are clearly to those of ordinary skill in the technical field to which the present invention belongs from the following description. It will be understandable.

In order to achieve the object of the present invention as described above, the position fixing means installed in the electrorefining reaction tank 200 of copper; And it is connected to the position fixing means, while receiving the copper pellets 10, while guiding the copper pellets 10 to contact the electrode plate in the reaction tank 200; electrolysis of copper pellets comprising a. A refining aid is provided.

In addition, the position fixing means, a pair of upper fixing plates 110 that are installed spaced apart from each other; And a seating groove 115 that is recessed in the lower portion of the upper fixing plate 110, and the seating groove 115 is seated on a horizontal beam 230 installed horizontally in the reaction tank 200 so that the position is fixed. I can.

In addition, the first plate 120 is assembled to the pair of upper fixing plate 110; And a second plate 130 assembled to the pair of upper fixing plates 110 while being spaced apart from the first plate 120, wherein the swash plate 140 includes a lower portion of the first plate 120 and the It may be installed between the lower portions of the second plate 130.

Further, the electrode plate is a positive electrode plate 220.

In addition, a plurality of copper pellets 10 may be accommodated between the swash plate 140 and the positive plate 220.

In addition, the swash plate 140 may include a vertical portion 260 extending vertically from a lower portion of the swash plate 140; And a closing portion extending from the lower portion of the vertical portion 260 toward the positive electrode plate 220, but extending to maintain a gap between the vertical portion 260 and the positive electrode plate 220 so that the copper pellet 10 can be inserted. (270); may further include.

In addition, the auxiliary device 100 may be made of a synthetic resin material or acrylic.

An object of the present invention as described above, as another embodiment, in the copper electrolytic refining apparatus, the above-described auxiliary device (100); A reaction tank 200 in which the auxiliary device 100 is fixed at the top; A negative electrode plate 210 and a positive electrode plate 220 installed to be spaced apart from each other in the reaction tank 200; And it can be achieved by an electrolytic refining apparatus using an auxiliary apparatus for copper pellets comprising; and an electrolyte solution 240 filled in the reaction tank 200.

In addition, the negative electrode plate 210 includes copper or stainless steel.

In addition, the positive electrode plate 220 may include one of ruthenium (Ru) coating, iridium (Ir) coating, and titanium.

In addition, the electrolyte solution 240 is an H ₂ SO ₄ solution.

One of the pair of upper fixing plates 110 is further extended with an electrode fixing part 320 for fixing the electrode plate.

According to a preferred embodiment of the present invention, it is possible to efficiently obtain ultra-high-purity copper by directly using high-purity copper in the form of pellets without melt-molding and in a small amount. Therefore, it is possible to save energy consumption due to melting.

However, the effects obtainable in the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those of ordinary skill in the art from the following description. I will be able to.

The following drawings attached in the present specification illustrate preferred embodiments of the present invention, and serve to further understand the technical idea of the present invention together with the detailed description of the present invention to be described later. It is limited only to and should not be interpreted.
L is a perspective view of an auxiliary apparatus 100 for electrorefining copper pellets according to an embodiment of the present invention,
Figure 2 is a side view of the auxiliary device 100 shown in Figure 1,
3 is a plan view of the auxiliary device 100 shown in FIG. 1;
Figure 4 is a front view of the auxiliary device 100 shown in Figure 1,
5 is a perspective view of a reaction tank 200 in which an auxiliary device 100 is installed according to an embodiment of the present invention,
6 is a side view showing the mutual relationship between the auxiliary device 100, the anode plate 220 and the copper pellet 10 in the reaction tank of FIG. 5;
7 is a side view showing a modified embodiment of FIG. 6.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art may easily implement the present invention. However, since the description of the present invention is merely an embodiment for structural or functional description, the scope of the present invention should not be construed as being limited by the embodiments described in the text. That is, since the embodiments can be variously changed and have various forms, the scope of the present invention should be understood to include equivalents capable of realizing the technical idea. In addition, since the object or effect presented in the present invention does not mean that a specific embodiment should include all or only such effects, the scope of the present invention should not be understood as being limited thereto.

The meaning of the terms described in the present invention should be understood as follows.

Terms such as "first" and "second" are used to distinguish one component from other components, and the scope of rights is not limited by these terms. For example, a first component may be referred to as a second component, and similarly, a second component may be referred to as a first component. When a component is referred to as being "connected" to another component, it should be understood that although it may be directly connected to the other component, another component may exist in the middle. On the other hand, when a component is referred to as being "directly connected" to another component, it should be understood that there is no other component in the middle. On the other hand, other expressions describing the relationship between components, that is, "between" and "just between" or "neighboring to" and "directly neighboring to" should be interpreted as well.

Singular expressions are to be understood as including plural expressions unless the context clearly indicates otherwise, and terms such as "comprises" or "have" refer to the specified features, numbers, steps, actions, components, parts, or these. It is to be understood that it is intended to designate that a combination exists and does not preclude the presence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

All terms used herein have the same meaning as commonly understood by one of ordinary skill in the field to which the present invention belongs, unless otherwise defined. Terms defined in commonly used dictionaries should be interpreted as having meanings in the context of related technologies, and cannot be interpreted as having an ideal or excessively formal meaning unless explicitly defined in the present invention.

1 is a perspective view of an auxiliary apparatus 100 for electrorefining copper pellets according to an embodiment of the present invention, FIG. 2 is a side view of the auxiliary apparatus 100 shown in FIG. 1, and FIG. 3 is It is a plan view of the device 100, and FIG. 4 is a front view of the auxiliary device 100 shown in FIG. 1.

1 to 4, the auxiliary device 100 is made of a stable material that does not participate in the electrolytic reaction, such as acrylic, synthetic resin, rubber.

Among the auxiliary devices 100, a pair of upper fixing plates 110 are formed to be spaced apart, and four semi-circular seating grooves 115 are recessed at the lower end. The seating groove 115 is mounted on the horizontal beam 230 to fix the position of the auxiliary device 100.

The electrode fixing portion 320 extends downward from one of the pair of upper fixing plates 110 to form a predetermined gap with the inclined plate end portion 145. The electrode fixing part 320 functions to support and fix the positive electrode plate 220.

The first plate 120 and the second plate 130 have the same shape, are spaced apart from each other, and are assembled to the upper fixing plate 110 in a grid-fit form (fit into a slot). The lower portions of the first plate 120 and the second plate 130 extend integrally and protrude so as to be inclined. The swash plate 140 is formed under this. The swash plate 140 forms an inclination in the range of 30 degrees and 60 degrees with respect to the vertical direction, and serves to push the copper pellets 10 toward the positive electrode plate 220.

Both ends of the grid fixing part 300 are fixed across the first plate 120 and the first plate 130, and three to five are installed spaced apart from each other. The lattice fixing part 300 functions to store a large amount of copper pellets 10, and functions as a passage through which copper ions generated by oxidation at a small speed can easily move through spaced spaces.

5 is a perspective view of a reaction tank 200 equipped with an auxiliary device 100 according to an embodiment of the present invention. As shown in FIG. 5, the reaction tank 200 has a rectangular parallelepiped shape, and a space is formed inside to accommodate the electrolyte solution 240. In the interior of the reaction tank 200, an electrolyte solution 240 may be provided with a stirring device (not shown) to accelerate the reaction.

The cathode plate 210 and the anode plate 220 are installed in the reaction tank 200 while being spaced apart to face each other and immersed in the electrolyte solution 240. In a specific embodiment, the negative electrode plate 210 is a plate made of copper or stainless steel, and has a terminal formed thereon. In addition, the positive electrode plate 220 is an inert metal plate including at least one of ruthenium (Ru) coating, iridium (Ir) coating, and titanium. Terminals are also formed on the positive electrode plate 220.

The electrolyte solution 240 is a H ₂ SO ₄ solution having a concentration of 0.5 M.

A plurality of horizontal beams 230 are installed horizontally in the reaction tank 200 to support the exterior of the reaction tank 200 and function to fix the position of the auxiliary device 100.

6 is a side view showing the mutual relationship between the auxiliary device 100, the anode plate 220, and the copper pellet 10 in the reaction tank of FIG. 5. As shown in FIG. 6, the inclined plate end portion 145 extending from the lower portion of the first plate 120 and the second plate 130 extends so as not to contact the positive plate 220. The copper pellets 10 are introduced from the upper portion of the reaction tank 200 and are accommodated between the swash plate 140 and the positive electrode plate 220. At this time, the copper pellets 10 are directly in contact with the positive electrode plate 220 so as to play a small role.

The copper pellet 10 is 99% or more of high purity copper, has a small cylindrical shape, and has a short length. These copper pellets 10 are put into the reaction tank 200 in the range of 5 to 30.

At this time, a chemical reaction of [Chemical Formula 1] occurs in the positive electrode plate 220.

[Formula 1]

^{Cu 0 → Cu 2 + + 2e} -

In addition, in the negative electrode plate 210, a chemical reaction of [Chemical Formula 2] occurs.

[Formula 2]

^{Cu 2 + + 2e - → Cu} 0

7 is a side view showing a modified embodiment of FIG. 6. As shown in Figure 7, the end of the modified inclined plate 140b extends in the vertical direction to form a vertical portion 260, and the end of the vertical portion 260 extends in the horizontal direction to form a closing portion 270 do. At this time, the closing portion 270 extends from the lower portion of the vertical portion 260 toward the positive electrode plate 220, but the gap between the vertical portion 260 and the positive electrode plate 220 so that the copper pellet 10 can be inserted Is extended to keep it. That is, the vertical slot 250, which is the distance between the vertical portion 260 and the positive plate 220, is slightly larger than the diameter of the copper pellet 10, so that the copper pellets 10 can be inserted in a row in the vertical slot 250. And make sure to come into contact with the positive electrode plate 220.

[Table 1] shows the result data of electrolytic refining using copper pellets 10 having a purity of 99% or more, the inert metal plate described above as the positive electrode plate 220, and the copper plate as the negative electrode plate 210.

Kinds CD Cr Cu Fe Ni Pb Zn Sum Copper alloy
(%) Copper pellets
(mg/Kg) N/A N/A 49,456,570 153,750 N/A 21,210 N/A 49,631,530 99.65 Electrolytic refining
(mg/Kg) N/A N/A 50,184,470 N/A N/A 27,670 N/A 50,212,140 99.94

As shown in [Table 1], no other components other than lead (Pb) were detected, and the copper content was 99.94% among the other seven metal elements analyzed, compared to the copper content (99.65%) of the copper pellet 10 (99.65%). I could see that it was higher. The recovery rate in this experiment was about 60%.

Detailed description of the preferred embodiments of the present invention disclosed as described above has been provided to enable those skilled in the art to implement and practice the present invention. Although the above has been described with reference to preferred embodiments of the present invention, those skilled in the art will understand that various modifications and changes can be made to the present invention without departing from the scope of the present invention. For example, a person skilled in the art may use the components described in the above-described embodiments in a manner that combines them with each other. Accordingly, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

The present invention may be embodied in other specific forms without departing from the spirit and essential features of the present invention. Therefore, the detailed description above should not be construed as restrictive in all respects and should be considered as illustrative. The scope of the present invention should be determined by reasonable interpretation of the appended claims, and all changes within the equivalent scope of the present invention are included in the scope of the present invention. The invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein. In addition, the embodiments may be configured by combining claims that do not have an explicit citation relationship in the claims, or may be included as new claims by amendment after filing.

10: copper pellet,
100: auxiliary device,
110: upper fixing plate,
115: seating groove,
120: first edition,
130: 2nd edition,
140: swash plate,
140b: deformed slope plate,
145: inclined plate end,
200: reaction tank,
210: negative plate,
220: positive plate,
230: horizontal beam,
240: electrolyte,
250: vertical slot,
260: vertical part,
270: finish,
300: grid fixing,
320: electrode fixing unit.

Claims (12)

Position fixing means installed in the copper electrorefining reaction tank 200; And
A copper pellet comprising: a swash plate 140 connected to the position fixing means and accommodating the copper pellet 10 and guiding the copper pellet 10 to come into contact with the electrode plate in the reaction tank 200. Electrorefining auxiliary device of The method of claim 1,
The position fixing means,
A pair of upper fixing plates 110 installed spaced apart from each other; And
Consisting of; a seating groove 115 formed in the lower portion of the upper fixing plate 110,
The seating groove 115 is an electrolytic refining auxiliary device for copper pellets, characterized in that the position is fixed by being seated on a horizontal beam 230 installed horizontally in the reaction tank 200. The method of claim 2,
A first plate 120 assembled to the pair of upper fixing plates 110; And
A second plate 130 assembled to the pair of upper fixing plates 110 while being spaced apart from the first plate 120; further includes,
The swash plate 140 is an auxiliary apparatus for electrorefining copper pellets, characterized in that it is installed between the lower portion of the first plate 120 and the lower portion of the second plate 130. The method of claim 1,
The electrode plate is an auxiliary apparatus for electrorefining copper pellets, characterized in that the positive electrode plate 220. The method of claim 4,
An auxiliary apparatus for electrorefining copper pellets, characterized in that a plurality of the copper pellets (10) are accommodated between the swash plate (140) and the positive plate (220). The method of claim 5,
The swash plate 140,
A vertical portion 260 extending vertically from the lower portion of the swash plate 140; And
Extending toward the positive electrode plate 220 from the lower portion of the vertical portion 260, so as to maintain a gap between the vertical portion 260 and the positive electrode plate 220 such that the copper pellets 10 can be inserted. An auxiliary apparatus for electrolytic refining of copper pellets, characterized in that it further comprises an extended closing portion 270. The method according to any one of claims 1 to 6,
The auxiliary device 100 is an auxiliary device for electrorefining copper pellets, characterized in that it is made of a synthetic resin material or acrylic. In the copper electrorefining apparatus,
An auxiliary device (100) according to any one of claims 1 to 6;
A reaction tank 200 in which the auxiliary device 100 is fixed at an upper portion;
A negative electrode plate 210 and a positive electrode plate 220 installed to be spaced apart from each other in the reaction tank 200; And
An electrolytic refining apparatus using an auxiliary apparatus for copper pellets, comprising: an electrolyte solution 240 filled in the reaction tank 200. The method of claim 8,
The negative electrode plate 210 is an electrolytic refining apparatus using a copper pellet auxiliary device, characterized in that it contains copper or stainless steel. The method of claim 8,
The positive electrode plate 220 is an electrolytic refining apparatus using an auxiliary device for copper pellets, characterized in that it contains one of ruthenium (Ru) coating, iridium (Ir) coating, and titanium. The method of claim 8,
The electrolytic solution 240 is an electrolytic refining apparatus using an auxiliary apparatus for copper pellets, characterized in that the _{H 2} SO _{4 solution.} The method of claim 2,
Electrolytic refining apparatus using an auxiliary apparatus for copper pellets, characterized in that an electrode fixing part 320 for fixing the electrode plate is further extended to one of the pair of upper fixing plates 110.

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