JPH1180853A - Recovery of antimony from sulfide form - Google Patents

Abstract

PROBLEM TO BE SOLVED: To separate impurity components such as Cu, As, Bi or the like and to recover Sb as simple substance by subjecting a sulfide form contg at least. Cu, As and Bi to oxidative leaching in the presence of alkali, adding alkali to the leach liquor to regulate the pH therein to >=specified value, executing oxidation treatment and separating and recovering Sb. SOLUTION: As the one of a sulfide form, antimony sulfide can be given. This is oxidized in the presence of alkali to leach As and Sb, Cu and Bi remain in the residue, after solid-liq. separation, furthermore, only as for the leach liquor, the pH is regulated to 1 by the addition of alkali, and oxidation treatment is executed. In this way, Sb only is precipitated, and the leach liquor contg. As is subjected to solid-liq. separation. The oxidative leaching and oxidation treatment are executed in such a manner that air is blown into the soln., and, preferably, the amt. of air to be blown is regulated to 0.1 to 1.0 m<3> /min per m<3> soln., and the temp. of the soln. is regulated to 50 to 80 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for separating and recovering antimony from a sulfide form containing antimony, and more particularly, to a method for separating antimony from an sulfide form formed as a non-ferrous smelting intermediate. The present invention relates to a method for separating and recovering hydroxides.

[0002]

2. Description of the Related Art In recent years, antimony (Sb) has attracted attention as a material for compound semiconductors, and its demand has been increasing.

[0003] Mainly, stibnite containing antimony (Sb ₂ S
₃ ) Smelting using raw materials, and further producing crude antimony by a dry method in the refining process, and then obtaining high-grade antimony by an electrolytic method or the like.

[0004] In addition, various intermediates are generated in the non-ferrous smelting process of copper and zinc. Among them, intermediates in the form of sulfide include antimony, arsenic, bismuth and the like in addition to copper and the like. Is a major feature. Among the various impurities in the form of sulfides such as smelting intermediates, it has been difficult to separate and recover antimony from conventional impurities, particularly those containing arsenic and bismuth.

[0005] However, various methods have been proposed to separate and recover antimony from other metals contained in non-ferrous smelting intermediates, raw material ores and the like for the production of high-grade antimony. For example, as a method of separating and recovering arsenic from a sulfide-based smelting intermediate containing arsenic, copper, zinc, bismuth, antimony, and the like, a sulfide-based smelting intermediate is controlled as a slurry to have a pH of 5 to 8 and controlled. A method has been proposed in which only arsenic is separated and recovered by air oxidation while suppressing extraction of antimony, antimony, and bismuth (JP-A-54-160590).
No.). Also, there is disclosed a method of separating arsenic, copper, antimony, and the like by employing an autoclave, which is an expensive reactor (CIM Bulletin; Vol. 78, No.
884 (1985) pp. 84-93).

[0006]

However, individually separating and recovering antimony by the above method has the following problems.

In the method proposed in Japanese Patent Application Laid-Open No. 54-160590, it is difficult to separate and recover antimony alone because antimony behaves together with copper and bismuth. Also, the method of using an autoclave is
There is a problem that the operation process is inefficient and it is difficult to remove bismuth.

The present invention has been made to solve the above-mentioned drawbacks, and an object of the present invention is to provide a method for separating impurity components such as copper, arsenic, and bismuth from a sulfide form to recover antimony alone.

[0009]

Means for Solving the Problems To solve the above problems, the invention according to claim 1 includes, in addition to antimony,
Arsenic and antimony are leached by oxidizing sulfides containing at least copper, arsenic, bismuth, etc. in the presence of alkali, leaving copper and bismuth in the residue, and adding only leachate to the alkali after solid-liquid separation. This is a method for recovering antimony in which only antimony is precipitated by adjusting the pH to 11 or more and then oxidizing, and a leachate containing arsenic is separated into a solid and a liquid. This provides a method of separating copper, bismuth, arsenic and antimony and recovering only antimony alone. Further, the quality of the recovered antimony can be increased.

The invention according to claim 2 is a method for recovering antimony in which the oxidative leaching and the oxidizing treatment blow air into a solution.

According to a third aspect of the present invention, in the oxidative leaching and the oxidizing treatment, 0.1% per m ³ of the solution is used.
This is a method for collecting antimony in which air is blown to 1.0 m ³ / min. Thereby, at the time of oxidative leaching, leaching of copper and bismuth can be suppressed, and the quality of the leaching solution can be improved.
Further, in the oxidation treatment, the quality of antimony to be recovered while suppressing the precipitation of arsenic can be improved. Further, antimony can be efficiently and inexpensively collected by the effect of stirring the blown air.

The invention according to claim 4 is a method for recovering antimony, wherein the temperature of the solution is in the range of 50 to 80 ° C. Thereby, the impurity concentrations of copper, bismuth, and arsenic can be kept low, and the quality of recovered antimony can be increased.

According to a fifth aspect of the present invention, the sulfide form is antimony sulfide (Sb ₂ S ₃ , Sb ₂ S ₅ ).
This is a method for recovering antimony when

Here, the alkali is a substance having strong basicity, specifically, caustic soda (NaOH), sodium carbonate (Na ₂ CO ₃ ), ammonia (NH ₃ ) and the like. Particularly, caustic soda is preferred. The reason for leaching with an alkali is that it easily acts on the target metal and requires only a small amount, so that it does not corrode containers or the like.

The oxidation in the oxidizing leaching and oxidizing treatment is performed by adding an oxidizing agent. As the oxidizing agent, F
e ³⁺ , MnO ₂ , KMnO ₄ , oxygen (O ₂ ), air, hydrogen peroxide solution (H ₂ O ₂ ) and the like. In particular, air is preferred.

[0016] The sulfide form includes antimony-containing ore such as stibnite, sediment containing antimony generated under the cathode of electrolytic refining of copper and the like, and exhaust gas and dust during the dry smelting of copper and the like. , Copper, etc. during hydrometallurgy.

The leaching can be performed by a leaching apparatus equipped with a rotary blade capable of blowing air under atmospheric pressure.

The apparatus for solid-liquid separation can be performed by a usual filtration apparatus such as a filter press.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be specifically described below with reference to FIG. Here, 1.69 dry-t and 0.47 dry-t of other intermediates were used as sulfides. Other intermediates are
It is waste oxysulfide generated in the sulfuric acid process during copper dry smelting.
The composition of the sulfide form is shown in Table 1.

[0020]

[Table 1] The sulfide form was leached by adding 450 kg of caustic soda while blowing 3.0 m ³ / min of air into a stirred leaching tank filled with 10 m ³ of industrial water. Table 2 shows the composition of the leaching solution.
Shown in

[0021]

[Table 2] This shows that the leaching of copper and bismuth is suppressed. Blowing amount of air solution 1 m ³ per 0.
Is a 3m ³ / min, can be blown in the range of 0.1 ~1.0m ³ / min. In this case, if it is less than 0.1 m ³ / min, the effect of oxidation does not appear because the blowing amount is small.
If it is more than 1.0 m ³ / min, the efficiency of oxidation by air is reduced, and the blowing power is increased, which is not preferable. 450 kg of caustic soda was added as an alkali, the solution temperature was initially adjusted to 60 ° C., and the mixture was leached with stirring for 5 hours. The composition of the leaching solution is shown below.

Here, the pH is preferably in the range of 7.0 to 9.0. If the pH is less than 7.0, leaching of arsenic and antimony is unfavorably slow, and if the pH is higher than 9.0, the leaching of sulfur becomes remarkable. The solution temperature is
A range from 50C to 80C is preferred. If the temperature exceeds 80 ° C., the cost of steam energy is increased, and if the temperature is lower than 50 ° C., the leaching reaction speed becomes slow and it is not efficient.

After the oxidative leaching treatment, solid-liquid separation was performed by a filter press to obtain a leachate of 13 m ³ and a residue of 1.40 dry-t. Table 3 shows the composition of the residue.

[0024]

[Table 3] This shows that arsenic and antimony were leached out, but copper and bismuth were not leached out and remained in the residue.

Subsequently, 12 m ³ of an alkaline leachate containing antimony and arsenic was adjusted to pH 11 with caustic soda, the temperature of the solution was adjusted to 60 ° C., and 3.6 m ³ of air was further blown in for oxidation treatment. The effects of the treatment time on the concentrations of antimony and arsenic in the leachate at this time are shown in FIGS. 2 and 3, respectively.
FIG. 2 shows that most of the antimony in the leachate was not dissolved in the solution in 15 minutes. According to FIG.
In the case of arsenic, there is almost no effect of time, and it can be seen that arsenic remains in the solution. Therefore, arsenic remained in the liquid as it was, but antimony precipitated. Table 4 shows the composition of the solution after the oxidation treatment.

[0026]

[Table 4] Here, the pH of the solution needs to be 11 or more.
If the pH is less than 11, the processing time becomes longer, which is not efficient. Blowing amount of air solution 1 m ³ per 0.
Is a 3m ³ / min, can be blown in the range of 0.1 ~1.0m ³ / min. In this case, if it is less than 0.1 m ³ / min, it takes too much time to remove antimony. If the amount is more than 1.0 m ³ / min, the cost of the blowing power increases.

[0027]

According to the present invention, in addition to copper, antimony,
It is possible to separate and recover antimony from sulfide forms including arsenic, bismuth, etc.
Each of the bismuths became antimony-free, and the degree of freedom in the treatment method was increased.

[Brief description of the drawings]

FIG. 1 is a flow sheet showing a method for removing antimony.

FIG. 2 shows the effect of the treatment time of the oxidation treatment of the purified liquid precipitate on the alkali leachate on the antimony concentration of the treated liquid.

FIG. 3 shows the effect of the treatment time of the oxidation treatment of the purified liquor on the alkali leachate on the arsenic concentration of the treated liquor.

Claims (5)

[Claims] 1. A sulfide form containing at least copper, arsenic and bismuth is leached by oxidation in the presence of an alkali, and the leachate after solid-liquid separation is adjusted to pH 11 or more by adding an alkali, and then oxidized. A method for recovering antimony from a sulfide form. 2. The method for recovering antimony according to claim 1, wherein said oxidizing leaching and said oxidizing treatment blow air into a solution. 3. The antimony recovery method according to claim 2, wherein in the oxidizing leaching and the oxidizing treatment, 0.1 to 1.0 m ³ / min of air is blown per 1 m ³ of the solution. Collection method. 4. The method for recovering antimony according to claim 1, wherein the temperature of the solution is in the range of 50 to 80 ° C. 5. The method for recovering antimony according to claim 1, wherein the sulfide form is antimony sulfide.