JPS6123248B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for treating matte generated during dry smelting, and more specifically, it involves treating zinc matte or copper matte with sulfuric acid to elute impurity iron compounds, and utilizing hydrogen sulfide gas generated at this time. This relates to a treatment method that recovers high-grade pine that does not contain hydrous silicic acid by leaving valuable metals such as copper, lead, and silver as acid-insoluble sulfides, and by using sulfuric acid at a specified concentration. It is. Recently, as an energy-saving measure, the smelting method has changed from the conventional blast furnace method to the flash furnace method, and it has become impossible to supply raw materials with a large amount of iron compounds as before. Therefore, low-grade raw materials such as pine, which contain less than 10% copper, must be significantly reduced in volume as raw materials unless they are treated to improve their quality. However, no effective method for treating pine has been established so far. In other words, up until now, the quality of copper and silver has been improved by the flotation method, but with this method, if the emphasis is placed on increasing the quality, the actual yield rate will decrease, and it is difficult to achieve both improvement in quality and increase in the actual yield rate. I couldn't do it. In addition, the magnetic separation method cannot separate iron from copper and silver, and the pine produced during the heat treatment cannot be separated into individual pieces even if crushed to less than 300 mesh. Separation was impossible. The present invention was made in order to eliminate such drawbacks, and its gist is that sulfuric acid with a concentration of 7 to 12N is added to pine such as zinc pine or copper pine, and the iron content in the pine is reduced by the sulfuric acid. This is a method of treating pine that improves the quality and yield of Au, Ag, Cu, Pb, etc. by leaching out the zinc content. It is an object of the present invention to provide a method for treating pine that not only improves the quality of nonferrous metals but also significantly improves the actual yield of these metals. The processing method of the present invention will be explained below.

[Table] However, only Au and Ag are (g/ton). Typical components of pine are as shown in Table 1. Since pine is generally produced in the form of a lump, it is ground into 60 meshes using a crusher and then mixed with 5N~
Add _{19N H2SO4} . When HNO ₃ is used as a solvent, valuable metals such as Cu, Ag, and Pb are also eluted, and when HCI is used, hydrous silicic acid is produced, resulting in inconvenience. Therefore H ₂ SO ₄ is suitable. however
Since the concentration of H ₂ SO ₄ has a large effect, Tables 2 and 3 show various effects of the concentration of H ₂ SO ₄ .
The elution conditions in this table are as follows. Imatsuto: 10g B Solvent: Concentrated H ₂ SO ₄ C Reaction temperature: 30℃ D Reaction time: 3 hours

【table】

【table】

[Table] When the H ₂ SO ₄ concentration exceeded 12N, the solid-liquid ratio decreased, the pulp concentration became too high, the viscosity increased, and the reaction tended to be insufficient. Further, since Fe is eluted and supersaturation is reached, crystallization of FeSO ₄ .7H ₂ O begins to proceed. On the other hand, when the H ₂ SO ₄ concentration becomes 7N or less, the elution rate of Fe and Zn decreases even if the added equivalent is the same, especially
Zn elution is suppressed. In addition, the formation of hydrous silicic acid becomes noticeable and the eluted residue becomes less sensitive. Next, the relationship between the amount of H ₂ SO ₄ added and elution is that Fe accounts for about 50% in pine and most of it is FeS.
(Cu ₂ S)--FeO. FeS is relatively easily eluted by H ₂ SO ₄ and has the element of releasing H ₂ S gas upon decomposition, which converts dissolved Cu, Ag, and Pb into insoluble sulfides. From the examples shown in Tables 2 and 3, it is clear that the elution rate differs depending on the H ₂ SO ₄ concentration even if the amount added is the same, and it is also greatly influenced by the equivalent amount added. I understand that. The amount of H ₂ SO ₄ added is the same as Fe contained in pine.
Approximately sufficient results were obtained at around 1.5 equivalents for any H ₂ SO ₄ concentration relative to the Zn content. That is, the elution rate of Fe reached approximately 90% or more, and it was possible to achieve an elution rate of 80% for Zn. In addition, the Cu content in the elution residue is 30 to 33%.
We were able to improve the quality by approximately three times compared to the 10% Cu before treatment. It was found that by adjusting the concentration and amount of H ₂ SO ₄ added, it was possible to change the Zn elution rate from 7% to 90%. Regarding Ag, although qualitative analysis was performed for all Examples, it was not detected in the eluate.
It can be assumed that, like Cu and Pb, Ag and Au are approximately three times as high in quality. The following Example 1 shows a process performed based on the above experiment. Example 1 Table 4 below shows the processing conditions, and Table 5 shows the results of processing under these conditions.

【table】

[Table] As mentioned above, according to the present invention, the
Fe reacts with H ₂ SO ₄ and becomes FeSO ₄ and is eluted, and when this solution is left to cool from 60℃ to room temperature (20℃),
It crystallizes as FeSO _{4.7H 2} O. Also FeSO ₄
Yellow iron oxide FeO.OH, magnetite (Fe ₃ O ₄ ), etc. can be easily produced by air oxidation while adjusting the pH of the solution. Furthermore, it is also possible to produce ferrite and iron oxide (Fe ₂ O ₃ )' for pigments, and it has the advantage of being able to use Fe as effectively as Cu, Ag, and Au. In this way, the present invention can process pine to produce Cu, Ag, Au, etc., which was considered impossible with previous processing methods.
Improves Pb grade by more than 3 times, significantly reduces copper smelting costs, and reduces Fe content, which has a negative impact on copper smelting, to about 90%
%, and this Fe can now be used effectively to produce yellow iron oxide. In addition, by effectively removing Fe, Cu, Ag,
This improves the quality of Au, etc., and greatly improves the actual yield of these components in the copper smelting process, resulting in a greater contribution to the smelting industry.

Claims (1)

[Claims] 1. Pines such as zinc pine and copper pine with a concentration of 7 to
By adding 12N sulfuric acid, the iron and zinc contained in the pine are eluted and removed by the sulfuric acid to improve the quality and yield of Au, Ag, Cu, Pb, etc. contained in the pine. How to treat pine trees. 2 Claims characterized in that Cu, Pb, and Ag partially dissolved in the H ₂ S gas generated by decomposing the FeS component in the iron component are recovered as sulfides insoluble in sulfuric acid. The method for treating pine according to item 1. 3. The method for treating pine according to claim 1, wherein the silicic acid compound contained in the pine is treated with the sulfuric acid to improve the permeability of the silicic acid as silicic acid with low water content. 4 After eluting the above iron content as a FeSO ₄ solution,
The method for treating pine according to claim 1, characterized in that yellow iron oxide or magnetic iron oxide is produced by adjusting the pH of the FeSO ₄ solution and performing air oxidation.