JP3424885B2 - Copper electrolytic slime treatment method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating electrolytic slime recovered in a copper electrolysis or lead electrolysis step, and more particularly to a method of treating a noble metal mainly containing silver from an electrolytic slime recovered in a copper electrolysis or lead electrolysis step. Regarding collecting

[0002]

2. Description of the Related Art In the electrolytic refining process of copper smelting or lead smelting, as the process progresses, foreign substances separated from the anode accumulate in the electrolytic cell as electrolytic slime. Since various electrolytic metals including silver are contained in this electrolytic slime, the operation of collecting the electrolytic slime and separating and extracting the useful metal from the electrolytic slime is routinely performed. That is, the copper electrolytic slime recovered in the copper electrolytic refining step contains Cu, Se, and Pb as main components, and additionally contains Sb, Bi, Te, Au, and Ag. Particularly in the copper smelting process, Sb is a metal that is difficult to remove, and in the copper electrolytic refining process, it is a metal that greatly affects the quality of electrolytic copper.

Therefore, in general, first, a copper extraction treatment is performed in a sulfuric acid bath to separate and extract Cu from copper electrolytic slime to separate from an extraction residue, and subsequently, the extraction residue is roasted to produce Se. Is volatilized and separated. As a result, a roasted precipitate having a low Cu and Se content is produced. The roasted starch produced by the above treatment is mainly composed of lead electrolytic slime containing mainly Sb, Bi, Pb, Cu and Ag, and various noble metal-containing repeated products generated in the treatment step of copper electrolysis or lead electrolytic slime. After being mixed into a mixture, silica, iron scraps, and coke are further added, and the mixture is heated and melted to generate precious lead containing precious metal and FeO—SiO ₂ slag by reduction.

The composition of the slag is determined so that the fluidization temperature is as low as possible in order to minimize the loss of precious metal to the slag. The noble lead produced as described above is transferred to a volatilization furnace and subjected to melting treatment by heavy oil combustion at 700 to 800 ° C. The molten noble lead is then agitated to transfer about 80% of the contained Sb into the volatile scavenger or float, and is converted to low antimony noble lead having a low Sb content. The low antimony noble lead obtained as described above was transferred to a centralization furnace, and after residual Sb, Pb and Bi were removed by an oxidation treatment, an alkaline flux was further added, and tellurium converted to an alkali salt was added. It is separated, and finally, Pb is added and the dense Cu is separated to leave a melt containing Ag as a main composition. Then, a noble metal anode for silver electrolysis is obtained by pouring the above-mentioned melt into a mold.

When various noble metal-containing repeats generated in the step of treating electrolytic slime produced by copper electrolysis or lead electrolysis are treated as described above, noble lead is treated in a volatilization furnace. Since the Sb volatilization separation speed is slow,
If the time required for operation is too long and the slag generated in the volatilization furnace becomes large, the amount of precious lead taken out of the slag when the slag is scraped out of the volatilization furnace increases. However, it has been pointed out that the actual yield of the product is lowered.

As a means for separating Sb from the noble metal-containing repetitive product, an alkaline flux is added to the molten metal during the reduction melting or the oxidation melting in the silver-separating furnace to add Sb to the slag. Although it is possible to collect and process the slag, it is not preferable because the impurity load will be increased when the produced slag is returned to the copper or lead smelting step again.

Further, when a large amount of alkaline flux is used for the melting treatment, the refractory material of the furnace body used for the melting treatment is greatly damaged, and there is a problem that the life of the furnace body is shortened. Separately, although it is possible to consider wet treatment as a method of treating high-grade gold-silver containing recycle products recovered in copper smelting or lead smelting processes, enormous costs are required when considering environmental pollution due to wastewater treatment. It is obvious that it is not preferable.

According to the conventional method in which the mixture is not treated according to the content of Sb, the content of Sb in the produced noble lead is 15 to 25% by weight, and the content of noble lead in the noble lead is 15% by weight. The Pb content was 30 to 40% by weight. On the other hand, the weight% ratio S of Sb and Pb contained in the above-mentioned noble lead
b / Pb showed 0.4 to 0.8.

[0009]

SUMMARY OF THE INVENTION An object of the present invention has been proposed in view of the above problems, and is to remove Sb from electrolytic slime recovered by copper smelting or lead smelting. Another object of the present invention is to provide a method for treating electrolytic slime which has a high Sb removal rate and enables efficient Sb separation and removal treatment, and has a high precious metal recovery efficiency.

[0010]

[Means for Solving the Problems] In order to achieve the above object, the present invention produces a noble lead by reducing and melting a roasting substance obtained by decoppering and roasting copper electrolytic slime. In the method for treating a copper electrolytic slime for volatilizing and silver-dispersing, the roasted product is divided into a high-grade Sb-containing material and a low-grade Sb-containing material, and the high-grade Sb-containing material is mixed with lead electrolytic slime for reduction melting. Of the high antimony noble lead produced
The weight percent ratio Sb / Pb of zimon and lead becomes 1.0 or more.
Then, the high antimony noble lead is converted to Sb by the volatilization treatment.
After removing the silver, silver is separated, and the low-grade Sb-containing material is reduced and melted,
Provided is a method for treating a copper electrolytic slime, which comprises dividing the produced low antimony noble lead into silver without removing Sb by volatilization.

Further, the present invention collects the decoppered product of the copper electrolytic slime obtained by subjecting the copper electrolytic slime to the decoppering process, and then deoxidizing the copper electrolytic slime to remove the selenium by roasting treatment. To give a roasted starch, and to the roasted starch, a high-quality gold-silver containing repeated product recovered in the copper smelting step and a lead electrolytic slime recovered in the lead electrolysis step are added to form a mixture, Silica stone, iron scrap, and coke are added to the mixture to heat the mixture to produce noble lead, and then the noble lead is transferred to a volatilization furnace, after which the noble lead is volatilized to produce noble lead. More antimony is removed, the noble lead is changed to low antimony noble lead, and then the low antimony noble lead is transferred to a centralization furnace, and the low antimony is given by applying an oxidation treatment accompanied by heating and stirring. Lead and bismuth rather than precious lead Removed, further, tellurium is removed as an alkali salt by addition of an alkaline flux, finally, the copper is removed as Mitsu陀 by adding lead,
In the method of treating electrolytic slime recovered in the copper electrolysis or lead electrolysis step of casting the remaining melt in a mold of a predetermined shape to obtain an anode for silver electrolysis, first, in the copper smelting step which is one of the processing raw materials The high-quality gold-silver-containing repetitive product recovered by the above method is separated into a low antimony repetitive product and a high antimony repetitive product according to the content of antimony, and the low antimony repetitive product is mixed with the roasted precipitate to form a low antimony mixture, The low antimony mixture is further added with silica, iron scrap, and coke, and subjected to reduction melting treatment to produce low antimony noble lead, while the high antimony repeated product is the lead recovered in the lead electrolysis step. Electrolytic slime is mixed into a high antimony mixture, and the high antimony mixture is
Furthermore, silica, iron scraps, and coke are added, and reduction melting treatment is performed to generate high antimony precious lead, and the high antimony precious lead is transferred to a volatilization furnace and volatilized to remove antimony. , Converted to low antimony noble lead, and then both the low antimony noble lead produced from the low antimony mixture and the low antimony noble lead produced from the high antimony mixture are both transferred to a centralization furnace to proceed the process. Provided is a method for treating electrolytic slime collected in a characteristic copper electrolysis or lead electrolysis step.

[0012] Also in the above-mentioned present invention, the weight percent ratio Sb of antimony and lead contained in high antimony noble lead
It is preferable that / Pb be 1.0 or more .

In the present invention, the addition amount of silica, iron scrap and coke added to the low antimony mixture or the high antimony mixture is 2 to 7% by weight with respect to the low antimony mixture or the high antimony mixture, respectively. 18
It is preferably in the range of 2% to 5% by weight.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, (1) the composition of slag (floating residue) generated in a volatilization furnace which is a step of removing antimony is mainly composed of lead oxide and antimony oxide,
Under the condition that the quality of antimony in the smoke ash collected in the volatilization furnace is 65% or more, this floating dust is likely to occur, and (2) the noble lead obtained by reducing and melting the slime and the repetitive material in the system. By keeping the antimony / lead of 1 in a weight ratio of 1 or more, the generation of floating debris is suppressed, the antimony activity in the noble lead increases, and the volatilization rate increases.
Based on the test results obtained by the inventor.

Therefore, the high-grade antimony-containing material is usually mixed with a lead electrolytic slime mainly having an Sb quality of 30% or more and a Pb content of 10% or less, and a predetermined flux, a reducing agent and an iron scrap or coke as a slag forming agent are added. Then, reduce and melt. The produced molten metal is held in a volatilization furnace until the antimony quality in the molten material becomes 10% or less, preferably 5% or less. Since electric furnace slag is repeatedly used for copper smelting, the antimony grade in the slag is low and the amount thereof is low. Specifically, with respect to high-grade antimony-containing material and lead electrolytic slime, 2 to 7%, preferably 5% of silicate ore, 3 to 18%, preferably 9% of iron scrap,
And 2-5% coke is added. The amount of coke added is adjusted according to the degree of slime oxidation.

On the other hand, the low-grade antimony-containing material is usually S
b Grade of 10% or less and Pb of 30% or more are mixed with roasted starch mainly of copper electrolytically produced slime that has been decoppered and deselenized, and a predetermined amount of flux, iron scrap, and silicate ore are added, and reduction melting is performed. . The produced metal is directly subjected to oxidative refining in a branching furnace. It is necessary to perform melt reduction so that the quality of antimony in the electric furnace metal is 10% or less, and the amount of additives is the same standard as for high-grade products, but the reducing agent is adjusted according to the degree of slime oxidation.

Therefore, according to the present invention, when a mixture of electrolytic slime and a high-grade gold-silver-containing repetitive material recovered in the copper smelting or lead smelting step is treated to recover a useful metal, Sb is contained depending on the amount of Sb contained. Content is 10% by weight
The low antimony mixture of less than 1% and the high antimony mixture of Sb content of 10% by weight or more are fractionated, and the high antimony mixture and the low antimony mixture are separately treated.
Therefore, high antimony noble lead is recovered from the high antimony mixture and low antimony noble lead is recovered from the low antimony mixture. Then, only the high antimony noble lead is further subjected to the Sb scavenging process in the volatilization furnace to be the low antimony noble lead. In this way, the low antimony noble lead obtained by dividing the high antimony mixture or the low antimony mixture as a raw material into two systems and recovering each is processed in a silver-separating furnace to obtain a silver electrolysis anode.

Further, according to the present invention, when a mixture of electrolytic slime and a high-grade gold-silver-containing repetitive product is treated to recover a useful metal, the Sb content is low and the Sb content is less than 10% by weight. The antimony mixture and the high antimony mixture having an Sb content of 10% by weight or more are separately treated, and the low antimony mixture having a low Sb content is subjected to the process without performing the Sb volatilization treatment. The amount of antimony mixture processed in the volatilization furnace is reduced and Sb / Pb in high antimony noble lead is reduced.
By adjusting the ratio to 1.0 or more, when Sb is volatilized and collected from high antimony noble lead by volatilization treatment,
When removing Sb from high antimony noble lead, the Sb removal rate (kg / hr · m ² ) is significantly improved.

Further, according to the present invention, the slag generation rate (SD) wt% during the treatment in the volatilization furnace is significantly reduced, and as a result, the amount of the noble metal that is caught in the slag and excluded from the system is reduced. However, the recovery rate of the target precious metal is improved. Further, since the amount of processing in the repeated processing is inevitably reduced, the weight of work-in-process can be significantly reduced, which can contribute to effective utilization of the storage location.

Here, the Sb removal rate (RS) kg / hr
Xm ² is the Sb weight in the low antimony noble lead obtained by completing the volatilization treatment from the Sb weight (WA) kg in the high antimony noble lead charged into the volatilization furnace, as shown in Formula 1. Volatile discharge weight (WC) kg of Sb from high antimony noble lead obtained by volatilization treatment, obtained by subtracting (WB) kg,
It is divided by a value obtained by multiplying the operation time (R) hr of the volatilization furnace by the surface area (S) m ² of the melt in the volatilization furnace. Sb
When comparing the removal rates, the Sb weight volatilized and discharged from the melt having a unit surface area per unit time is
b Determine the size of the removal rate. RS = (WA-WB) / R × S = WC / R × S (1)

Furthermore, the slag generation rate (DS) during the treatment with the volatilization furnace
The weight% is, as shown in Equation 2, divided by the weight of slag produced (SW) obtained by the volatilization furnace treatment by the weight of produced noble lead (PD) obtained by the volatilization furnace treatment, and 100 is obtained. It was obtained by multiplying. DS = (SW / PD) × 100 (2)

In the present invention, the addition amount of silica, iron scrap, and coke to be added to the low antimony mixture or the high antimony mixture is 2 to 7% by weight with respect to the low antimony mixture or the high antimony mixture, respectively. 3-
By defining 18% by weight and 2 to 5% by weight, it is possible to reduce both the Sb content rate and the absolute Sb content in the slag. In this case, it is more preferable that the addition amount of silica is 5% by weight and the addition amount of iron scrap is 9% by weight, and the addition amount of coke is adjusted within the range of 2 to 5% by weight depending on the oxidation degree of electrolytic slime. Preferably.

[0023]

EXAMPLES Examples will be described in detail below. [Example 1] As shown in Table 1, roasted starch 3000K
g, two kinds of repeater total 530 kg, electric furnace smoke 270
Kg and iron scrap 393 Kg, silica stone 200 Kg,
100 kg of coke is melted by heating to 1150 to 1250 ° C., 2300 kg of precious lead, 950 kg of slag and smoke ash 2
70 kg was obtained. Since no lead electrolytic slime was mixed in, the antimony quality of this noble lead was 7.9%. Therefore, it was processed by a conventional technique in a weight-separating furnace without passing through a volatilizing furnace.

Example 2 As shown in Table 2, the Sb content was 34.0% by weight and the Pb content was 8.0% by weight.
Lead electrolytic slime 1200 kg, Sb content 17.0 wt%, Pb content 22.0 wt% slag recycle 1000 kg, Sb content 15.0 wt%, Pb 750 kg of a dense repetitive material having a content of 45.0% by weight and a Bi-based repetitive material 580 k having an Sb content of 4.4% by weight and a Pb content of 12.1% by weight.
g, 270 kg of smoke ash having a Sb content of 14.0% by weight and a Pb content of 40.0% by weight, and Fe scrap 327
kg, 200 kg of silica and 100 kg of coke are mixed to form a high antimony mixture, and the high antimony mixture is heated and melted at 1200 ° C. to obtain a Sb content of 2
2780 kg of high antimony noble lead having a Pb content of 23.8% by weight and 792 kg of slag;
270 kg of smoke ash was produced.

The high antimony noble lead obtained in this case contains 2.9 kg of Au and 266.3 kg of Ag, and further contains 700 kg of Sb and 662 kg of Pb. , Sb / in high antimony noble lead
The Pb ratio was 1.06. High antimony precious lead 2 above
When the furnace part was volatilized at 780 ° C. for 59 hrs so that the melt surface area (S) in the volatilization furnace was 3 m ² , the Sb removal rate (RS) was 6.4 kg / hr × m ² . Therefore, the Sb removal rate (R
S) showed an improvement of about 30% compared with 5.0 kg / hr × m ² . The slag generation rate (DS) is 10.3
% By weight, and the slag generation rate (D
S) was reduced to about 1/4 compared to 25.0% by weight.
The noble lead emitted from the volatilization furnace was processed in a conventional concentration furnace.

Example 3 As shown in Table 3, the Sb content was 32.5% by weight and the Pb content was 7.0% by weight.
Lead electrolytic slime 3500kg, Sb content 27.0wt%, Pb content 35.0wt% 500kg recycle product, Fe scraps 404kg, silica stone 2
00 kg and 100 kg of coke are mixed to obtain a high antimony mixture, and the high antimony mixture is 1230
The content of Sb is 42.9% by weight after being melted by heating at ℃,
2850 kg of high antimony noble lead having a Pb content of 10.6% by weight, 826 kg of slag, and 200 kg of smoke ash were produced.

The high antimony noble lead obtained in this case contains 1.8 kg of Au and 574.2 kg of Ag, and further, Sb of 1223 kg and Pb.
Containing 301kg of Sb in high antimony noble lead
The / Pb ratio was 4.07. When the above two high antimony noble lead furnaces were volatilized at 780 ° C. for 50 hours with the melt surface area (S) in the volatilization furnace being 3 m ² , the Sb removal rate (RS) was 15. 0 kg / hr × m
^2, which was about 3 times the Sb removal rate (RS) of 5.0 kg / hr × m ^{2 obtained} by the conventional method. The slag generation rate (DS) was 10.0% by weight, and the slag generation rate (D
S) was reduced to a value of about 1/4 compared to 25.0% by weight. The noble lead emitted from the volatilization furnace was processed in a conventional concentration furnace.

[Example 4] When the weight% ratio of Sb to Pb in the high antimony noble lead was changed between 1 and 2.8, and volatilization was performed at 780 ° C for 44 hours,
Sb removal rate (RS) obtained by measurement kg / hr × m
² and the slag formation rate (DS) wt% show the results as shown in Table 4, and the Sb removal rate (RS) is 1.3 times higher than the value measured when treated by the conventional method. 2.4
In addition to showing a double high value, the slag generation rate (DS) is reduced to a value of about 1/4 in each case.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

[0033]

According to the present invention, when recovering noble metals and various useful metals from copper electrolysis or lead electrolysis slime, the removal rate of Sb by the volatilization treatment is greatly improved, and therefore the work can be speeded up. Can work efficiently. Further, since the absolute amount of slag generated in the volatilization furnace is reduced, as a result, the amount of precious metal and various useful metals recovered for each processing unit can be increased and the amount of work in progress can be reduced. Furthermore, since the process proceeds without volatilizing low antimony noble lead, which has a high grade of noble metal, it is possible to reduce the amount of noble metal in-process, and shorten the number of days for recovery processing to significantly reduce the processing cost. I chose

[Brief description of drawings]

FIG. 1 is a flowchart showing the steps of mixing / reducing and melting a roasted starch according to the present invention and the subsequent steps.

FIG. 2 is a flowchart showing a part of a treatment process of a byproduct of copper electrolysis.

FIG. 3 is a graph showing the relationship between the Sb / Pb ratio in noble lead, the Sb removal rate, and the slag formation rate.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C22B 11/02 C22B 11/02 30/02 30/02 // C25C 1/12 C25C 1/12 (58) Fields investigated (Int .Cl. ⁷ , DB name) C22B 1/00-61/00

Claims (4)

(57) [Claims] 1. A method for treating a copper electrolytic slime in which a roasted product obtained by decoppering and roasting a copper electrolytic slime is reduced and melted to produce noble lead, and the noble lead is volatilized and divided into silver. High-quality anti anti-monkey products with antimony quality exceeding 10%
Mon-containing substances and antimony with a low quality grade of 10% or less
The high-grade antimony-containing material is divided into the thymone-containing material and the high-grade antimony-containing material is mixed with lead electrolytic slime and reduced and melted.
/ Pb is set to 1.0 or more, and the high antimony noble lead is reduced to a low concentration by removing antimony by volatilization.
A graded antimony-containing material is a method for treating copper electrolytic slime, which comprises reducing and melting low-antimony noble lead that has been produced, and then performing silver concentration without removing antimony by volatilization. 2. A decoppered product of the copper electrolytic slime obtained by subjecting the copper electrolytic slime to a decoppering treatment, and the decoppered product of the copper electrolytic slime is subjected to deselenium by a roasting treatment to be roasted. Collected in the copper smelting process in the roasted product
A silver-containing repeating substance gold, adding and lead electrolysis slime collected in lead electrowinning process to prepare a mixture, to produce a noble lead by the reduction melting process of heating by adding the Keiseki and iron scrap and coke in the mixture, Next, the precious lead is transferred to a volatilization furnace, and thereafter,
Antimony was removed from the noble lead by volatilizing the noble lead, and the noble lead was changed to low antimony noble lead, and then the low antimony noble lead was transferred to a centralization furnace, followed by heating and stirring. Lead and bismuth are removed from the low antimony noble lead by applying an oxidation treatment, and further,
Tellurium is removed as an alkaline salt by adding an alkaline flux, and finally copper is removed as a dense material by adding lead, and the remaining melt is cast into a mold of a predetermined shape to obtain an anode for silver electrolysis. In the method of treating electrolytic slime recovered in the copper electrolysis or lead electrolysis process, containing gold and silver recovered in the copper smelting process, which is one of the processing raw materials
Antimony content by mixing repeated products with the roasted product
Of less than 10% by weight of a low antimony mixture, and
Silica, iron scrap, and coke are added, and reduction melting is performed to produce low antimony noble lead, while the copper smelting step is performed.
The antimony content was increased by mixing the gold-silver containing repeats collected in 1. and the lead electrolytic slime collected in the lead electrolysis step.
A high-antimony mixture of 10% by weight or more is further added, and silica, iron scraps, and coke are added to carry out reduction melting treatment to produce high-antimony precious lead, which is transferred to a volatilization furnace and volatilized. Antimony is extracted and eliminated by processing to convert it into low antimony noble lead, and the low antimony noble lead produced from the low antimony mixture and the low antimony noble lead produced from the high antimony mixture are transferred to a centralization furnace. A method for treating electrolytic slime recovered in a copper electrolysis or lead electrolysis step, which is characterized by the above. 3. The treatment of copper electrolytic slime according to claim 2, wherein the weight% ratio Sb / Pb of antimony and lead contained in the high antimony noble lead is 1.0 or more. Method. 4. The addition amount of silica, iron scrap, and coke added to the low-antimony mixture and the high-antimony mixture is 2 to 7% by weight, 3 to 18% by weight, and 2 to 2% with respect to the low-antimony mixture and the high-antimony mixture, respectively. method of processing a copper electrolysis slime according to claim 2-3, wherein the 5 percent by weight.