JPS5842737A - Recovering method for gallium - Google Patents

Abstract

PURPOSE:To efficiently recover Ga from an Al salt soln. contg. Ga by passing the soln. through a column packed with a chelating ion exchange resin at a specified space velocity or below to allow Ga to be adsorbed on the resin and eluting the Ga. CONSTITUTION:An Al salt soln. contg. Ga such as a soln. of an Al compound manufactured by the Bayer process using Al(OH)3 or alumina as starting material is adjusted to <=3.5pH, and the soln. is passed through a column packed with a chelating ion exchange resin at <= about 5.01/hr space velocity (SV) to allow Ga to be adsorbed on the resin. The chelating ion exchange resin is prepared by introducing an aminocarboxylic acid such as iminodiacetic acid as a functional group into phenol, styrene or epoxy resin. The adsorbed Ga is eluted with >=6 N hydrochloric acid or the like.

Description

[Detailed description of the invention] The present invention relates to a method for recovering gallium.

Gallium has been produced in recent years due to the development of electronic technology.

Although the number of minerals containing gallium or gallium compounds as a main component has not yet been discovered,
It is accompanied by trace amounts of other metal ores. For example, bauxite, which is an aluminum magnet, also contains a small amount of gallium. Also.

It is also found in trace amounts in coal smoke ash, slag from zinc smelting, and Germanic ore. Attempts have been made to separate and recover these trace amounts of galifu.
Solvent extraction methods, mercury amalgam methods, carbonic acid blowing methods, etc. have been proposed or used. Scold #! : Each of these methods has its drawbacks. That is, in the solvent extraction method.

Difficulties in handling the solvent used, the unit cost of the solvent, and when the extraction target is an aluminum salt solution.

Disadvantages include organic contamination of aluminum salts after gallium extraction, mercury amalgam method has various contaminations caused by mercury, and carbon dioxide gas blowing method has drawbacks such as complicated operations. It has the disadvantage of poor gallium recovery efficiency.

On the other hand, it is conceivable to separate and recover gallium using ion exchange [1i1], but the separation efficiency of gallium and aluminum is poor and this method cannot be put to practical use.

Therefore, as a result of intensive research into a method for efficiently recovering gallium from an aluminum salt solution containing chloride by eliminating these drawbacks, the inventors of the present application have developed an ion exchange resin column filled with a chelating ion exchange resin. The present inventors have discovered that gallium and aluminum can be efficiently separated when the liquid is passed at a specific space velocity.

That is, in the present invention, an aluminum salt solution containing gallium is fed into an ion exchange resin column filled with a chelating ion exchange resin at a space velocity (hereinafter referred to as Sv) of about 5.0.
This method of recovering gallium is characterized by adsorbing gallium onto a chelating ion exchange resin by passing a liquid through the resin at a rate of 1/Hr or less, and then eluting the adsorbed gallium.

As the aluminum salt bath solution containing gallium in the present invention, for example, water produced by the Bayer process,
Examples include solutions of aluminum compounds using aluminized aluminum or alumina as starting materials, and acidic or weakly alkaline extracts of gallium-containing alumina resources.

Examples of chelating ion exchange resins used in the present invention include phenolic styrene, epoxy, and acrylic μ-ester/I/threads as functional groups such as diethylenetriamine, triethylenetethumine, tetofethylenepentamine, and pentafluoride. Amines such as ethylenehexamine, aminocarboxylic acids such as iminodiacetic acid, dibrobanolamine.

Examples include chelating ion exchange resins incorporating alcohol amines such as urea, thiourea, and phosphoric acid.
In particular, a chelating ion exchange resin incorporating Amitsuka p-boxylic acid, which has high selectivity for gallium, is desirable.

In order to recover gallium from an aluminum salt solution containing gallium in the present invention, first, an ion exchange resin tower filled with a chelating ion exchange resin is charged at an Sv of about 5.01/H.
The SV is generally around 10.01/Hr when a normal solution is passed through an ion exchange resin tower filled with a chelating ion exchange resin or an ion exchange resin. When an aluminum salt solution containing gallium is passed through at an SV of around 10.01/Hr, the separation efficiency between gallium and AtV miniram is very poor, and it cannot be put to practical use. Approximately 5.01/)
(Separation efficiency improves if the value is less than r, especially about 2.0
If the liquid is passed at around 1/Hr, further around 1.01/Hr, the separation efficiency will be very improved. The direction of liquid flow at this time may be either an upward flow or a downward flow. Regarding the temperature of the aluminum salt solution, the higher the temperature, the better the separation of gallium and aluminum, but considering the protection of the chelating ion exchange resin, which is an organic substance,
C is desirable, and the pH of the aluminum salt solution is:
Considering that gallium is sufficiently dissolved and the chelate resin is a type of cation exchange resin, it is 6.5.
It is preferable to adjust it to the following, and it is especially desirable to adjust it to 1-5.

By rubbing once in this manner, almost only gallium can be adsorbed onto the chelating ion exchange resin.

Next, in the present invention, it is necessary to elute the adsorbed gallium. For example, 9.

Elution is carried out with an acid solution, and the cuff method or patch method can be used as the elution method, but the five-cuff method is preferable because the five-cuff method is used during adsorption. At this time, the contact speed between the acid solution and the chelating ion exchange resin is 21/Hr or less in space velocity (!'3V), especially 0.
．． 5 to 11/Hr is preferable because it is convenient and allows efficient elution.

Examples of the acid solution used to elute gallium in the present invention include aqueous solutions of strongly dissociative mineral acids such as hydrochloric acid and nitric acid, aqueous solutions of organic acids such as acetic acid and citric acid, and aqueous solutions of hydrochloric acid and hydrogen fluoride. It is also possible to use 6
It is most desirable to elute with hydrochloric acid at a concentration above the specified level because in addition to the action of the acid, the complex-forming power of hydrochloric acid is also sluggish, and a highly concentrated gallium salt solution can be obtained in a relatively short time.

According to the present invention, gallium and aluminum can be efficiently separated, and in particular, the gallium concentration in the recovered liquid is 300.
Since the concentration is more than 7g of 0N, metal gallium can be obtained by electrolyzing this. Even if the gallium concentration in the recovered liquid is 3000 W/g or less, if the concentration ratio (weight) of gallium and aluminum is around 1 = 14, it is possible to crystallize aluminum by physical concentration such as evaporation. Since metal gallium can be analyzed in the same manner as above, metallic gallium can be obtained.

The present invention will be specifically explained using the following examples.

Example 1 pH of gallium-containing aluminum salt solution with sulfuric acid aqueous solution
After adjusting to 2.5, it was filtered using qualitative filter paper, and the filtrate was treated with chelating ion exchange resin UNISEREC LIR-5.
0 (Functional group is iminodiacetic acid, Unitika Co., Ltd. ail)
After passing 180 times the amount of the resin in a K-downward flow at 5V11/Hr, the resin was washed with water for 1.5 hours at S V 21/Hr, and a 6N hydrochloric acid aqueous solution was passed at 5V11/Hr for 6 hours. gallium was recovered.

The results are shown in Table 1.

Table 1 It is clear from Table 1 that the concentration of gallium in the recovered solution 9 was extremely high, and it was possible to electrolyze this to obtain metallic gallium.

Example 2 An aluminum salt solution containing 10 q/II of gallium was treated with a chelating ion exchange resin, Uniselect UR-5.
0 (has iminodiacetic acid as a functional group)

(manufactured by Unitika Co., Ltd.) filled with 60 mm inner diameter 9 mm length 1
gl 5 Qell glass column with downward flow.
A volume of liquid up to 120 times that of the resin was passed at v51/Hr to adsorb gallium and aluminum. Then S V 51/i
(Rinse the resin with water for 50 minutes at
/Hr in a downward flow for 4 hours to recover gallium.

The results are shown in Table 2.

Table 2 It is clear from Table 2 that the removal rate of gallium in the aluminum salt solution was 7296, and the ratio of gallium to aluminum in the stock solution was 1/460, but in the 9 recovered solution it was 1/10.5. ing. This recovered solution could be concentrated to obtain metallic gallium. Comparative Example 1 The process was carried out in exactly the same manner as in Example 2, except that the aluminum salt solution containing 10 q/l of liu A was passed through at SV 101 /Hr. A recovered liquid was obtained.

The results are shown in Table 3.

Table 3 From Table 3, the removal rate of potassium in the aluminum salt solution is 3
2%, the adsorption rate on the chelating ion exchange resin is less than half, and there is little merit in the adsorption operation, and the ratio of gallium to aluminum in the stock solution was 1/460, but in the recovered solution it was 1/2%. 24.5, and even if this was concentrated, the metal lithium could not be obtained.

Patent applicant: Unitika Co., Ltd.

Claims (2)

[Claims] (1) An aluminum salt solution containing gallium is passed through an ion exchange resin column filled with 118M of chelating ion exchange resin at a space velocity (87) of approximately 5.01/Hr or less to convert it into a chelating ion exchange resin. A method for recovering gallium, which comprises adsorbing gallium and then eluting the adsorbed gallium. (2) The recovery method according to claim 1, wherein the pR of the aluminum salt solution containing gallium is adjusted to 3.5 or less.