JPS59169932A - Collection of gallium - Google Patents

Abstract

PURPOSE:To achieve the effective adsorption of Ga, and to lower the equilibrium concentration of Ga, by contacting a solution containing Ga with a chelate resin having an atomic group of a specific formula in the molecule. CONSTITUTION:A chelate resin having an atomic group containing two or more N atoms and represented by the formula (n is integer of 2-10) (e.g. 2-10C polyethylene-polyamino group, guanidine group, amidino group, hydrazi group, hydrazino group, hydrazono group, azo group) in the molecule is synthesized, and is made to contact with a solution containing Ga. Ga can be efficiently adsorbed and the equilibrium concentration of Ga can be lowered by this process.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for recovering gallium from solutions containing potassium.

More specifically, it relates to a method of adsorbing and recovering gallium in a solution using a special chelate resin.

Commercial production of potassium is carried out using alumina production Bayer liquor, so-called aqueous sodium aluminate solution, and aqueous zinc ore acid leaching solution as raw materials. Conventionally, there are two methods for recovering gallium from an aqueous solution of sodium aluminate: electrolysis using mercury as a cathode, converting gallium in the solution into amalgam, hydrolyzing the amalgam with caustic alkali, and producing a galmino acid alkali. The aqueous solution is then electrolyzed and recovered, and carbon dioxide gas is blown into the sodium aluminate aqueous solution to mainly precipitate the alumina content in the sodium aluminate aqueous solution, and carbon dioxide gas is blown into the 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 galconoic acid alkali solution is then electrolyzed and recovered. In addition, the method for recovering gallium from an aqueous zinc ore acid leaching solution involves roasting the zinc concentrate, then extracting most of the zinc from the zinc leaching residue, which is then subjected to sulfuric acid leaching, decopper removal, and then multiple extractions. A method has been adopted in which the gallium cake obtained through the process is bath-dissolved in an alkali, and the resulting aqueous alkali galconoic acid solution is electrolyzed and recovered.

However, the former method of recovering gallium from an aqueous sodium aluminate solution has the disadvantage that mercury in a large amount is dissolved and lost in the aqueous sodium aluminate 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. or,
When using zinc ore acid leachate as a target, there is a drawback that it requires a complicated extraction process because it contains various impurity elements.

Recently, as a method for recovering potassium from Bayer's solution, gallium has been recovered from an aqueous sodium aluminate solution by liquid-liquid extraction using an extractant consisting essentially of water-insoluble substituted hydroxyquinolines and an extraction bath consisting of an organic solvent. Methods have been proposed (Japanese Unexamined Patent Publication No. 5'l-'32411, Shuma 5+3-52289, Shuma 54-99).
Publication No. 726, etc.).

However, in this method, the reagent used has poor alkali resistance, the substituents decompose during long-term use, water solubility increases, and the recovery rate of the reagent and gallium decreases, and the gallium recovery reagent used is a liquid. Therefore, a considerable amount of the recovery reagent is dispersed and dissolved in the sodium aluminate aqueous solution and lost, and there is also the disadvantage that the quality of the aluminum hydroxide may be adversely affected by the extraction agent being mixed in during the buyer process. This has not yet been industrially satisfied.

In view of these circumstances, the present inventors conducted extensive research in order to find a method for recovering potassium that overcomes the disadvantages mentioned above, and as a result, they discovered that a chelate resin having a specific functional group selectively adsorbs gallium. , we have completed the present invention.

That is, the present invention provides -N-((J2)n-N- and four forces -N-N- and/or
or -N=N-1111 (n represents an integer from 2 to 1O) A chelate resin having an atomic group having two or more nitrogen atoms as the minimum constituent unit is brought into contact with a solution containing gallium. The object of the present invention is to provide a method for collecting gallium contained in a solution.

The chelate resin used in the present invention is not particularly limited as long as it has an atomic group having two or more hydroxyl atoms represented by the above general formula.

Typical chelate resins include styrene, ethylene, propylene, vinyl chloride, acrylonitrile, α-chloroacrylonitrile, which have amine-reactive groups such as chloromethyl group, nitrile group, chlorine, bromine, and other halogen atoms;
A polymer containing a monomer such as vinylidene cyanide or methacrylonitrile (hereinafter referred to as a resin having a do7mine-reactive group) has a primary or secondary amino group, and (n is An amine compound having an atomic group with two or more nitrogen atoms whose minimum constituent unit is (representing an integer from 2 to 1O), such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, occumethylene Diamine, nonamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenepentamine, hexamethylenediamine, guanidine, hydrazine, 2-diethylenetriaminopyridine, l-amino-3-triethylenetetraminonaphthalene, 1- cyethylenetriaminophenazine,
4-diethylenetriaminobenzamidine, 3-phenylformasan, biguanide Nl-ethyl-N2-methylbenzamidine, N-phenylbenzamitracine,
Formazan, phenylhydrazine, 2,4-pyridinediamine, 1,8-diaminocarbazole, 1,8.5-
Examples include polymers obtained by reacting 1-lyamine-2-ethylenediamine and derivatives of these amine compounds.

Therefore, gallium can be adsorbed by the chelate resin having a functional group of the present invention from strongly basic aqueous sodium aluminate solutions used in the Bayer method alumina production process or acidic gallium-containing solutions such as zinc ore acid leachate. It is completely unexpected that the chelate resin of the present invention would be extremely effective in recovering gallium from strongly basic or acidic gallium-containing aqueous solutions, since the ability to remove gallium has never been proposed in the past. Ta.

In carrying out the method of the present invention, the potassium-containing solution to be brought into contact with the KIRE-1 resin is usually a strongly basic or potassium-containing solution.
An acidic gallium-containing aqueous solution of 1i 0.5 to 3 is used, but of course other potassium-containing solutions can also be used.

In particular, the treatment liquid used in the method of the present invention is a potassium-containing sodium aluminate aqueous solution (composition; Ga: 0.01 to 0.59/l) used in the production process of Bayer process alumina.

Zn: 20~80Q/i-, pno,! 5-3) Ka&
- Suitable.

In carrying out the method of the present invention, the contact between the KIRE-1 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 in which the chelate resin is immersed in a solution containing potassium, a method in which a gallium-containing solution is introduced 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 KIRE-1 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 oil of the chelate resin used, etc. Electricity can be installed by conducting experiments.

In general, the amount of chelate/resin used may be selected as appropriate.

The contact temperature between the chelate resin and the potassium-containing solution is not particularly limited, but it is usually carried out at a temperature of 10 to 100°C.

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, ethylenediaminetetraacetic acid, etc., or separated by heating to separate the chelate resin and gallium. Separate.

The gallium separated and recovered as described above can then be converted into sodium carmate using a known method, for example, and electrolyzed to recover potassium metal.

According to the method of the present invention as detailed above, the adsorption capacity for gallium is significantly greater than that of known gallium chelating agents, and the potassium equilibrium concentration can be lowered.

Further, the chelate resin of the present invention has an effect that the waste adsorption property for gallium is significantly superior to that of known chelating agents.

In addition, the chelate resin of the present invention has alno acid resistance and acid resistance, so it has the advantage that it is particularly suitable for recovering potassium from Bayer first step solution and zinc ore acid leachate. There is.

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 Acrylonitrile-divinylbenzene copolymer was
An aqueous solution of diethylenetriamine with a weight percent concentration of 1
1 g of a resin having a diethylene triamino group (hereinafter referred to as chelate resin A) obtained by reacting at 20° C. to 140° C. for 4 hours was mixed with Ga 301 W/l, zn.
2a, io.

It was added to 50% of zinc ore acid leachate containing mvt at pH-2.6, shaken for 3 hours, filtered, and analyzed for Qa and Zn in the solution, and the results shown in Table 1 were obtained. .

Table 1 Example 2 Chelate resin B: A guanidino group-containing resin obtained by reacting a chloromethylated styrene-divinylbenzene copolymer with guanidine carbonate in a 10% sodium hydroxide water bath at 100 to 105°C for 4 hours. resin.

Chelate resin C: A resin having guanidino groups and hydrazino groups obtained by reacting an acrylonitrile-polyethylene glycol dimethacrylate copolymer with guanidine nitrate and hydrazine in an aqueous solvent at 95 to 100°C for 8 hours.

Chelate Resin D: A resin having diethylenetriamino groups and amidino groups obtained by reacting an acrylonitrile-divinylbenzene copolymer with 4-diethylenetriaminobenzamidine in a water solvent under pressure at 120 to 180°C for 11 hours.

Chelate resin E Chlormedylated styrene-divinylbenzene 3-phenylformazane to phenylformazane copolymer . □1,8o～. . . . ,2-a1 This resin has a formazan group obtained by the reaction.

Chelate resin F; Biguanide is added to chloromethylated styrene-divinylbenzene copolymer in an aqueous solvent at a concentration of 90 to io
Resin with guanidino group obtained by reaction at °C for 6 hours.

Chelate resin G; Hexamethylenetetramine was added to vinylidene cyanide-divinylbenzene copolymer in an aqueous solvent for 1
A resin having hexamethylenetetramino groups obtained by reaction at 20 to 150°C for 2 hours.

1 g of each of the above chelate resins was brought into contact with 50 - of the zinc ore acid leachate in the same manner as in Example 1, and the Ga in the P solution was
, did you analyze Zn? ．． = As shown in Table 2, the result power is 5 and the talent is tj.

Table 2 Examples 8-14 Chelate trees used in Examples 1-7 A, B, C, D,
E, F, G (7) each 5 9 woGa 223rtq/
l.

A4 Contains 44.790Q/L (1 part sodium aluminate solution from the alumina production process using the ear method)
00m/! In addition, after shaking for 13 hours, it was filtered to remove Q in the P solution.
When performing the At analysis, the results shown in Table 3 were obtained.

Table 8 Procedural amendment - (method) % formula % l Indication of the case 1982 Patent barrel 43700 No. 2 Name of the invention Method for collecting gallium 3 Person making the amendment Relationship to the case Patent applicant Kitahama, Higashi-ku, Osaka City 5-15 (209) Sumitomo Chemical Co., Ltd. Representative Takeshi Hijikata 4 Agent 5-15 Kitahama, Higashi-ku, Osaka Showa Month, Day, 1939 (voluntary) 6 Full text of the specification to be amended 7 Engraving of the specification of the contents of the amendment (No change in content)

Claims (1)

[Claims] (IJ) A chelate resin having an atomic group having two or more nitrogen atoms whose minimum constituent unit is μN (n is an integer from 2 to 10) in the molecule is combined with a gallium-containing solution. A method for collecting gallium contained in a solution, characterized by contacting the gallium contained in a solution. (2) The atomic group having two or more nitrogen atoms in the molecule is a polyethylene polyamino group, a guanidino group, or an amidino group having 2 to 10 carbon atoms. , hydrazi group, hydrazino group, hydrazino group, azo group, −+−+−P・・・・−・”
The method for collecting gallium according to claim 1, characterized in that a chelate resin having at least one atomic group selected from among the above is used. (3) The method for collecting potassium 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.