JP3381244B2 - Method for recovering antimony and bismuth from copper electrolyte - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to Sb and B contained as impurities in a copper electrolytic solution used in copper electrolytic refining.
The present invention relates to improvement of a method for selectively recovering i.

[0002]

2. Description of the Related Art In electrolytic copper refining, S in copper electrolytic solution
If the concentration of impurities such as b, Bi, and Fe exceeds a certain value, the quality of the electrolytic copper product is adversely affected.
Purification of a copper electrolytic solution that removes these impurities is performed.
This cleaning solution is mainly performed by a copper removal electrolytic method. However, this method has drawbacks such as low power efficiency and unfavorable working environment. As a method of solving these drawbacks, in recent years, sodium sulfite has been used as an electrolytic solution, and the copper electrolytic solution is brought into contact with a chelate resin capable of adsorbing Sb, Bi and Fe, or a chelate resin capable of selectively adsorbing Sb. In addition, a method has been proposed in which Sb and Bi are separated from the copper electrolytic solution and recovered by bringing the chelating resin into contact with an eluent (JP-A-60-
50192, JP-A-2-141541 and the like). However, since the above-mentioned adjustment method uses hydrochloric acid as an eluent, it cannot replace costly decopperization. Further, it is difficult to maintain the potential adjusted by the entrainment of air at a desired value.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above problems and to control the concentration of Fe ions contained in a copper electrolytic solution as much as possible in the method of recovering Sb and Bi described above. It is an object of the present invention to provide a method capable of adjusting the oxidation-reduction potential of the copper electrolytic solution so as to be simple.

[0004]

In order to achieve the above object, the present invention provides Sb, Bi and Fe as impurities.
By dipping a copper material in a copper electrolytic solution containing, reduce trivalent iron ions and adjust the redox potential of the copper electrolytic solution to less than 650 mV, and contact the copper electrolytic solution with a chelate resin, In this method, Sb and Bi are adsorbed, and then the chelating resin is brought into contact with an eluent to elute and recover Sb and Bi.

[0005]

1 is a flow chart of the process according to the present invention.
Shown in. In the present invention, first, as impurities, Sb, B
Redox potential (ORP) of copper electrolyte containing i and Fe
Is adjusted to less than 650 mV (vs. SCE (vs. saturated sweet and dry electrode)), it is important to adjust the redox potential by immersing a copper material in the copper electrolytic solution. By doing so, trivalent Fe existing in the copper electrolytic solution is reduced to divalent. Cu which is dissolved from the copper material into the copper electrolytic solution by this reduction is a main component element of the copper electrolytic solution and is not dissolved as an impurity element. Therefore, it does not affect the control of the concentration of impurity ions contained in the copper electrolytic solution. From this point, the copper material is preferably pure copper.
The shape of the copper material immersed in the copper electrolytic solution is a lump, a plate,
Various materials such as powder can be used.

Next, the copper electrolyte whose potential is adjusted as described above is brought into contact with the chelate resin to adsorb Sb and Bi to the chelate resin. Most of Fe is divalent, and its adsorption amount is extremely small. As a chelate resin, a known trade name, Eporus MX-, manufactured by Miyoshi Yushi Co., Ltd.
2, Duolite C-467 manufactured by Sumitomo Chemical Co., Ltd., Uniselec UR-3300 manufactured by Unitika Ltd., and the like. In this way, an aqueous solution containing sodium chloride and sulfuric acid or an aqueous solution containing thiourea and sulfuric acid can be used as an eluent for eluting Sb and Bi from the chelate resin having Sb and Bi adsorbed thereon. Since these eluents are cheap and easy to recycle, the cost of cleaning can be reduced.

In the aqueous solution containing sodium chloride and sulfuric acid, the sodium chloride concentration is preferably 60 to 180 g / l, more preferably 120 to 180 g / l. The concentration of sulfuric acid is preferably 30 to 200 g / l, 50
-200 g / l is more preferable. Further, in the aqueous solution containing thiourea and sulfuric acid, the thiourea concentration is 5 to 20 g.
/ L is preferable, and 10 to 20 g / l is more preferable. The concentration of sulfuric acid is preferably 25 to 300 g / l, and 1
50 to 200 g / l is more preferable. If the temperature at which the eluent is brought into contact with the chelate resin is too low, Sb
And the elution reaction of Bi becomes slow. On the other hand, if the eluent is an aqueous solution containing sodium chloride and sulfuric acid, the elution rate of Sb and Bi does not improve at 40 ° C. or higher if the eluent is an aqueous solution containing thiourea and sulfuric acid. In particular, the decomposition of thiourea becomes remarkable at 50 ° C. or higher. Therefore, when the eluent is an aqueous solution containing sodium chloride and sulfuric acid, the temperature is preferably 10 to 60 ° C, and 30 to 40 ° C.
Is more preferable. When the eluent is an aqueous solution containing thiourea and sulfuric acid, the temperature is preferably 25 to 60 ° C and 3
0-50 degreeC is more preferable.

[0008]

【Example】

[Examples 1 to 4 and Comparative Examples 1 to 4] The functional group of the chelate resin Epolas MX-2 manufactured by Miyoshi Yushi Co., Ltd. was hydrogen type.
Next, 200 g / l of ferric sulfate was dissolved in sulfuric acid to obtain trivalent Fe ion concentrations of 0.4 g / l, 0.8 g / l, and 1.6.
Four kinds of aqueous solutions of g / l and 2.4 g / l were prepared, and each was divided into two equal parts. Each of the two equally divided aqueous solutions was left as it was (Comparative Examples 1, 2, 3, 4), and the copper plate was immersed in the other aqueous solution to lower the oxidation-reduction potential (Example 1,
2, 3, 4). The potential of the aqueous solution as it is is 650 m
V, and the immersion amount of the copper plate was about 580 mV. The chelate resin was immersed in each of the two aqueous solutions and stirred at 40 ° C. for 60 minutes. Next, the chelate resin and the aqueous solution were separated, and the amount of iron adsorbed on each chelate resin was determined. The obtained results are shown in Table 1.

[0009]

[Table 1]

It can be seen from Table 1 that the redox potential of the copper electrolyte can be effectively lowered and the adsorption of Fe can be suppressed by immersing the copper plate in the copper electrolyte.

[Embodiment 5] Eporus MX manufactured by Miyoshi Yushi Co., Ltd.
The functional group of the chelate resin of -2 was hydrogen type. next,
20 ml of this resin is used as a copper electrolytic solution (Sb 0.55 g / l, B
i 0.52 g / l) 400 ml at 60 ° C
Stir for 0 minutes. After washing this resin with pure water, 200 g of sodium chloride and 100 g / l of sulfuric acid were added.
Immerse it in 10 ml of aqueous solution and stir at 10 ° C for 60 minutes to remove Sb.
And Bi were eluted. As a result, the recovery rate of Sb and Bi is 5
It was 2.3% by weight.

[Examples 6 to 9] The elution temperature was 25 ° C and 4
It carried out like Example 5 except having set it as 0 ° C, 50 ° C, and 60 ° C. The results are shown in Table 2.

[0013]

[Table 2]

[Examples 10 to 15] The same procedure as in Example 6 was carried out at 25 ° C except that the sodium chloride concentration and the sulfuric acid concentration were as shown in Table 3. Table 3 shows the results obtained.
It was shown to.

[0015]

Table 3 Eluent concentration Sb + Bi recovery rate (g / l) (wt%) NaCl H ₂ SO ₄ Example 10 60 100 100 2.2 Example 11 120 30 43.2 Example 12 120 50 53.7 Example Example 6 120 100 54.5 Example 13 120 120 55.2 Example 14 120 200 80.8 Example 15 180 180 100 79.0

In Examples 14 and 15, N
The aCl had a saturated concentration. From Table 2 and Table 3,
The aqueous solution containing sodium chloride and sulfuric acid is Sb and Bi.
It can be seen that it is preferable as an eluent for eluting.

[Examples 16 to 19] In the same manner as in Example 5, the chelate resin having Sb and Bi adsorbed thereon was washed with water and then 200 ml of an aqueous solution containing 20 g / l of thiourea and 200 g / l of sulfuric acid. Sb and Bi were eluted by immersing in and being stirred for 60 minutes at each temperature shown in Table 4. The recovery rates of the obtained Sb and Bi are shown in Table 4.

[0018]

[Table 4]

In Example 19, the recovery rate of Sb + Bi decreased. This is probably because thiourea was partially decomposed.

[Examples 20 to 28] The same procedure as in Example 17 was carried out at 40 ° C except that the thiourea concentration and the sulfuric acid concentration were as shown in Table 5. The obtained results are shown in Table 5 together.

[0021]

Table 5 in the eluent concentration Sb + Bi recovery (g / l) (wt%) thiourea H ₂ SO ₄ Example 20 5 200 11.4 Example 21 10 25 2.1 Example 22 10 50 5.8 Example 23 10 100 13.4 Example 24 10 150 21.5 Example 25 10 200 30.2 Example 26 10 300 20.6 Example 27 15 15 200 36.5 Example 17 20 200 2002.1 Example 28 20 300 42.6

From Tables 4 and 5, it can be seen that an aqueous solution containing thiourea and sulfuric acid is preferable as an eluent for eluting Sb and Bi.

Example 29 A column was filled with 100 ml of chelating resin, Duolite C-467 manufactured by Sumitomo Chemical Co., Ltd., and the chelating resin had a hydrogen group as a functional group. Next, about 50 g of a copper plate is immersed to reduce iron ions from trivalent to divalent, Sb is 0.55 g / l, Bi is 0.52 g.
/ L, Fe ²⁺ became 0.4 g / l copper electrolytic solution (oxidation-reduction potential 580 mV) was passed through the column. Regarding the liquid passing conditions, the liquid passing temperature was 60 ° C., the liquid passing speed was SV10 (10 liter (l) / hr per 1 liter (l) of resin), and the liquid passing amount was BV100. Further, pure water at 60 ° C. was passed through the column at a flow rate of BV20 to wash the chelate resin to completely remove the copper electrolytic solution. Then, an aqueous solution containing 10 g / l of thiourea and 200 g / l of sulfuric acid was passed through the column. Regarding the liquid passing conditions, the liquid passing temperature was 40 ° C., the liquid passing speed was SV3, and the liquid passing amount was BV20. As a result, the recovery rate of Sb + Bi is 19.8% by weight.
Met.

[Example 30] Chelating resin 10 Epolas MX-2 manufactured by Miyoshi Yushi Co., Ltd.
The column was filled with 0 ml, and the chelate resin had a functional group of hydrogen type. Next, about 50 g of a copper plate is immersed to reduce the iron ions from trivalent to divalent, Sb is 0.55 g / l, B
A copper electrolyte solution (oxidation-reduction potential of 580 mV) in which i was 0.52 g / l and Fe ²⁺ was 0.4 g / l was passed through the column. The liquid passing conditions are as follows: the liquid passing temperature is 60 ° C and the liquid passing speed is SV.
10 (10 liters (l) per 1 liter (l) of resin
/ Hr), and the flow rate was BV100 (100 liters (l) per 1 liter (l) of resin). Further, pure water at 60 ° C. was passed through the column at a flow rate of BV20 to wash the chelate resin to completely remove the copper electrolytic solution. After this, 180 g of sodium chloride,
An aqueous solution containing 100 g / l of sulfuric acid was passed through the column. The liquid passing conditions are a liquid passing temperature of 40 ° C and a liquid passing speed of SV3.
And the flow rate was BV15. As a result, Sb + B
The recovery rate of i was 91.6% by weight. Incidentally, FIG. 2 elution solution concentration of Sb and Bi to passing liquid amount reaches BV15
Shown in.

[Example 31] A chelating resin called Eporus MX-2 manufactured by Miyoshi Yushi Co., Ltd. was used.
It was packed in a 0 ml column and made into a hydrogen type. Sulfuric acid to sulfuric acid second
Iron is dissolved in 200 g / l to prepare a trivalent iron ion synthesis solution, and about 50 g of a copper plate is immersed in the solution to reduce the ferric ion from trivalent to divalent, and then the solution is passed through the column to obtain antimony. ,
Bismuth was adsorbed on the chelate resin. Then, after the pure water was washed with BV20 (20 l / l resin) at 60 ° C. to completely remove the copper electrolytic solution, SV3 (40 V) was used at 40 ° C. with a mixed solution of thiourea 10 g / l and sulfuric acid 200 g / l. 3 liters
/ Hr / l resin) and BV20 (20 l / l resin) were passed through, and the recovery rates of antimony and bismuth were examined. The result is shown in FIG. That is, FIG. 3 shows thiourea 10 g.
/ L, 200g / l sulfuric acid mixture flow rate is 40 ℃ B
Antimony up to V20, shows elution solution concentration of bismuth. As shown in FIG. 3, it can be seen that antimony and bismuth are eluted.

[Experimental Examples 32 to 35, Comparative Examples 5 to 8] The functional group of the Unitika UR-3300 chelate resin was a hydrogen type. Dissolve ferric sulfate in 200 g / l sulfuric acid for 3
A valent iron ion synthetic solution was prepared and divided into two equal parts. A copper plate was put in one of the synthetic solutions, and the other was left as it was, and the chelate resin was put in at 40 ° C. and stirred for 60 minutes. The iron ion concentration was 0.4 g / l (Example 32, Comparative example 5),
0.8 g / l (Example 33, Comparative Example 6), 1.6 g / l
(Example 34, Comparative Example 7) 2.4 g / l (Example 3)
The above-mentioned synthetic solutions were prepared for four kinds of No. 5, Comparative Example 8).
FIG. 4 shows the adsorption amount (g / resin l) of UR-3300 with and without a copper plate (Example) and the value of the oxidation-reduction potential (ORP) at the end of adsorption and iron ion. The concentration is shown. As can be seen from FIG. 4, the copper plate suppresses the adsorption of iron ions on the chelate resin. That is, when a copper plate was added, the iron ion concentration at the end of adsorption was only 0.3 g / l or less of the initial concentration (remaining as Fe ²⁺ ), and the adsorption amount (F
e ³⁺ ) is 6 g / l of resin or less, whereas when the copper plate is not inserted, the iron ion concentration at the end of adsorption is significantly reduced, and the amount of adsorption to the chelate resin is large. Further, when the copper plate is not inserted, it is recognized that the redox potential (ORP) is 650 mV or more even when the iron ion concentration approaches 0 as a result of adsorption. As a result of putting the chelate resin in which the adsorption of iron ions is suppressed in the eluent and stirring, the recovered metals consisted essentially of Sb and Bi, and Fe was extremely small.

[0027]

EFFECT OF THE INVENTION Sb and Bi from the copper electrolyte of the present invention
According to the recovery method of No. 3, since the pure copper material is immersed in the copper electrolytic solution, the iron in the copper electrolytic solution brought into contact with the chelate resin is reduced from trivalent to divalent, so that the impurity ions contained in the copper electrolytic solution are reduced. Concentration management is extremely simple. Therefore, the recovery of Sb and Bi from the copper electrolytic solution can be performed extremely efficiently.

[Brief description of drawings]

FIG. 1 is a flow chart showing the process of the present invention.

[Fig. 2] Sb and Bi with sodium chloride / sulfuric acid mixture
To indicate the state of elution, a liquid passing amount graph plotting the relationship (BV) and the elution solution concentration (elution curve).

3 is a passed through amount to indicate the state of elution of Sb and Bi according thiourea sulfate mixture graph plotting the relationship between the elution solution concentration for (BV) (elution curve).

FIG. 4 shows the Fe concentration before adsorption of 0.4 g / l and 0.8 g / l, respectively, to show the effect of immersing a copper plate in a copper electrolyte.
1, 1.6 g / l, 2.4 g / l, the adsorption amount after adsorption of the chelate resin on the copper electrolyte solution, the redox potential and Fe
It is a graph which shows a density with and without a copper plate immersion.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-60-50192 (JP, A) JP-A-60-180918 (JP, A) JP-A-63-171899 (JP, A) JP-A-63- 286599 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C22B 1/00-61/00

Claims (5)

(57) [Claims] 1. By dipping a copper material in a copper electrolyte solution containing Sb, Bi and Fe as impurities, trivalent iron ions are reduced and the redox potential of the copper electrolyte solution is reduced to 65.
It is characterized in that the copper electrolyte is brought into contact with a chelate resin to adsorb Sb and Bi, and then the chelate resin is brought into contact with an eluent to elute and recover Sb and Bi by adjusting to less than 0 mV. Sb and B from copper electrolyte
A method of recovering i. 2. The method for recovering Sb and Bi from the copper electrolytic solution according to claim 1, wherein the copper material is a lump, a plate, or a powder. 3. The method for recovering Sb and Bi from the copper electrolytic solution according to claim 1, wherein the eluent is an aqueous solution containing sodium chloride and sulfuric acid or an aqueous solution containing thiourea and sulfuric acid. 4. An aqueous solution containing sodium chloride and sulfuric acid,
The method for recovering Sb and Bi from the copper electrolytic solution according to claim 3, wherein the sodium chloride concentration is 60 to 180 g / l, the sulfuric acid concentration is 30 to 200 g / l, and the temperature is 10 to 60 ° C. 5. The aqueous solution containing thiourea and sulfuric acid has a thio urea concentration of 5 to 20 g / l and a sulfuric acid concentration of 25 to 300 g.
/ L and the temperature is 25 to 60 ° C, The method for recovering Sb and Bi from the copper electrolytic solution according to claim 3.