JPS6157899B2 - - 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, it relates to a method of adsorbing and recovering gallium in a solution using a special chelate resin. Commercial production of gallium is carried out using Bayer liquid for alumina production, so-called aqueous sodium aluminate solution, as a raw material. Since the concentration of gallium in Bayer's liquid is about 10 to 500 mg, it is an extremely useful raw material. However, there are two conventional methods for recovering gallium from this aqueous sodium aluminate solution: electrolysis using mercury as a cathode, converting gallium in the solution into amalgam, hydrolyzing the amalgam with caustic alkali, and producing garmin. A method in which an acid-alkali aqueous solution is then electrolyzed, and a method in which carbon dioxide gas is blown into a sodium aluminate aqueous solution to mainly precipitate the alumina content of the sodium aluminate aqueous solution, and carbon dioxide gas is blown into a solution with an increased ratio of alumina content and gallium content. A method has been adopted in which the alumina and gallium components are coprecipitated, the coprecipitate is dissolved in caustic alkali, and the resulting aqueous aqueous galmic acid solution is then electrolyzed. However, the former method 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 uses carbon dioxide to dissolve the mercury in the sodium aluminate aqueous solution. It has the disadvantage that the caustic alkali content is lost due to carbonation, so it is not fully satisfied industrially. Recently, a method for recovering gallium from a sodium aluminate solution by liquid-liquid extraction using an extractant consisting essentially of a water-insoluble substituted hydroxyquinoline and an extraction solvent consisting of an organic solvent has been proposed as a method for recovering gallium from Bayer's liquid. It has been proposed (Japanese Unexamined Patent Publications No. 51-32411, 52289-1989, 99726-1983, etc.). However, with this method, the amount of gallium recovered per reagent used is not industrially sufficient, the amount of gallium recovered is not industrially sufficient, or the selective adsorption of gallium is not necessarily high, making it difficult to use. Since the gallium recovery reagent is a liquid, there is a disadvantage that a considerable amount of the recovery reagent is dissolved in the aqueous sodium aluminate solution and lost, and this method is not industrially satisfactory. In view of these circumstances, the present inventors conducted intensive research in order to find a method for recovering gallium that overcomes the above-mentioned disadvantages, and as a result, they found that a chelate resin having a specific functional group was found to be highly selective for gallium in a strongly basic solution. They discovered that it adsorbs, and completed the method of the present invention. That is, in the present invention, A=
A chelate resin that has a functional group that can form a chelate bond via the NOH group and the A functional group and gallium (excluding chelate resins that have an amidoxime group) or a chelate resin that has a metal salt of the above functional group. An object of the present invention is to provide a method for recovering gallium contained in a solution, which comprises contacting with a strongly basic solution containing gallium. The chelate resin used in the present invention has a functional group in the molecule that can form a chelate bond with A=NOH group and B above A functional group via gallium (excluding chelate resins having an amidoxime group). Alternatively, the chelate resin is not particularly limited as long as it has a metal salt of the functional group. As the functional group of B, for example,

[Formula] =N-R ₁ [In the formula, R ₁ and R ₂ are hydrogen and an organic group (generally an alkyl group, an alkylene group, and a funinyl group, especially an alkyl group having 1 to 20 carbon atoms or hydrogen)
shows. However, the case where both R ₁ and R ₂ are hydrogen is excluded. ]≡N, -OH, -SH, =NOH,

[Formula] -NHOH, -NH- _NH2 , _-CS2H , -COOH, _-SO3H ,

[Formula] -CHO, -O-, -S-, -P(OR) ₂ , -PO(OR) ₂ , -PH(OR) ₃
(wherein R represents the same or different hydrogen, phenyl group, alkyl group or amino group). In particular, the functional group of B is

[Formula] = N-R ₁ , ≡N, -OH, -CS ₂ H,

[Formula] = NOH etc. are suitable. The chelate resin having a metal salt of the above-mentioned functional group of the present invention is a metal salt of the above-mentioned A and/or B functional group or a metal salt formed by a chelate bond between the above-mentioned A and B. There are no particular restrictions on the metal as long as the bonding force is weaker than the bonding force between the A and B functional groups and gallium. As the metal of the metal salt, alkali metals and alkaline earth metals such as sodium, potassium, calcium, and magnesium are generally used. Examples of such chelate resins include styrene-divinylbenzene copolymers having aldehyde groups and ketone groups, phenol resins, resins obtained by reacting hydroxylamine with polymers such as polyethylene and polypropylene, chloromethyl groups, sulfonyl chloride groups, and carbonyl groups. Polymers such as styrene-divinylbenzene copolymers, phenol resins, polyethylene, polypropylene, polyvinyl chloride, etc. that have amine-reactive groups such as chloride groups, isocyanate groups, epoxy groups, and aldehyde groups (hereinafter referred to as amine-reactive groups) ) containing at least an amino group, an imino group, such as aminoacetaldoxime, iminodiacetaldoxime, aminobenzaldoxime, aminoalkylbenzaldoxime, aminobenzhydroxamic acid, aminoalkylbenzhydroxamic acid, etc. One A in the molecule =
Compounds with NOH groups, resins reacted with mixtures of the above compounds, alkylaminobenzaldoxime, formylbenzaldoxime, benzaldoxime, benzhydroxamic acid, alkylaminobenzaldoxime, alkylaminobenzhydroxamic acid, alkylamino Methanebenzaldoxime, alkylaminomethanebenzhydroxamic acid, alkylaminoethanebenzaldoxime, alkylaminoethanebenzhydroxamic acid, formylbenzaldoxime, formylbenzacetaldoxime, benzisoxazole acetaldoxime, benzisoxazole acetate Hydroxamic acid oxime, benzisoxazole acetohydroxamic acid, phenylsulfinyl acetaldoxime, alkylaminophenyl sulfinyl acetaldoxime, alkylaminophenylmethylsulfinyl acetaldoxime, alkylaminophenyl ethyl sulfinyl At least one A=NOH in the molecule such as acetaldoxime, alkylaminophenylcarbonylacetaldoxime, alkylaminomethylphenylcarbonylacetaldoxime, benzyldioxime, benzyloxime, benzimidazoylthioacetaldoxime, etc. A compound having a group,
a mixture of said compound or said compound and aniline;
Condensation reaction resins of mixtures of resorcinol, 3-aminopyridine, 4-aminopyridine, 4-aminobenzenesulfonic acid, and 4-aminocarboxylic acids with formalin, epichlorohydrin, epibromhydrin, etc., and sodium and potassium of these resins. , alkali metals such as calcium and magnesium, alkaline earth metal salts, and the like. However, it has never been proposed that gallium can be adsorbed and removed from a strongly basic gallium-containing aqueous solution such as a sodium aluminate aqueous solution used in the Bayer method alumina production process using a chelate resin. It was completely unexpected that chelating resins would be so effective in recovering gallium from strongly basic gallium-containing aqueous solutions. In carrying out the method of the present invention, a strongly basic gallium-containing aqueous solution is usually used as the gallium-containing solution brought into contact with the chelate resin, but of course other gallium-containing solutions can also be used. In particular, the treatment liquid used in the method of the present invention is a gallium-containing sodium aluminate aqueous solution (composition; Ga; 0.01 to 0.5 g/, A
₂ O ₃ ; 50 to 120 g/, Na ₂ O/100 to 200 g/)
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 into a column filled with a chelate resin, etc. are generally employed. However, from the viewpoint of processing operations, a method in which the 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 conducting preliminary experiments. 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 is usually 10 to 100°C.
carried out at a temperature of Further, the contact time is not particularly limited, and 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 and recovered with hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sodium sulfide, iminodiacetic acid, ethylenediamine, tetraacetic acid, etc., or by heating separation. Gallium is separated from the chelate resin by separating the chelate resin and gallium. The gallium separated and recovered as described above can then be recovered as gallium metal by a known method, for example, by electrolysis with sodium galmate. According to the method of the present invention as described in detail above, the adsorption capacity for gallium is significantly greater than that of known gallium chelating agents, and the equilibrium gallium concentration can be lowered. Furthermore, since the adsorbent of the present invention is a resin, it has the advantage that gallium can be recovered by a simple operation method, and has great industrial value. Furthermore, the chelate resin of the present invention has an effect that the selective adsorption of gallium is significantly superior to that of known chelating agents. Further, since the chelate resin of the present invention has alkali resistance, it has the advantage that it is particularly suitable for recovering gallium from Bayer process liquid. EXAMPLES The method of the present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. Example 1 A resin having =NOH groups, _-NH2 groups, and -OH groups (hereinafter this polymer is referred to as chelate resin A) obtained by reacting 2-aminomethylbenzaldoxime, resorcin, and formalin. 10c.c., inner diameter
Packed into a 12m/mφ column and poured from the top of the column.
When 100 c.c. of a sodium aluminate aqueous solution from the alumina production process using the Bayer method containing 189 ppm of Ga, 42000 ppm of A, and 123,800 ppm of Na was passed through the solution for 2 hours and the effluent was analyzed for Ga and A, the first
The results shown in the table were obtained.

[Table] Examples 2 to 11 Chelate resin B; =NOH group and -NHOH group obtained by reacting 1,2-benzisoxazole-3-acetohydroxamic acid oxime, resorcinol, and formalin and ≡
A resin with N groups and -OH groups. Chelate resin C: =NOH group, -NHOH group, ≡N group, and -OH group obtained by reacting 5-fluoro-1,2-benzisoxazole-3-acetohydroxamic acid oxime, phenol, and formalin. resin. Chelate resin D: Resin having Na metal salt of =NOH group and -CS ₂ H group obtained by reacting vinylamidoxime-divinylbenzene copolymer with carbon disulfide and then treating with alkali with an aqueous sodium hydroxide solution. . Chelate resin E: A polycondensation resin of benzoyliminoethane diamide dioxime, aniline, and formalin is reacted with monochloroacetic acid, and then treated with alkali with an aqueous calcium hydroxide solution to form =NOH groups and -
A resin with a COOH-based Ca metal salt. Chelate resin F: =NOH group obtained by reacting 1,2-benzisoxazole-3-acetohydroxamic acid, 3-aminopyridine, resorcinol, and formalin and -
A resin with NH ₂ groups, ≡N groups, and -OH groups. Chelate resin G: 8-formylquinoline, benzaldehyde, and formalin are reacted to form a resin, and then hydroxylamine is reacted to form a = NOH group.

[Formula] A resin having a group. Chelate resin H: =NOH group obtained by reacting 2-hydroxybenzaldoxime, resorcinol, and formalin and -
Resin with OH group. Chelate resin I: =NOH group obtained by reacting 2-(N-methylaminoethyl)benzaldoxime, N-methylaniline, and formalin.

[Formula] A resin having a group. Chelate resin J: =NOH obtained by reacting 2-formylbenzaldoxime, benzyldioxime, and formalin
base and

[Formula] A resin having a group. Chelate resin K; 3== per unit resin obtained by reacting benzyldioxime, benzaldoxime, and formalin
Resin with NOH group. The above chelate resins were analyzed for Ga and A by passing 100 c.c. of sodium aluminate aqueous solution over 2 hours in the same manner as in Example 1, and the results shown in Table 2 were obtained.

[Table] Example 12 10 g of chelate resin A was added to 100 c.c. of the same sodium aluminate aqueous solution used in Example 1, and after shaking for 1 hour, the chelate resin and aqueous layer were separated, and the aqueous layer was The remaining Ga and A concentrations were analyzed. The results are shown in Table 4. Comparative Examples 1 to 2 Instead of the chelate resin A used in the method of Example 1, a strong basic ion exchange resin Duolite A-161 (manufactured by Diamond Shamlok Co., Ltd.) and a dithiocarbamate type chelate resin Sumikylate Q-10 were used. Example using (manufactured by Sumitomo Chemical)
Gallium was adsorbed in the same manner as in 12. The results are shown in Table 4. Comparative example 3 Kelex 100 (manufactured by Mesazu Atsushi Land Chemical Co., Ltd.: Structural formula Ga consisting of 10g of n-deganol and 80g of kerosene
The extractant was added to 100 c.c. of the same sodium aluminate aqueous solution used in Example 1, and after shaking for 1 hour, the aqueous layer and oil layer were separated, and the aqueous layer remained on the aqueous layer side.
The concentrations of Ga and A were analyzed. The results are shown in Table 4.

[Table] Comparative Example 4 The same procedure as in Example 1 was carried out except that Uniselect UR-50 (having iminodiacetate as a functional group, manufactured by Unitika Co., Ltd.) was used as the chelate resin. As a result, the adsorption recovery rates of Ga and A were respectively
They were 0.5% and 0.2%. As shown in Examples 1 to 12 and Comparative Examples 1 to 4, the chelating resin of the present invention can be used in a highly basic aqueous solution such as a sodium aluminate aqueous solution from the Bayer method alumina manufacturing process, or a solution containing a large amount of coexisting ions. Among them, it is possible to selectively adsorb and remove Ga metal ions up to the desired concentration, and the chelating function does not deteriorate even after repeated use, making it superior to known chelating agents. It's obvious.

Claims (1)

[Scope of Claims] 1. A chelate resin having in its molecule A=NOH group and B a functional group capable of forming a chelate bond via A functional group and gallium (excluding chelate resins having an amidoxime group) Alternatively, a method for recovering gallium contained in a solution, which comprises bringing a chelate resin containing a metal salt of the functional group into contact with a strongly basic solution containing gallium. 2 B The functional group that can form a chelate bond with the A functional group via gallium is [Formula] = N- R ₁ (wherein R ₁ and R ₂ each represent the same or different hydrogen or organic group. , except when both R ₁ and R ₂ are hydrogen.) ≡N, -OH, -SH, =NOH, [Formula] -NHOH, -NH-NH ₂ -CS ₂ H, -COOH, -SO ₃ H,
[Formula] -CHO, -O-, -S-, -P (OR) ₂ , -PO (OR) ₂ , -PH (OR) ₃ , (wherein R is the same or different hydrogen, phenyl group, alkyl 2. The method for recovering gallium according to claim 1, wherein the method is: 3 B The functional group that can form a chelate bond with the A functional group via gallium is [Formula] = N- R ₁ (wherein R ₁ and R ₂ each represent the same or different hydrogen or organic group. , except when both R ₁ and R ₂ are hydrogen), ≡N, -OH, -CS ₂ H,
The method for recovering gallium according to claim 1 or 2, characterized in that [Formula]=NOH. 4. A chelate resin in which A=NOH group and B functional group A and a functional group capable of forming a chelate bond via gallium are bonded to the same carbon in the molecule. The method for recovering gallium according to item 1, 2 or 3. 5. Claims 1, 2, and 3, wherein the gallium-containing solution is a sodium aluminate aqueous solution used in the Bayer method alumina manufacturing process.
Or the gallium recovery method described in Section 4.