JPH08253825A - Method for selectively recovering antimony and bithmuth from copper electrolyte - Google Patents

Abstract

PURPOSE: To selectively and separately recover Sb and Bi by bringing a copper electrolyte contg. Sb and Bi into contact with chelating resin to adsorb Sb and Bi in a specified ratio and eluting Sb and Bi successively from the resin with the respective eluting solutions. CONSTITUTION: The Sb and Bi as the impurities contained in a copper electrolyte used in the electrorefining of copper are recovered. In this case, the copper electrolyte is brought into contact with a chelating resin to adsorb Sb nd Bi in <=1.3 weight ratio of Sb to Bi. An aq. soln. contg. 10-20g/L thiourea and 150-200g/L sulfuric acid and kept at 30-40 deg.C is brought into contact with the resin to preferentially elute Bi in the soln. An aq. soln. contg. 120-180g/L sodium chloride and 50-100g/L sulfuric acid and kept at 30-40 deg.C is then brought into contact with the resin to elute Sb in the soln. Consequently, Sb and Bi are selectively and separately recovered at a low cost.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for separately recovering Sb (antimony) and Bi (bismuth) contained as impurities in a copper electrolytic solution used in copper electrolytic refining.

[0002]

2. Description of the Related Art In electrolytic copper refining, S in copper electrolytic solution
When the concentration of impurities such as b and Bi exceeds a certain value,
Since it has a bad influence on the quality of the product, electrolytic copper, a copper electrolyte is purified to remove these impurities. This cleaning solution is performed by the decoppering electrolytic method. However,
This method has drawbacks such as low power efficiency and unfavorable working environment. As a method for solving these drawbacks, in recent years, a chelate resin capable of adsorbing Sb and Bi is brought into contact with a copper electrolyte to adsorb Sb and Bi, and then an eluent is applied to the chelate resin adsorbing Sb and Bi. A method has been proposed in which Sb and Bi are separated from the copper electrolytic solution and recovered by bringing them into contact with each other (see, for example, Japanese Patent Laid-Open Publication No. 6-58242).
0-50192).

However, this method requires Sb and B
Since i is eluted simultaneously, the treated product obtained by subjecting this eluate to neutralization, electrowinning, etc. is a mixture of Sb and Bi. However, Sb and Bi are components that have various important uses such as alloy additives, semiconductor materials, and pharmaceuticals, and their mutual inclusions become impurities. Therefore, it is desired to recover Sb and Bi separately from the copper electrolyte with good selectivity. In this regard, a technique of using a chelate resin that selectively adsorbs Sb has been proposed (JP-A-2-141541). However, this technique uses hydrochloric acid to elute the adsorbed Sb. When hydrochloric acid is recycled by distillation or the like, it causes a problem of corrosion of the equipment, and since it is expensive, the recycling cost increases.

[0004]

Therefore, in view of the above circumstances, an object of the present invention is to provide a method capable of separately recovering Sb and Bi separately from each other with good selectivity and at a low cost.

[0005]

In order to achieve the above object, the present invention makes a chelate resin capable of adsorbing Sb and Bi contact a copper electrolyte to adsorb Sb and Bi, and then the chelate. In the method for recovering Sb and Bi by contacting a resin with an eluent, (1)
Sb and Bi are adsorbed so that the weight ratio Sb / Bi of the adsorbed amount becomes 1.3 or less, (2) Bi is preferentially eluted at the time of elution, and then S is removed from the chelate resin after Bi elution.
Elute b. Here, the Bi eluent that preferentially elutes Bi is an aqueous solution containing thiourea and sulfuric acid.
The Sb eluent that elutes Sb from the chelate resin after i is an aqueous solution containing sodium chloride and sulfuric acid. Then, the aqueous solution containing thiourea and sulfuric acid has a thiourea concentration of 1
The aqueous solution containing sodium chloride and sulfuric acid has a sodium chloride concentration of 120 to 180 g / l and a sulfuric acid concentration of 50 to 1 and an aqueous solution of 0 to 20 g / l and a sulfuric acid concentration of 150 to 200 g / l.
It is preferably 00 g / l. The temperature is 30-40
C is preferred. Further, in order to collect Sb in an aqueous solution of the same system as Bi while concentrating Sb, the Sb eluent obtained by elution with an aqueous solution containing sodium chloride and sulfuric acid is contacted with an anion exchange resin to adsorb Sb, Sb is eluted and recovered from the anion exchange resin having adsorbed thereinto using an aqueous solution containing thiourea and sulfuric acid.

In order to solve the above problems, the present invention brings a copper electrolyte into contact with a column filled with a chelate resin capable of adsorbing Sb and Bi, and dissolves Sb and Bi dissolved in the copper electrolyte. To the chelate resin in the column, and preferably the adsorption weight ratio Sb / Bi of Sb / Bi is 1.3.
Is adsorbed to exceed 50 to 6 from above the column.
After washing the chelate resin with warm water at 0 ° C., a Bi eluent is passed from the bottom of the column to recover Bi selectively and at a high concentration. B used in the present invention
The i eluent is composed of sulfuric acid and sodium chloride, and has a sulfuric acid concentration of 20 to 30 g / l and a sodium chloride concentration of 120 to 180 g / l. The amount and speed of the eluent to be passed differ depending on the amount of resin used and the amount adsorbed, so it is necessary to select the conditions in advance. The elution is judged to be completed when the Bi concentration in the eluent is 0.01 g / l or less.

[0007]

The process of the present invention will be described with reference to FIG. In addition to Sb and Bi as impurities, the copper electrolytic solution usually contains F
Since a large amount of e is contained as a trivalent ion, the above 3
The amount of Fe adsorbed is reduced by reducing the valence of Fe to divalent (step 1). A copper electrolyte is brought into contact with a chelate resin capable of adsorbing Sb and Bi to adsorb Sb and Bi (step 2). Examples of the chelate resin include EPORAS MX-2, a product name by Miyoshi Yushi Co., Ltd., Duolite C-467, a product name by Sumitomo Chemical Co., Ltd., and UNICELEC UR-3300, a product name by Unitika.

In step 2, when the copper electrolyte is brought into contact with the chelate resin to adsorb Sb and Bi,
It is important that the adsorption (weight) ratio Sb / Bi of the Sb and Bi is 1.3 or less. For this purpose, it is preferable to adjust the copper electrolytic solution to Sb / Bi ≦ 1.3 before the step 1. The adsorption ratio in step 2 is Sb
When /Bi>1.3, Sb is liable to be eluted due to an increase in the amount of the copper electrolytic solution passed during the elution of Bi in step 3, and the selectivity thereof is significantly impaired. Although the reason for this is unknown, S is not present at the place where Bi is adsorbed on the chelating resin.
It is considered that this Sb is easily eluted when b is replaced.

Regarding the behaviors of Sb and Bi with the increase of the amount of the copper electrolytic solution passing through the chelate resin in the step 2,
explain. The Sb / Bi of the copper electrolyte to be contacted is about 1.1.
As the liquid flow rate increases, the adsorbed amount of Sb, Bi and Sb and Bi (Sb + Bi), and the weight ratio Sb / Bi of the adsorbed amount change as shown in FIG. That is, the adsorbed amount of Sb gradually increases while decreasing the increasing rate as indicated by the white circle mark. The amount of adsorbed Bi increases as shown by the triangular mark, reaches a maximum at a certain liquid flow rate, and then decreases. Further, the Sb + Bi adsorption amount increases as shown by the double circle mark to reach saturation, and then becomes flat. Further, the weight ratio Sb / Bi of the adsorbed amount increases from around the liquid passing amount where the adsorbed amount of Bi is maximized as indicated by the black circle mark. From this, it is considered that the adsorption of Sb is stronger than that of Bi. That is, it is speculated that when the copper electrolyte is passed after the adsorption of Bi and Sb on the chelate resin is saturated, the adsorbed Bi is desorbed and Sb is newly adsorbed there. .

Therefore, as shown in FIG.
When b / Bi is about 1.1, the adsorbed Sb can be adjusted by adjusting the flow rate to BV50 or less at which the adsorption of Sb and Bi is saturated.
The / Bi ratio can be maintained at 1.1. The adsorbed Sb / Bi ratio is increased by increasing the liquid flow amount. If the initial Sb / Bi ratio of the copper electrolyte is greater than 1.3, it becomes difficult to maintain the adsorbed Sb / Bi ratio at 1.3 or less. Sb and Bi
The reason why the weight ratio Sb / Bi of the adsorbed amount is set to 1.3 or less is to elute Bi from the chelate resin having Sb and Bi adsorbed thereto with good selectivity. When the adsorption ratio exceeds 1.3, not only the above-mentioned desorption of Bi becomes large and the Bi adsorption rate and thus the recovery rate decrease, but also Sb newly adsorbed at the location where Bi is desorbed,
Since it easily elutes in the subsequent elution process, it becomes difficult to separately collect Sb and Bi with high selectivity.

Thus, in order to selectively recover Bi from the above chelate resin having Sb / Bi adsorbed at an Sb / Bi ratio of 1.3 or less, a Bi eluent is contacted with the chelate resin to elute (step 3). ). At this time, an aqueous solution containing thiourea and sulfuric acid is preferable as the Bi eluent. In the aqueous solution containing thiourea and sulfuric acid, the thiourea concentration is 5 to 20 g / l, preferably 10 to 20 g / l.
The concentration of sulfuric acid is 25 to 300 g / l, preferably 150 to 200 g / l. If the temperature at which the Bi eluent is brought into contact with the chelate resin is too low, the Bi elution reaction becomes slow. On the other hand, if it is too high, the decomposition of thiourea becomes remarkable and the elution rate is not improved. Therefore, the temperature of the Bi eluent is 25 to 60 ° C., preferably 30.
-40 degreeC.

After the Bi is eluted and recovered, the Sb still adsorbed and remaining is eluted. Therefore, an aqueous solution containing sodium chloride and sulfuric acid is used as the Sb eluent to remove the Sb.
Are collected by elution (step 4). In this Sb eluent,
The sodium chloride concentration is 60 to 180 g / l, preferably 120 to 180 g / l. And the concentration of sulfuric acid is 3
The amount is 0 to 200 g / l, preferably 50 to 200 g / l. The temperature of the Sb eluent is 10 to 60 ° C., preferably 30.
-40 degreeC. If the temperature is too low, the elution efficiency will be poor, and if it is too high, the elution efficiency will not be improved. The Sb eluent thus obtained has a low Sb concentration. Therefore, in order to concentrate the Sb, the Sb is added to the anion exchange resin.
Contact the eluent to adsorb Sb (step 5), and then
A second Sb eluent containing thiourea and sulfuric acid is preferably contacted with the anion exchange resin having adsorbed Sb (step 6). As a result, Sb can be concentrated and Sb and Bi can be separately recovered with the same eluent.

Next, in the method in which the Bi eluent is passed through the bottom of the column filled with the chelate resin, the eluents of sulfuric acid and sodium chloride are used.
The reason for setting the amount to ˜30 g / l is that if it is lower than this range, the elution amount of Bi decreases, and if it is higher than this range, Sb is eluted and mixed. Also, the sodium chloride concentration is 120 to 180 g /
The reason for setting l is that if it is lower than this range, the elution amount of Bi decreases, and if it is higher than this range, sodium chloride is saturated and sodium chloride cannot be dissolved.

When Sb and Bi in the copper electrolytic solution are adsorbed by the chelate resin, the copper electrolytic solution is passed from the top to the bottom of the column filled with the chelate resin. At this time, if the flow rate is increased, in normal column operation, as described above,
The phenomenon that the adsorbed Bi replaces Sb in the solution is observed. Bi desorbed by this substitution phenomenon is re-adsorbed at the lower part of the column. Therefore, as the copper electrolytic solution is passed through the column to adsorb the chelate resin, the Bi distribution adsorbed by the chelate resin tends to be concentrated in the lower part of the column.
Water for washing has a difference in specific gravity between water and copper electrolyte,
The heavy copper electrolyte is passed through the top of the column so that the heavy copper electrolyte is always pushed downward, and the copper electrolyte remaining in the column is completely removed. By this operation, it is possible to efficiently prevent the mixing of the wash water and the residual electrolytic solution. The Bi eluent that is passed through the column after being washed to elute Bi is, for example, 30 g of sulfuric acid.
/ L and 150g / l of sodium chloride, the specific gravity is much higher than that of the water remaining in the column, and the residual wash water and the eluent may flow from the bottom of the column rather than from the top of the column. Can be suppressed and the elution becomes efficient. Furthermore, as described above, it is considered that the above concentration range works efficiently for Bi adsorbed in the lower part of the column. In general, the elution of Bi from the chelate resin causes the adsorbed BiO ⁺ to be desorbed by forming a chloride complex such as BiCl ₄ ⁻ , and H ⁺ ions are adsorbed at the adsorption site. In the dilute sulfuric acid used in the present invention, a large amount of H ⁺ is consumed by the resin that adsorbs a large amount of Bi in the lower part of the column, and Cl ⁻ ions are also generated due to the complexation equilibrium with the eliminated Bi. Consumed.
Therefore, when the eluent entered from the bottom moves to the top of the column where a large amount of Sb is adsorbed, free H ⁺ that can be adsorbed at the adsorption site and Cl ⁻ that can react with Sb to form a chloride complex are generated. Since both are decreasing, Sb is effective
It is considered that the elution of

[0015]

【Example】

Example 1 According to FIG. 1, Sb and Bi were added from the copper electrolytic solution.
Was recovered. 100 ml of chelate resin (Sumitomo Chemical Co., Ltd., trade name: Duolite C-467) was filled in the column to make the functional group into a hydrogen type. The copper electrolytic solution contains Sb of 0.
The trivalent Fe ion was reduced to divalent by dipping a copper plate containing 55 g / l and 0.52 g / l of Bi (step 1). A copper electrolyte containing Sb and Bi was passed through the column and brought into contact with the chelate resin to adsorb Sb and Bi on the chelate resin (step 2). The liquid passing conditions are as follows: the liquid passing temperature is 60 ° C., and the liquid passing speed is 10 liter (l) / hr (S) per 1 liter (l) of resin.
V10) and the flow rate is 5 per liter (l) of resin
The volume was 0 liter (l) (BV50).

As a result, the adsorption amount of Sb and Bi is
25.6g and 23.2g per liter (l) respectively
And the adsorption ratio Sb / Bi (weight) was 1.10. Next, an aqueous solution containing 10 g / l of thiourea and 200 g / l of sulfuric acid was passed as a Bi eluent into the column filled with the chelate resin having the above Sb and Bi adsorbed thereon, and brought into contact with the chelate resin. , Bi were eluted (step 3). Regarding the liquid passing conditions, the liquid passing temperature was 40 ° C., the liquid passing speed was SV3, and the liquid passing amount was BV10. For Bi eluents up to BV10, Sb and Bi in Bi eluent
Was analyzed for changes in concentration. The results are shown in FIG. As a result, the Sb concentration and Bi concentration of the Bi eluent were 0.04 g / l and 0.72 g / l, respectively, and the elution rates of Sb and Bi were 1.4 wt% and 80.1 wt%, respectively. there were.

Further, pure water is passed through a column filled with the chelate resin after eluting Bi at 40 ° C. with a flow rate of BV10.
By passing water as the above and washing the chelate resin,
The aqueous solution containing thiourea and sulfuric acid used for the elution was completely removed. After this, an aqueous solution containing 180 g / l of sodium chloride and 100 g / l of sulfuric acid was added to the column.
Sb was eluted by passing it as an eluent of b and contacting with the chelate resin (step 4). Liquid passing conditions are as follows: the liquid passing temperature is 40 ° C, the liquid passing speed is SV3, and the liquid passing amount is BV.
It was set to 22. Sb in the first Sb eluent up to BV22
And the change in Bi concentration were analyzed. The results of plotting these are shown in FIG. It can be seen from FIG. 4 that Sb can be efficiently eluted from the chelate resin that selectively elutes Bi by using an aqueous solution containing sodium chloride and sulfuric acid, and can be selectively separated from Bi. As a result, the Sb concentration of this first Sb eluent was 0.34 g / l, and
The elution rate of b was 92.8% by weight.

In order to concentrate Sb of the first Sb eluent, the eluent is once brought into contact with an anion exchange resin to adsorb Sb (step 5), and then the adsorbed Sb is adsorbed.
b was eluted with an aqueous solution containing thiourea and sulfuric acid (step 6). That is, anion exchange resin (manufactured by Organo,
Product name: IRA-410) A column filled with 100 ml was passed through the above eluent at 40 ° C. with a passing rate of SV3 and a passing rate of BV90, and brought into contact with the anion exchange resin (step 5). . Adsorption amount of Sb and Bi and B when the first Sb eluent was brought into contact with the anion exchange resin up to BV90
The relationship with V is shown in FIG.

Subsequently, an aqueous solution containing 10 g / l of thiourea and 200 g / l of sulfuric acid as the second Sb eluent was passed through the column packed with the anion exchange resin having adsorbed Sb, Sb was eluted by contact with anion exchange resin (step 6). Regarding the liquid passing conditions, the liquid passing temperature was 40 ° C., the liquid passing speed was SV3, and the liquid passing amount was BV23. The change in Sb and Bi concentrations up to BV23 in the second Sb eluent was analyzed. The results of plotting these are shown in FIG. As a result, the Sb concentration of this second Sb eluent was 0.67 g / l. Second S
The Sb concentration of the b eluent was twice as concentrated as the first Sb eluent.

[Example 2, Comparative Examples 1 and 2] 20 BV
The copper electrolyte was brought into contact with the chelate resin in the same manner as in Example 1 except that (Example 2), 100 (Comparative Example 1) and 160 (Comparative Example 2) were used. The obtained results are shown together in Table 1. FIG. 2 is a result of plotting these.

[0021]

[Table 1] Adsorption amount Adsorption ratio BV (g / resin l) Sb / Bi Sb Bi Sb + Bi (weight) Example 2 20 10.2 8.2 18.4 1.24 Example 1 50 25.6 23.2 48.8 1.10 Comparative Example 1 100 29.1 18.9 48.0 1.54 Comparative Example 2 160 33.1 16.8 49.9 1.97

From the above examples and comparative examples, the following can be seen. That is, (1) Sb, B up to BV of 50
The amount of adsorption of i and Sb + Bi increases. (2) The adsorbed amount of Sb + Bi is saturated when the BV is about 50, and remains flat when the BV exceeds 50. (3) When BV exceeds 50, the amount of Bi adsorbed gradually decreases, while the amount of Sb adsorbed gradually increases by almost the amount decreased. (4) When the BV exceeds 50, the adsorption ratio Sb / Bi increases. From these facts, once the amount of Sb + Bi adsorbed reaches saturation, Bi once adsorbed is desorbed and Sb adsorption occurs instead. Therefore, in order to recover Bi from the copper electrolyte,
It can be seen that it is necessary to finish the contact of the copper electrolytic solution with the chelating resin before the liquid passing amount at which the adsorption amount of Bi starts to decrease.

[Examples 3, 4 and Comparative Example 3] The adsorption ratio Sb / Bi (weight) was changed to 1.13 (Example 3), 1.30 (Example 4), and 1 by changing the liquid flow rate BV. .64 (Comparative Example 3), except that the copper electrolyte was brought into contact with the chelate resin and Bi was eluted in the same manner as in Example 1. The obtained results are shown in Table 2.

[0024]

[Table 2] Adsorption amount Adsorption ratio Elution rate in Bi eluent (g / resin l) Sb / Bi concentration ratio Sb / Bi (wt%) Sb Bi (weight) (g / l) / (g / l) Sb Bi Example 3 25.8 22.8 1.13 0.020 1.4 80.1 Example 4 28.8 22.1 1.30 0.026 1.7 85.1 Comparative Example 3 32.8 20.0 1.64 0.86 49.6 94.5 Example 1 25.6 23.2 1.10 0.06 1.4 80.1

From the above, the following can be understood. That is, the adsorption ratio Sb / Bi (weight) is 1.13 and 1.3.
It was possible to elute Bi from Sb with good selectivity by using a solution containing thiourea and sulfuric acid from the chelate resin of No. 0. On the other hand, the adsorption ratio Sb / Bi (weight) is 1.6.
From the chelate resin of No. 4, Bi could not be eluted from Sb with good selective separation. When judged comprehensively,
It can be seen that Bi can be selectively eluted by setting the adsorption ratio to 1.3 or less.

[Example 5, Comparative Example 4] Chelate resin: 1 liter of "Eporus MX-2" manufactured by Miyoshi Yushi Co., Ltd. was packed in a column. Sb 0.5-0.6 g / l, Bi 0.3-
After the copper electrolytic solution having a concentration of 0.4 g / l was passed through a copper plate column at 60 ° C. for reduction, the Sb / Bi adsorption ratio was 1.4.
It was adsorbed to the chelate resin in the column so that it was in the range of ˜1.9 (adsorption amount: Sb 20 g / resin liter, Bi: 14 g / resin liter). To wash the chelate resin, warm water was passed from above the column. Then, an eluent containing 30 g / l of sulfuric acid and 150 g / l of sodium chloride was used to pass Sb and B through the column from above (Comparative Example 4) and below (Example 5).
The elution amount of i was investigated. FIG. 7 shows the elution curves of Bi in the upper case (Comparative Example 4) and the lower case (Example 5). As shown in FIG. 7, when the liquid is passed through from the lower side of the column, the Bi concentration is about twice as high as when the liquid is passed from above. Figure 7
Corresponding to, upper insertion (Comparative Example 4), lower insertion (Example 5)
Table 3 shows the maximum concentration of Bi, the Sb concentration at that time, and the Bi / Sb concentration ratio. As can be seen from Table 3, the lower insertion (Example 5) has a higher Bi / Sb concentration ratio, the elution of Sb can be suppressed more than the upper insertion (Comparative Example 4), and Bi can be recovered in high purity.

[0027]

[Table 3]

[0028]

EFFECT OF THE INVENTION Sb and Bi from the copper electrolyte of the present invention
According to the selective recovery method described in (1), the weight ratio Sb / Bi of the adsorbed amounts of Sb and Bi to be adsorbed on the chelate resin is set to 1.3 or less, Bi is eluted first, and then Sb is eluted. Sb and Bi can be separately recovered from the electrolytic solution efficiently and with high selectivity. In particular, Bi
Use of an inexpensive and easily recyclable aqueous solution containing thiourea and sulfuric acid or an aqueous solution containing sodium chloride and sulfuric acid as a Bi eluent for the purpose of eluting Sb and an Sb eluent for the purpose of eluting Sb You can
In addition, according to the present invention, from a chelate resin having Sb and Bi adsorbed thereto, sulfuric acid
Bi can be selectively and highly concentrated with a sodium chloride mixed solution.

[Brief description of drawings]

FIG. 1 is a flowchart showing steps in Example 1 for recovering Sb and Bi from a copper electrolytic solution.

FIG. 2 is a graph in which the relationship between the adsorption amount of Sb and Bi adsorbed on the chelate resin and the adsorption ratio Sb / Bi and the passing amount BV of the copper electrolyte solution is plotted.

FIG. 3 is a graph plotting the relationship between the passing amount BV of Bi eluent and the concentration.

FIG. 4 is a graph plotting a relationship between a passing amount BV and a concentration of a first Sb eluent.

FIG. 5 is a graph plotting the relationship between the adsorption amounts of Sb and Bi adsorbed on the anion exchange resin and the flow rate BV of the first Sb eluent.

FIG. 6 is a graph plotting a relationship between a passing amount BV and a concentration of a second Sb eluent.

FIG. 7 is a graph of a Bi elution curve showing the relationship between the liquid passing amount and the eluent concentration when a mixed solution of sulfuric acid and sodium chloride is passed from above and below the column.

Claims (8)

[Claims] 1. A copper electrolyte is brought into contact with a chelate resin capable of adsorbing Sb and Bi to adsorb Sb and Bi,
Next, in the method for recovering Sb and Bi by bringing the chelating resin into contact with an eluent, (1) S
b and Bi are adsorbed at a weight ratio Sb / Bi of 1.
It is set to 3 or less, and (2) when eluting, Bi is preferentially eluted, and then Sb is eluted from the chelating resin after Bi is eluted.
A method of selectively collecting. 2. A Bi eluent that preferentially elutes Bi is
The method for selectively recovering Sb and Bi from the copper electrolytic solution according to claim 1, which is an aqueous solution containing thiourea and sulfuric acid. 3. The Sb eluent that elutes Sb from the chelate resin after Bi elution is an aqueous solution containing sodium chloride and sulfuric acid.
A method of selectively collecting. 4. The aqueous solution containing thiourea and sulfuric acid has a thiourea concentration of 10 to 20 g / l and a sulfuric acid concentration of 150 to 200.
The method for selectively recovering Sb and Bi from the copper electrolytic solution according to claim 2, which is g / l and the temperature is 30 to 40 ° C. 5. An aqueous solution containing sodium chloride and sulfuric acid,
The method for selectively recovering Sb and Bi from the copper electrolytic solution according to claim 3, wherein the sodium chloride concentration is 120 to 180 g / l, the sulfuric acid concentration is 50 to 100 g / l, and the temperature is 30 to 40 ° C. 6. The method according to claim 3, wherein an Sb eluent obtained by eluting with an aqueous solution containing sodium chloride and sulfuric acid is brought into contact with an anion exchange resin to adsorb Sb. 7. The method according to claim 6, wherein Sb is eluted and recovered from the anion exchange resin having Sb adsorbed, using an aqueous solution containing thiourea and sulfuric acid. 8. A column filled with a chelate resin capable of adsorbing Sb and Bi is contacted with a copper electrolytic solution to adsorb Sb and Bi dissolved in the copper electrolytic solution onto the chelate resin, and the upper part of the column. After washing the chelate resin by passing warm water of 50 to 60 ° C., sulfuric acid 20 to 30 g /
1, B containing 120 to 180 g / l of sodium chloride
By passing the eluent from the bottom of the column,
A recovery method for selectively eluting and recovering Bi.