JPH0735595B2 - Method for treating sulfuric acid acidic solution containing antimony and bismuth - Google Patents

Description

TECHNICAL FIELD The present invention selectively separates and removes soluble antimony and bismuth from impurities accumulated in a sulfuric acid acidic solution of an electrolytic solution in an electrolytic step of copper smelting by a simple operation. It is about the method.

(Prior art and its problems) In electrolytic refining of copper, the anode as an anode contains many metals such as gold, silver, nickel, selenium, tellurium, bismuth, antimony, and arsenic, in addition to the target metal copper. Has been. A part of them elutes together with copper and accumulates as an impurity in the electrolytic solution to hinder the electrolysis of copper. Therefore, in order to keep these eluted impurities below a certain concentration, it is necessary to purify the electrolytic solution.

Conventionally, the most common method for purifying copper electrolytic solution is to electrolyze the copper electrolytic solution using an insoluble anode such as lead and remove it as decoppered slime. Neutralization method of adding, sulfide precipitation method of blowing hydrogen sulfide gas into the electrolytic solution to remove it as a sulfide precipitate, and further concentrating the electrolytic solution concentrated with antimony and bismuth special impurities to crystallize copper sulfate crystals. There is a method of producing tampan which removes the impurities together with the coprecipitated impurities. However, in each of these methods, along with impurities to be removed, a much larger amount of copper is accompanied and removed, so that the copper is re-introduced to the previous stage of copper smelting to be recovered, and repeatedly treated, It was not satisfactory for the purpose of removing impurities from the system.

(Object of the Invention) As a result of the present inventors' investigations to solve the above-mentioned problems of the prior art and to provide a method for selectively separating and removing antimony and bismuth contained in a copper electrolytic solution by a simple operation. ,
The inventors have found that the above object can be achieved by subjecting the electrolytic solution to an oxidation treatment, and arrived at the present invention.

(Structure of Invention) That is, the gist of the present invention is to treat an acidic sulfuric acid solution containing antimony and bismuth with an oxidizing agent,
A method for treating an acidic sulfuric acid solution containing antimony and bismuth, characterized in that the antimony and bismuth are separated and removed as a precipitate.

As described above, according to the present invention, by adding an oxidizing agent such as hydrogen peroxide solution, hypochlorous acid, hypochlorite, etc. to a copper electrolytic solution, or by blowing an ozone gas, antimony and viscous are extracted from the solution. Is selectively separated. Therefore, the present invention is particularly suitable for the case where a large amount of antimony and bismuth as impurities in the anode reach the control limit of the concentration in the electrolytic solution. The reaction mechanism of this separation of antimony and bismuth and the morphology of the product are not clear.

The temperature of the electrolyte solution in which the above-mentioned oxidizing agent is added or blown is not particularly limited, but is preferably 40 ° C to 60 ° C. In addition, the electrolytic solution from which antimony and bismuth have been removed by the oxidizing agent treatment can be sent as it is to the copper removal electrolytic step or the electrolytic step.

Next, the present invention will be described more specifically with reference to Examples, but these Examples do not limit the scope of the present invention.

Example 1 500 ml of a copper electrolyte containing 40 g of Cu40 g / l, Ni15 g / l, As4.5 g / l, Sb0.55 g / l, Bi0.21 g / l and free sulfuric acid 212 g / l was placed in a beaker of 1,
To each beaker, 35% hydrogen peroxide solution, 25% hypochlorous acid and sodium hypochlorite were added, and stirred for 5 hours in a constant temperature bath at 60 ° C. Table 1 shows the analysis results of antimony and bismuth in the electrolytic solution that was over-separated after the stirring treatment.

Example 2 By the same method as in Example 1, the electrolytic solution having the same composition as in Example 1 was changed to a liquid temperature of 40 ° C., 60 ° C., 80 ° C. and 90 ° C., and 35% hydrogen peroxide solution was used as an oxidant. 5 ml was added and stirred for 5 hours. The results obtained are shown in Table 2.

Example 3 Electrolyte solution 1 having the same composition as in Example 1 was placed in a 2 liter beaker, 10 ml of 35% hydrogen peroxide solution was added as an oxidant, and the mixture was immersed in a constant temperature bath at 60 ° C. for stirring and stirring time Fig. 1 shows the relationship between the concentrations of antimony and bismuth.

Example 4 Cu 40 g / l, Ni 15.5 g / l, As 4.7 g / l, Sb 0.58 g / l, Bi 0.09 g / l, free sulfuric acid 218 g / l copper electrolyte solution 1 was placed in a three-necked flask. , Blow ozone gas at a rate of 2.5g / Hr for 3 hours,
Stir for 5 hours. During stirring, the temperature of the electrolytic solution was kept at 60 ° C. by the mantle heater.

The relationship between the stirring time and the antimony and bismuth concentrations is shown in FIG.

(Effects of the Invention) The present invention has the following effects due to the above configuration.

(1) Antimony and bismuth in the copper electrolyte can be selectively separated by a simple operation.

(2) Since only an oxidizing agent such as ozone gas or hydrogen peroxide solution is added, there is no consumption of free sulfuric acid and mixing of different metals into the liquid unlike the conventional neutralization method.

[Brief description of drawings]

Fig. 1 shows Cu40g / l, Ni15.5g / l, As4.7g / l, Sb0.58g / l, Bi0.0
A graph showing the relationship between the stirring time and the Sb and Bi concentrations (g / l) in the electrolytic solution when ozone gas was blown into the copper electrolytic solution containing 9 g / l and free sulfuric acid 218 g / l, The figure shows the stirring time and the Bb and Bi concentrations (g in the electrolytic solution) when ozone gas was blown into the copper electrolytic solution with the same composition as that of Fig. 1 at 2.5 g / Hr.
It is a graph which shows the relationship with / l).

Claims (2)

[Claims] 1. A method for treating an acidic sulfuric acid solution containing antimony and bismuth, which comprises treating an acidic sulfuric acid solution containing antimony and bismuth with an oxidizing agent to separate and remove the antimony and bismuth as a precipitate. 2. The treatment method according to claim 1, wherein the oxidizing agent is one selected from the group consisting of ozone, aqueous hydrogen peroxide, hypochlorous acid, and hypochlorite.