JPH0470258B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for recovering gallium from a solution containing gallium. More specifically, the present invention relates to a method of adsorbing and recovering gallium in a solution using a special chelate resin. Commercial production of gallium is based on alumina production Bayer liquid, so-called aqueous sodium aluminate solution,
Alternatively, it is carried out using an acid-leached aqueous solution of slag containing gallium such as zinc or copper as a raw material. Two methods have been conventionally employed to recover gallium from an aqueous sodium aluminate solution. That is, a method of electrolyzing mercury as a cathode, converting gallium in the liquid into amalgam, hydrolyzing this amalgam with caustic alkali, and then electrolyzing and recovering the resulting alkaline garmic acid aqueous solution; Blow in carbon dioxide gas to mainly precipitate the alumina in the sodium aluminate aqueous solution. Blow in carbon dioxide into a solution with a high ratio of gallium to alumina to co-precipitate the alumina and gallium. This is a method in which galmic acid is dissolved in caustic alkali, and the resulting aqueous alkaline galmic acid solution is then electrolyzed and recovered. In addition, when recovering gallium from an aqueous acid leaching solution of gallium-containing slag, such as zinc or copper, for example, zinc concentrate is roasted, and then the zinc leaching residue from which most of the zinc is extracted is further subjected to sulfuric acid leaching and decopper removal. After that, the gallium cake obtained through a plurality of extraction steps is dissolved in an alkali, and the resulting aqueous alkali garminate solution is electrolyzed and recovered. However, the former method of recovering gallium from a sodium aluminate aqueous solution has the disadvantage that a large amount of mercury is dissolved and lost in the sodium aluminate aqueous solution during amalgamation, and the latter method The use of gas has the disadvantage that the caustic alkali content in the aqueous sodium aluminate solution is carbonated and lost. on the other hand,
When using an acid-leached aqueous solution of slag containing gallium such as zinc or copper, it has the disadvantage of requiring a complicated extraction process because it contains various impurity elements. Recently, as a method for recovering gallium from Bayer liquid, gallium is recovered from an aqueous sodium aluminate solution by liquid-liquid extraction using an extractant consisting essentially of water-insoluble substituted hydroxyquinolines and an extraction solvent consisting of an organic solvent. Methods have been proposed (JP-A-51-32411, JP-A-53-52289, JP-A-54-99726, etc.). However, in these methods, the reagent used has poor alkali resistance, the substituent group decomposes during long-term use, water solubility increases, and the recovery rate of the reagent and gallium decreases, and the gallium recovery reagent used is liquid. As a result, a considerable amount of the recovered reagent is dispersed and dissolved in the sodium aluminate aqueous solution and is lost.Furthermore, the quality of the aluminum hydroxide may be adversely affected due to the extraction agent being mixed in during the Bayer process. However, it has some drawbacks and is not yet industrially satisfactory. In view of these circumstances, the present inventors conducted extensive research to find a method for recovering gallium that overcomes the above-mentioned disadvantages, and as a result discovered that chelate resins having specific functional groups selectively adsorb gallium. The invention was completed. That is, the present invention provides (A) a hydroxyl group and (B) =
The present invention provides a method for recovering gallium contained in a solution, which is characterized by using a chelate resin having a functional group of O, =S, or -SH and bringing it into contact with a solution containing gallium. The chelate resin used in the present invention has (A) a hydroxyl group and (B) a functional group of =O, =S or -SH in the molecule. Both the (A) functional group and the (B) functional group are bonded to the carbon atoms that make up the ring, and the carbon atom to which the (A) functional group is bonded and the carbon atom to which the (B) functional group is bonded. Atoms are either directly bonded or bonded through only one carbon atom. In other words, the (A) functional group and the (B) functional group exist via two or three carbon atoms that constitute the ring. Such chelate resins include, for example, styrene-divinylbenzene copolymers containing (A) hydroxyl groups and (B) =O, =S, or -SH functional groups bonded to the ring atoms of halogen or compound compounds. A chelate resin reacted with a halomethyl derivative can be used. Cyclic compounds having both (A) and (B) functional groups include 1-hydroxyanthraquinone, 7
-Hydroxy-1-indanone, 8-hydroxy-α-tetralone, 8-hydroxy-1-decalone, 2-hydroxycyclohexanone, 3-hydroxycyclohexanone, 9,10-dithioxo-
1-Hydroxyanthraquinone, 7-hydroxy-1-thioindanone, 8-hydroxy-α-thiotetralone, 8-hydroxy-1-thiodecalone, 2-hydroxythiocyclohexanone, 3-
Hydroxythiocyclohexanone, 2-mercaptophenol, 3-mercaptophenol, 8-
Mercapto-1-naphthol, 2-mercapto-
1-naphthol, 1-hydroxy-2-mercaptoanthracene, 2-mercaptocyclohexanol, 8-mercapto-α-tetralol, 8-
Examples include mercapto-1-decarol and derivatives thereof. Alternatively, styrene, phenol, ethylene, propylene, vinyl chloride having a hydroxyl group, mercapto group, carboxy group, dithiocarboxy group, etc.
The above-mentioned (A) and
It is also possible to use a chelate resin in which a halogen, halomethyl, alkyl or arylsulfonyloxy, alkoxycarbonyl, or oxydicarbonyl derivative of a cyclic compound having a functional group (B) is reacted. Furthermore, it is also possible to use a chelate resin obtained by reacting a polymer having a halogen atom with a lithio- or halo-magnesiolated product of a halogen or haloalkyl derivative of a cyclic compound having a functional group (A) and (B). Therefore, the chelate having a functional group of the present invention can be obtained from a strong basic aqueous solution such as a sodium aluminate aqueous solution used in the Bayer process alumina manufacturing process, or an acidic gallium-containing aqueous solution such as an acid leaching aqueous solution of gallium-containing slag such as zinc or copper. Since it has never been proposed that gallium can be adsorbed and recovered by a resin, the chelate resin of the present invention is extremely effective in recovering gallium from strongly basic or acidic gallium-containing aqueous solutions. It was completely unexpected. In carrying out the method of the present invention, the gallium-containing solution brought into contact with the chelate resin is usually a strongly basic or acidic gallium-containing aqueous solution with a pH of 0.5 to 3, but of course other gallium-containing solutions may also be used. can also be applied. In particular, the treatment solution used in the method of the present invention is an acid-leached aqueous solution of zinc slag containing zinc, copper, etc. (composition: Ga: 0.01 to 0.5 g/, Zn: 20 to 80 g/,
pH 0.5 to 3) or a gallium-containing sodium aluminate aqueous solution produced in the Bayer method alumina manufacturing process is suitable. In carrying out the method of the present invention, the contact between the chelate resin and the gallium-containing solution may be carried out under appropriately selected conditions. The contact method is not particularly limited, and for example, a method of immersing a chelate resin in a solution containing gallium, a method of passing a gallium-containing solution through a column filled with a chelate resin, etc. are generally employed. Among these methods, from the viewpoint of treatment operations, a method in which a gallium-containing solution is passed through a column filled with a chelate resin is preferably employed. In carrying out the method of the present invention, the amount of chelate resin used is not particularly limited and varies depending on the gallium concentration in the gallium-containing solution to be treated, the type of chelate resin used, etc. It can be set by experimenting. Generally, the amount of chelate resin to be used may be selected as appropriate. The contact temperature between the chelate resin and the gallium-containing solution is not particularly limited, but it is usually carried out at a temperature of 10 to 100°C. Also, the contact time is not particularly limited;
A contact time of several seconds or more is usually sufficient. The chelate resin from which gallium has been adsorbed and collected by the method of the present invention is then eluted with hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sodium sulfide, iminodiacetic acid, ethylenediaminetetraacetic acid, etc., or the chelate resin and gallium are separated by heating. The gallium component is recovered by this method. The gallium separated and recovered as described above is
Then, it can be recovered as gallium metal by a known method, for example, by preparing it with sodium galmate and electrolyzing it. According to the method of the present invention as detailed above, compared to known gallium chelating agents, the adsorption capacity for gallium is extremely large, and the equilibrium concentration of gallium can be lowered. Furthermore, the chelate resin of the present invention has an effect that the selective adsorption property for gallium is significantly superior to that of known chelating agents. Furthermore, since the chelate resin of the present invention has alkali resistance and acid resistance, it has the advantage that it is particularly suitable for recovering gallium from Bayer process liquid or zinc ore acid leachate. Hereinafter, the method of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. Example 1 1-Hydroxyanthraquinone was chloromethylated with chloromethyl methyl ether in the presence of an anhydrous zinc chloride catalyst in a chloroform solvent, and then the chloromethylated 1-hydroxyanthraquinone was converted to styrene-divinyl in a nitrobenzene solvent and an anhydrous aluminum chloride catalyst. By reacting with a benzene copolymer, a polymer having -OH and =O groups in the molecule was obtained. Hereinafter, this polymer will be referred to as chelate resin A.
It is called. Contains Ga301mg/ and Zn23100mg/
1 g of the above chelate resin A was added to 50 ml of zinc ore leachate at pH 2.6, shaken for 3 hours, filtered, and analyzed for Ga and Zn in the solution. The results shown in Table 1 were obtained. Ta.

[Table] Example 2 After converting a hydroxycarbonylated styrene-divinylbenzene copolymer into a potassium salt, it was reacted with 3-hydroxy-4-mercaptophthalic anhydride in an acetonitrile solvent to convert -OH and -SH groups. A resin having the following properties was obtained. Hereinafter, this will be referred to as chelate resin B. Using 1 g of this chelate resin B, it was brought into contact with 50 ml of zinc ore acid leachate in the same manner as in Example 1, and Ga and Zn in the solution were analyzed.
The results shown in Table 2 were obtained.

[Table] Examples 3 and 4 Chelate resins A and B used in Examples 1 and 2
5g of each of Ga223mg/and Al44790mg/
The solution was added to 100 ml of an aqueous sodium aluminate solution from an alumina manufacturing process using the Bayer method, and the solution was shaken for 13 hours and then filtered. Ga and Al in the solution were analyzed, and the results shown in Table 3 were obtained.

【table】

Claims (1)

[Claims] 1 molecule contains (A) hydroxyl group and (B) =O, =S or -SH
has a functional group, both the (A) functional group and the (B) functional group are bonded to carbon atoms constituting the ring, and (A)
A chelate resin in which the carbon atom to which the functional group is bonded and the carbon atom to which the (B) functional group is bonded are directly bonded or bonded through only one carbon atom,
A method for recovering gallium contained in a solution, the method comprising contacting the solution with a solution containing gallium. 2. The method for recovering gallium according to claim 1, wherein (B) the functional group is -SH. 3. The method for recovering gallium according to claim 1 or 2, wherein the gallium-containing solution is an aqueous sodium aluminate solution or a zinc ore acid leachate in the Bayer process alumina manufacturing process.