KR101351105B1 - Electrolytic copper refining device, and electrolytic copper refining method using same - Google Patents

Abstract

An object of the present invention is to provide an electrolytic refining apparatus for copper capable of producing a copper of good quality at a good production cost and a method for electrolytic refining of copper using the same. The copper electrolytic refining apparatus 10 supplies an electrolytic solution 17 of copper, an electrolyte supply part 11 for supplying an electrolyte solution to the electrolytic cell 17, and an additive containing thiourea and hydrochloric acid to the electrolyte solution supply part 11. Glue dissolving tank 13 which continuously supplies the additive tank 12 and the glue aqueous solution produced by dissolving the glue continuously supplied to the electrolyte supply part 11 is provided.

Description

ELECTROLYTIC COPPER REFINING DEVICE, AND ELECTROLYTIC COPPER REFINING METHOD USING SAME

The present invention relates to an electrolytic purification device for copper and a method for electrolytic purification of copper using the same.

In electrolytic refining of copper, the glue for improving the external appearance of an electrophoretic surface is generally added to the electrolyte solution supplied to an electrolytic cell (for example, patent document 1 or 2). In addition to the glue, in addition to the glue, thiourea and hydrochloric acid for improving the appearance of the copper surface, and sulfuric acid for preventing corrosion of the glue are added to the electrolyte.

2 shows a schematic diagram of a conventional electrolytic refining apparatus 20 of copper. The conventional copper electrolytic refining apparatus 20 includes an electrolytic bath 27, an electrolyte supply part 21 for supplying an electrolyte solution to the electrolytic bath 27, and an additive bath 22 in which an additive for supplying the electrolyte solution supply part 21 is prepared. Hydrochloric acid in which the glue dissolution tank 23 to which the aqueous solution of glue supplied to the production 22 is adjusted, the thiourea dissolution tank 24 provided with the thiourea supplied to the additive tank 22, and the hydrochloric acid supplied to the additive tank 22 are installed. The sulfuric acid tank 26 in which the sulfuric acid supplied to the tank 25, the additive tank 22 was installed, and the pumps p'1-p'6 provided between each tank are provided. In the electrolytic refining apparatus 20, the glue first becomes an aqueous solution in the glue dissolving tank 23, and then is mixed with the additive in the additive tank 22 supplied with thiourea, hydrochloric acid and sulfuric acid. In this way, the additive solution is made in the additive tank 22, and then supplied to the electrolyte solution supply unit 21, and then the electrolyte solution containing the additive solution is supplied from the electrolyte solution supply unit 21 to the electrolytic cell 27. In addition, when making the glue aqueous solution in the glue dissolving tank 23, batch processing is performed by the manpower for the measurement operation of the glue and the input operation to the glue dissolving tank 23 by predetermined working time (normally once a day). In addition, adjustment of the additive solution is also performed at the same frequency.

Japanese Patent No. 4041571 Japanese Patent Application Publication No. 2005-307343

However, when the aqueous solution of glue is mixed in the additive solution, the additive solution contains hydrochloric acid or sulfuric acid, and the glue, which is an animal protein and a high molecular material, is decomposed by these acids to lower molecular weight. In addition, when a glue is added with electrolyte solution supply part alone in neutral aqueous solution, without mixing with hydrochloric acid or sulfuric acid, the glue has the property of being easy to corrode.

In this way, when an acid-low molecular glue or a corroded glue is added to the electrolytic solution, deterioration of the glue effect on electrophoresis leads to a deterioration in quality such as a poor product appearance and an increase in impurity quality. In addition, in order to maintain the quality of copper, when the amount of glue added is increased so as to avoid the effects of acid decomposition or corroded glue, an increase in electrolyte resistance due to excess glue in the electrolyte occurs, resulting in high voltage applied voltage. It must be done, which leads to an increase in power consumption.

Therefore, an object of this invention is to provide the electrolytic refining apparatus of copper which can manufacture the copper of favorable quality at a favorable manufacturing cost, and the electrolytic refining method of copper using the same.

As a result of earnest examination, the present inventors did not mix the glue with the acid, but separately added it to the electrolyte solution supply unit separately from the other additives, and carried out each step of weighing, dissolving, and adding the glue continuously, thereby decomposing by acid. It was found that the aqueous solution of the glue in the state of fresh polymer state can be suppressed and added to the electrolytic solution, and it was found that the copper copper of good quality can be produced at a good manufacturing cost.

The present invention completed on the basis of the above knowledge, in one aspect, the copper electrolytic bath, the electrolyte supply unit for supplying the electrolytic solution to the electrolytic bath, the additive tank for supplying the additive except the glue to the electrolyte supply unit, and the glue continuously dissolved It is an electrolytic refining apparatus of copper provided with the glue dissolving tank which continuously supplies the made aqueous solution of the glue to electrolyte solution supply part.

In one Embodiment of the copper electrolytic refining apparatus which concerns on this invention, the glue supply part which supplies a glue continuously to a glue dissolution tank is further provided.

In another embodiment of the copper electrolytic refining apparatus according to the present invention, the additive except for the glue contains thiourea and hydrochloric acid.

In another aspect, the present invention provides a process for supplying an additive except for glue to an electrolyte supply unit, a process for continuously dissolving glue during electrolytic purification and supplying continuously to an electrolyte supply unit, and an aqueous solution of an additive and glue except for glue It is an electrolytic refining method of copper containing the process of supplying the electrolyte solution to contain from an electrolyte solution supply part to an electrolytic bath of copper.

In one Embodiment of the electrolytic refining method of copper which concerns on this invention, the measurement of the glue used when manufacturing the aqueous solution of glue is performed continuously simultaneously with continuous supply and continuous melt | dissolution of glue.

According to the present invention, it is possible to add the glue alone to the electrolyte solution supply unit separately from other additives without mixing the glue with the acid, and to perform the steps of metering, dissolving, and adding the glue continuously, thereby decomposing by acid. It can suppress, and the fresh aqueous solution of the glue of a polymer state can be added to electrolyte solution, and the copper copper of favorable quality can be manufactured. Moreover, since it is an apparatus and a method which can add glue in a polymer state, it is not necessary to add glue excessively. Therefore, it contributes to lower power consumption, and also eliminates the need to use sulfuric acid, which has conventionally been used for preventing corrosion of glue, thereby contributing to the reduction of manufacturing cost.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the electrolytic refining apparatus of copper which concerns on this invention.
It is a schematic diagram of the conventional electrolytic refining apparatus of copper.

(Electrolytic purification device of copper)

The copper electrolytic refining apparatus 10 includes an electrolytic bath 17 of copper, an electrolyte supply unit 11, an additive bath 12, a glue dissolving tank 13, a thiourea dissolving tank 14, and a hydrochloric acid tank 15. ) And a glue supply unit 16. Between the electrolyte supply part 11 and the additive tank 12, between the electrolyte supply part 11 and the glue dissolution tank 13, between the additive tank 12 and the thiourea dissolution tank 14, the additive tank 12 and the hydrochloric acid tank 15 Between the electrolyte supply unit 11 and the electrolytic cell 17, pumps p1 to p5 serving as supply powers of the solutions are provided.

The additive tank 12 contains an aqueous solution of thiourea supplied by the thiourea dissolution tank 14 by the pump p3 and hydrochloric acid supplied by the pump p4 from the hydrochloric acid tank 15.

The glue supply part 16 measures and cuts the glue stored, and supplies it to the glue dissolution tank 13. The glue dissolving tank 13 contains an aqueous solution of glue formed by mixing the glue supplied from the glue supply unit 16 with hot water from a hot water supply unit (not shown).

The electrolyte solution supply part 11 contains electrolyte solution, the glue aqueous solution supplied from the glue dissolution tank 13 by the pump p2, and the additive solution supplied by the pump p1 from the additive tank 12. As shown in FIG. The additive solution consists of hydrochloric acid containing thiourea.

The electrolytic cell 17 is provided with the copper base plate which becomes an anode and the copper base plate which becomes a cathode for refine | purifying the copper copper used as a product by electrodepositing copper on an electrodeposition surface. In addition, the electrolytic solution is supplied to the electrolytic cell 17 by the pump p5 from the electrolytic solution supply section 11. Here, various things can be used for the base plate used as a negative electrode according to a use, For example, when performing electrolysis by a permanent cathode method (PC method), you may use a SUS board etc.

(Electrolytic purification method of copper)

Next, the electrolytic purification method of copper using the electrolytic purification apparatus 10 is demonstrated.

First, in the electrolytic refining apparatus 10 shown in FIG. 1, the thiourea dissolution tank 14 makes the aqueous solution of thiourea of predetermined concentration. In addition, hydrochloric acid of a predetermined concentration is made in the hydrochloric acid tank 15.

Subsequently, the aqueous solution and hydrochloric acid of thiourea are supplied to the additive tank 12 using pumps p3 and p4, and are stirred and mixed.

Next, hydrochloric acid containing thiourea in the additive tank 12 is supplied to the electrolyte solution supply unit 11 using the pump p1.

Here, the hydrochloric acid containing the thiourea from the additive tank 12 to the electrolyte supply part 11 may be supplied in a batch manner. That is, in the additive tank 12, what mixed and stored the aqueous solution of thiourea and hydrochloric acid, for example, for one day at a time, may be supplied to the electrolyte supply part 11. In addition, the said supply may be performed continuously. That is, in the additive tank 12, you may continuously mix the aqueous solution of thiourea and hydrochloric acid, and may supply a required amount to electrolyte solution supply part 11 every time.

On the other hand, the glue supply part 16 measures and cuts the glue stored, and supplies it continuously to the glue dissolution tank 13. Hot water from a hot water supply unit (not shown) is also continuously supplied to the glue dissolving tank 13. The supplied glue is stirred in the glue dissolving tank 13 together with hot water and dissolved in about 10 minutes to produce an aqueous solution of glue. Subsequently, the glue aqueous solution is supplied to the electrolyte solution supply part 11 using the pump p2.

At this time, the glue is weighed by the glue supply unit 16 at the same time as the supply of glue, dissolution of the glue in the glue dissolving tank 13 and supply of the glue aqueous solution from the glue dissolving tank 13 to the electrolyte solution supply unit 11. You may carry out continuously.

The hydrochloric acid containing thiourea supplied from the additive tank 12 and the glue aqueous solution continuously supplied from the glue dissolving tank 13 are stirred and mixed together with the electrolyte solution in the electrolyte solution supply unit 11. Subsequently, an electrolytic solution containing thiourea, hydrochloric acid and glue is supplied from the electrolytic solution supply section 11 to the electrolytic cell 17 by a pump p5, and electrolytic purification of copper in the electrolytic cell 17 using this electrolytic solution. Is done.

In the present invention, as described above, an aqueous solution of glue made by continuously dissolving the glue continuously supplied from the glue supply unit 16 in the glue dissolving tank 13 is continuously supplied to the electrolyte supply unit 11. Thus, since the dissolved glue is directly supplied to the electrolyte supply part 11 without mixing with hydrochloric acid in the additive tank 12, the glue cannot be decomposed by acid, and the glue can be used efficiently. In addition, there is no need to supply sulfuric acid for preventing corrosion of the glue to the additive bath 12. Therefore, manufacturing cost becomes favorable. In addition, since the glue continuously supplied is continuously dissolved and continuously supplied to the electrolyte supply unit 11, the time that the glue is dissolved in water is shortened until the electrolyte is supplied to the electrolyte supply unit 11, thereby suppressing the corrosion of the glue. It is possible to provide a copper of good quality. Moreover, since the metering of the glue used when producing the aqueous solution of glue is performed continuously simultaneously with continuous supply and continuous melt | dissolution of glue, manufacturing efficiency becomes favorable.

Hereinafter, although the Example of this invention is shown, these are provided in order to understand this invention more easily, and it does not intend that this invention is limited.

(Example)

As an example, the electrolytic refining apparatus of copper of the structure shown in FIG. 1 was prepared, and the electrolytic purification of copper was performed using this.

Specifically, first, 54 sheets of copper plate of length 1060 mm x width 990 mm x thickness 45 mm in an electrolytic cell of length 1280 mm x width 5550 mm x depth 1340 mm, 1040 mm x 1040 mm x thickness 10 mm 53 sheets of substrates were installed at intervals of 100 mm each.

Next, an aqueous solution of 0.83 mol / L thiourea was prepared in a thiourea dissolution tank, and 9.6 mol / L hydrochloric acid was prepared in a hydrochloric acid bath.

Next, an aqueous solution of thiourea and hydrochloric acid were supplied to an additive bath, followed by stirring and mixing. In addition, the liquid temperature in the additive tank was kept at 20-30 degreeC. The hydrochloric acid containing thiourea in the additive bath was made and stored in this way, and the required amount was supplied to the electrolyte supply unit.

In the glue supplying unit, the stored glue was weighed and cut and continuously supplied to the glue dissolving tank, and hot water was continuously supplied to the glue dissolving tank from the hot water supply unit. The supplied glue was stirred in a glue dissolution bath with hot water and dissolved in about 10 minutes. At this time, the aqueous solution of glue was adjusted to have a concentration of 0.5 mmol. Subsequently, the produced aqueous solution of the glue was continuously supplied to the electrolyte supply unit. In addition, the liquid temperature in the glue dissolution tank was maintained at 35-45 degreeC.

Subsequently, in the electrolyte supply portion, hydrochloric acid containing thiourea from the additive bath and glue aqueous solution continuously supplied from the glue dissolving tank were stirred and mixed with the electrolyte solution. Subsequently, an electrolytic solution containing thiourea, hydrochloric acid, and glue was supplied from the electrolytic solution supply section to the electrolytic cell, and electrolytic purification of copper was performed at an electric current density of 320 A / m 2 for 210 hours in the electrolytic cell using this electrolytic solution.

By the above-mentioned example, 6350 t of copper copper was obtained. The amount of glue used for this was 350 kg, and the amount of power consumed was 370 kWh.

(Comparative Example)

As a comparative example, the electrolytic refining apparatus of copper of the structure shown in FIG. 2 was prepared, and the electrolytic purification of copper was performed using this.

Specifically, first, 54 sheets of copper plate of length 1060 mm x width 990 mm x thickness 45 mm in an electrolytic cell of length 1280 mm x width 5550 mm x depth 1340 mm, 1040 mm x 1040 mm x thickness 10 mm 53 sheets of substrates were installed at intervals of 100 mm each.

Next, a 3 mmol / L glue aqueous solution was prepared in a glue dissolving tank, an aqueous solution of 0.85 mol / L thiourea was prepared in a thiourea dissolution tank, 10.0 mol / L hydrochloric acid was prepared in a hydrochloric acid bath, and a sulfuric acid bath was prepared. 10.0 mol / L of sulfuric acid was prepared.

Next, an aqueous solution of glue, an aqueous solution of thiourea, hydrochloric acid and sulfuric acid were supplied to an additive bath, followed by stirring and mixing. In addition, the liquid temperature in the additive tank was kept at 20-30 degreeC. The aqueous glue solution, the aqueous solution of thiourea, hydrochloric acid, and sulfuric acid in the additive bath were made and stored in this manner, and the required amount was supplied to the electrolyte supply portion.

Subsequently, the mixed solution of the glue aqueous solution, the aqueous solution of thiourea, hydrochloric acid, and sulfuric acid from the additive bath was stirred and mixed with the electrolyte solution in the electrolyte solution supply part. Subsequently, an electrolytic solution containing glue, thiourea, hydrochloric acid, and sulfuric acid was supplied from the electrolytic solution supply unit to the electrolytic cell, and electrolytic purification of copper was performed at an electric current density of 320 A / m 2 for 210 hours in the electrolytic cell using this electrolytic solution. .

By the comparative example mentioned above, 6350 t of copper copper was obtained. The amount of glue used for this was 410 kg and the power consumption was 378 kWh.

10: electrolytic purification device
11: electrolyte supply unit
12: additive tank
13: glue dissolving tank
14: thiourea dissolution tank
15: hydrochloric acid tank
16: glue supply
17: electrolyzer
p1 to p5: pump

Claims (5)

With electrolytic cell of copper,
An electrolyte supply unit for supplying an electrolyte containing an additive different from glue and an aqueous solution of glue to the electrolytic cell,
An additive tank for supplying an additive different from glue to the electrolyte supply unit,
The copper electrolytic refining apparatus provided with the glue dissolution tank which supplies the aqueous solution of the glue which melt | dissolved the glue continuously and produced to the said electrolyte supply part. The copper electrolytic refining apparatus according to claim 1, further comprising: a glue supply unit for continuously supplying glue to the glue dissolving tank. The electrolytic purification apparatus for copper according to claim 1 or 2, wherein the additive different from the glue includes thiourea and hydrochloric acid. Supplying an additive different from the glue to the electrolyte supply unit,
Dissolving the glue continuously in the electrolytic refining process, and supplying continuously to the electrolyte supply unit;
The electrolytic purification method of copper containing the process of supplying the electrolyte solution containing the additive different from the said glue and the aqueous solution of the said glue from the said electrolyte supply part to a copper electrolytic cell. The copper electrolytic refining method according to claim 4, wherein the weighing of the glue used when producing the aqueous solution of the glue is carried out simultaneously with the continuous supply and the continuous dissolution of the glue.

Images