JPS621571B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for recovering indium from a solution containing indium. More specifically, it relates to a method of adsorbing and recovering indium in a solution using a special chelate resin. Although indium is widely distributed on the earth, it does not exist in a naturally concentrated state, so it must be concentrated by some method that removes the major components and circulates a liquid containing trace components, or it must be concentrated in a very diluted state. A method is being considered for direct recovery from Industrial production of indium is from slag concentrated in the by-products of zinc and lead smelting. An industrial method for producing indium is, for example, by leaching lead blast furnace slag with sulfuric acid, separating it into a residue containing indium, lead, etc., and a solution containing components such as zinc, copper, cadmium, etc., and then further processing the above residue. Perform sulfuric acid leaching to dissolve indium and separate it from lead, add zinc oxide and sodium sulfide to the above indium-containing solution, perform neutralization and sulfidation to separate indium as a precipitate, and add sodium hydroxide to the precipitate. A method is known in which impurities are dissolved and removed, residual indium is again leached with sulfuric acid, treated with hydrogen sulfide to remove the impurities by precipitation, and then replaced with aluminum to obtain metallic indium by electrolysis. These ores, which are the most effective raw materials for indium, contain many different elements, so the process to produce indium is complicated as described above, and it is not easy to recover indium at low cost. do not have. Furthermore, as a method for recovering indium from an indium-containing solution, a method of adsorption and recovery using a chelate resin having an iminodiacetic acid type functional group is known (Anal chem. Acta. Analytica, Himika, Acta, 40 (1968) 479-485). ). However, the above method using a chelate resin having an iminodiacetic acid type functional group has drawbacks such as the amount of indium recovered per reagent used is not industrially sufficient and the selective adsorption of indium is not necessarily high. However, it has not yet been industrially satisfied. In view of these circumstances, the present inventors conducted extensive research to find a method for recovering indium that overcomes the above-mentioned disadvantages, and as a result, they found that a chelate resin having a specific functional group highly selectively adsorbs indium in an indium-containing solution. We have discovered that this is the case, and have completed the method of the present invention. That is, the present invention combines a chelate resin having at least one functional group selected from an oxime group, an aminoalkylene phosphate group, an oxine group, a dithiocarbamate group, and a metal salt of the functional group in its molecule with a solution containing indium. An object of the present invention is to provide a method for recovering indium contained in a solution, which is characterized by contacting the indium with the solution. The chelate resin used in the present invention is not particularly limited as long as it has an oxime group, an aminoalkylene phosphate group, an oxine group, a dithiocarbamate group, or a metal salt of the above functional group in the molecule. The chelate resin having a metal salt of the functional group of the present invention includes an oxime group, an aminoalkylene phosphate group,
This is particularly limited if the metal salt is formed by a chelate bond between the metal salt and an oxine group or a dithiocarbamate group, and the bonding force of the metal salt forming these salts is weaker than the bonding force between the functional group and indium. It's not a thing. As the metal of the metal salt, alkali metals and alkaline earth metals such as sodium, potassium, calcium, and magnesium are generally used. Chelate resins having oxime groups include aldehyde groups, styrene-divinylbenzene copolymers having ketone groups, phenol resins, resins obtained by reacting hydroxylamine with polymers such as polyethylene and polypropylene, chloromethyl groups, sulfonyl chloride groups, Polymers such as styrene-divinylbenzene copolymers, phenolic resins, polyethylene, polypropylene, polyvinyl chloride, etc. that have amine-reactive groups such as carbonyl chloride groups, isocyanate groups, epoxy groups, and aldehyde groups (hereinafter referred to as amine-reactive groups) (referred to as a resin having Compounds having one oxime group in the molecule, resins reacted with mixtures of the above compounds, alkylaminobenzaldoxime, formylbenzaldoxime, benzaldoxime, benzhydroxamic acid, alkylaminobenzaldoxime, alkylamino Benzhydroxamic acid, alkylaminomethane benzaldoxime, alkylaminomethane benzhydroxamic acid, alkylaminoethane benzaldoxime, alkylaminoethane benzhydroxamic acid, formylbenzaldoxime, formylbenzaacetaldoxime, benzisoxazole acetaldoxime , benzisoxazole acetohydroxamic acid oxime, benzisoxazole acetohydroxamic acid, phenylsulfinyl acetaldoxime, alkylaminophenyl sulfinyl acetaldoxime, alkylaminophenylmethylsulfinyl acetaldoxime, alkylamino At least in the molecule of phenylethylsulfinylacetaldoxime, alkylaminophenylcarbonylacetaldoxime, alkylaminomethylphenylcarbonylacetaldoxime, benzyldioxime, benzyloxime, benzimidazoylthioacetaldoxime, etc. a compound having one oxime group, a mixture of the above compounds, or a mixture of the above compound and aniline, resorcinol, 3-aminopyridine, 4-aminopyridine, 4-aminobenzenesulfonic acid, 4-aminocarboxylic acid and formalin; Condensation reaction resins with epichlorohydrin, epibromohydrin, etc., polymers of vinyl cyanide monomers such as acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, methacrylonitrile, etc., or copolymerization with vinyl cyanide monomers A resin containing an amidoxime group by reacting a copolymer with other possible ethylenically unsaturated monomers with hydroxylamine or a hydroxylamine derivative; acrylonitrile, α-chloroacrylonitrile,
Polymerization of vinyl cyanide derivatives made by reacting vinyl cyanide monomers such as vinylidene cyanide and methacrylonitrile with hydroxylamine or hydroxylamine derivatives and other ethylenically unsaturated monomers that can be homopolymerized or copolymerized. Resin with amine-reactive group; aminoacetonitrile, aminomalonitrile, diaminomaleonitrile, dicyandiamide, iminodiacetonitrile, 1-amino-2-cyanoethane, 4-aminobenzonitrile, 1-amino-3- A resin obtained by reacting a nitrile compound having an amino group or an imino group such as cyanopropane, and then reacting it with hydroxylamine or a hydroxylamine derivative; A resin obtained by reacting the product obtained by the reaction with a resin having an amine-reactive group; styrene-divinylbenzene having a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a dithiocarboxylic acid group, an alkylamino group, etc. A resin obtained by reacting a halogenated resin such as a polymer or a phenol resin with a product obtained by reacting the nitrile compound having an amino group or imino group with hydroxylamine or a hydroxylamine derivative; benzamidoxime, Benzylamino-N-methanediamide dioxime, benzylamino-N-ethanediamide dioxime, (2-benzimidazolylthio)acetone amidoxime, (2-benzimidazolylthio)ethyl amidoxime, (2-benzimidazolylthio)propylamidoxime, 1,2 -benzisoxazole-3-acetamidoxime,
5-Fluoro-1,2-benzisoxazole-
A compound having at least one amidoxime group in the molecule, such as 3-acetamidoxime, phenylsulfinyl acetamidoxime, (3-chlorophenylsulfinyl)-acetamidoxime, a mixture of the above compounds or a separately specified 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 Na, K of these resins. , alkali metals such as Ca, Mg, alkaline earth metal salts, and the like. Generally, resins having aminoalkylene phosphate groups include polyvinyl chloride, polyvinylidene chloride,
Aminated resin made by reacting an amino compound with chlorinated polyethylene, chlorinated polypropylene, chloromethylated styrene/divinylbenzene copolymer, etc.; an amino resin with an amine-reactive group and a primary or secondary amino group or an aminated resin such as an aniline resin, a guanidine resin, or an amino resin having a primary or secondary amino group in the resin, such as an amino acid group, or an alkylene phosphorylating agent. Na, K, Ca, Mg of these resins
Examples include alkali metal and alkaline earth metal salts such as . Chelate resins having oxine groups include vinyloxy polymers or other ethylenically unsaturated monomers copolymerizable with vinyloxine, such as styrene, divinylbenzene, acrylic esters, acrylonitrile, vinyl acetate, and ethylene glycol dimethacrylate. copolymers with; styrene-divinylbenzene copolymers with amine-reactive groups such as chloromethyl groups, sulfonyl chloride groups, carbonyl chloride groups, isocyanate groups, epoxy groups, aldehyde groups, phenolic resins, polyethylene, polypropylene, poly Polymers such as vinyl chloride (hereinafter referred to as resins with amine-reactive groups), 5-amino-8-hydroxyquinoline, 5
-ethylenediamino-8-hydroxyquinoline,
5-diethylenetriamino-8-hydroxyquinoline, 5-triethyltetraamino-8-hydroxyquinoline, 5-tetraethylpentaamino-
8-hydroxyquinoline, 5,7-diaminoethylenediamino-8-hydroxyquinoline, 5,7
-di(ethylenediamino)-8-hydroxyquinoline, 5,7-di(diethylenetriamino)-8
-Hydroxyquinoline, 5,7-di(triethyltetraamino)-8-hydroxyquinoline, 5.
A polymer obtained by reacting an aminated oxine such as 7-di(tetraethylpentaamino)-8-hydroxyquinoline; a condensation polymer of oxine or an oxine derivative and an aldehyde such as formaldehyde;
Condensation polymers with compounds capable of condensation polymerization such as phenol, resorcinol, urea, thiourea, melamine, guanidine, and aniline; ammonia, ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine in the resin having an amine-reactive group. , chloromethyl group, sulfonyl chloride group, carbonyl chloride group, isocyanate in the aminated resin having a primary or secondary amino group in the resin obtained by reacting amino compounds such as pentaethylenehexamine, hexamethylene diamine, guanidine, etc. Examples include polymers obtained by reacting oxine derivatives having a group, an epoxy group, an aldehyde group, or an amine-reactive group. For example, as a resin having a dithiocarbamate group, (A) a resin containing a halogen atom and (B) an amino compound that reacts with the resin and causes the resulting resin to have a primary or secondary amino group are reacted. A reaction product obtained by producing an aminated resin and then reacting the amino resin with carbon disulfide, a reaction product obtained by treating the reaction product with a base, or a mixture of these reaction products is treated with an acid. resins produced by
Examples include alkali metals such as Na, K, Ca, Mg, alkaline earth metal salts, and the like. More specifically, examples of resins containing halogen atoms include polyvinyl chloride,
Examples include halogen-containing resins such as polyvinylidene chloride, polyvinyl bromide, and polyvinyl iodide, and resins in which halogen atoms are introduced by halogenating resins that do not contain halogen atoms, such as polyethylene and polypropylene. Particularly preferably, a resin containing a chlorine atom as a halogen atom is used. Of course, (A) the above resin may be copolymerized with other compounds that can be copolymerized with the resin component, such as acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, and methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, etc. It may also be a polymer. (A) React with resin containing halogen atoms (B)
As the amino compound, any amino compound can be used as long as it reacts with the resin (A) and causes the resulting resin to have a primary or secondary amino group.
For example, ammonia, monomethylamine, monoethylamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, nonamethylenediamine, hydrazine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, aniline,
O-phenylenediamine, m-phenylenediamine, p-phenylenediamine, p・p′-diaminodiphenylmethane, 2・4-diaminotoluene,
Examples include aliphatic mono- or polyamines such as 2,6-diaminotoluene, aromatic mono- or polyamines, and derivatives thereof. However, it was completely unexpected that the chelate resin limited to the present invention would have an adsorption capacity of 10 times or more compared to the conventionally known iminodiacetic acid type chelate resin. When carrying out the method of the present invention, the pH of the indium-containing solution that is brought into contact with the chelate resin is usually
An aqueous solution containing indium of 8.5 or less is applied, but of course other indium-containing solutions can also be applied. Particularly suitable as the treatment liquid for the method of the present invention are those from sulfuric acid leachates such as zinc and lead smelting sludge, and seawater. In carrying out the method of the present invention, the contact between the chelate resin and the indium-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 indium, a method of passing an indium-containing solution through a column filled with a chelate resin, etc. are generally employed. However, from the viewpoint of processing operations, a method in which the indium-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 indium concentration in the indium-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 indium-containing solution is not particularly limited, but is usually between 0 and 100°C.
It is carried out at a temperature of °C. Further, the contact time is not particularly limited, and a contact time of several seconds or more is usually sufficient. Granular or spherical resins are preferably used, but resins in broken granule, fibrous, honeycomb, cloth, and liquid shapes can also be used depending on the purpose. The chelate resin from which indium 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 separated by heating. Indium is separated from the chelate resin by separating the chelate resin and indium. The indium separated and recovered as described above can then be recovered as indium metal by a known method, for example, by electrolysis with sulfate. According to the method of the present invention as detailed above, the adsorption capacity is 10 times or more than that of known iminodiacetic acid type chelate resins, and its industrial value is great. 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 =NOH group, -NH ₂ group and - obtained by reacting 167 parts by weight of 2-aminomethylbenzaldoxime, 22 parts by weight of resorcin, and 55 parts by weight of formaldehyde
10 c.c. of a resin having an OH group (hereinafter this polymer is referred to as chelate resin A) was packed into a column with an inner diameter of 12 m/mφ, and the column contained 102.2 ppm of indium from the top of the column.
When 100 c.c. of sulfuric acid aqueous solution with pH=1.0 was passed through the solution for 2 hours and the indium in the effluent was analyzed, 8.1 mg was found.
of indium was adsorbed. Examples 2 to 7 Chelate resin B; Commercially available chelate resin having an amidoxime group [Duolite CS-346 (manufactured by Diamond Shamlok Co., Ltd.)]. Chelate Resin C: Vinyl amidoxime polymer obtained by reaction of 53 parts by weight of polyacrylonitrile fiber, 70 parts by weight of hydroxylamine hydrochloride, and 400 parts by weight of a 10 weight percent aqueous sodium hydroxide solution. Chelate resin D: Contains an amine-reactive group obtained by chlorinating 140 parts by weight of Duolite A-101D (manufactured by Diamond Shamlok Co., Ltd.), a strongly basic ion exchange resin consisting of a methylamino group (CH ₃ ) ₃ N-, with chlorine. Aminated resin obtained by reacting amine resin with 100 parts by weight of diethylenetriamine, 40 parts by weight of phosphorous acid and 36
A chelate resin containing 68 parts by weight (undried) of aminoalkylene phosphate groups obtained by reacting 86 parts by weight of hydrochloric acid at a concentration of 86 parts by weight with 2 parts by weight of formalin at a concentration of 35% by weight, followed by alkali treatment with an aqueous solution of caustic soda. Chelate resin E: 100 parts by weight of vinylidene chloride resin powder with a particle size of 100 mesh or less and 200 parts by weight of ethylenediamine.
After adding 50 parts by weight of water and carrying out the reaction at 80 to 120°C for 3 hours, the reaction product was filtered, washed with water, and dried to obtain 112 parts by weight of a yellow-brown aminated vinylidene chloride resin. Next, 56 parts by weight of this aminated vinylidene chloride resin and 100 parts by weight of carbon disulfide were reacted at 41 to 44°C for 2 hours, followed by filtering, washing with water, and drying to obtain 80.5 parts by weight of a yellowish brown resin. As a result of elemental analysis and quantitative analysis of dithiocarbamate groups, it was found that this resin contained 29.5% by weight of carbon disulfide. This resin is called chelate resin E. Chelate resin F: 20 parts by weight of chelate resin E and 50 parts by weight of a 10% by weight aqueous sodium hydroxide solution were heat-treated at 35 to 40°C for 5 minutes, then filtered, washed with water, and dried with phosphorus.
21.8 parts by weight of a yellow-brown resin was obtained. This resin is called chelate resin F. Chelate resin G; 5-vinyl-8-hydroxyquinoline 87 mol%
A copolymer with a composition of 13% by mole of divinylbenzene and divinylbenzene. When each of the above chelate resins was analyzed for indium by passing 100 c.c. of an aqueous solution of indium in sulfuric acid over 2 hours in the same manner as in Example 1, the results shown in Table 1 were obtained.

【table】

[Table] Examples 8 to 12 0.05 g of resins A, B, D, E, and G in 50 ml of sulfuric acid aqueous solution with PH = 1.0 containing 102.2 ppm indium
After stirring and contacting the mixture at room temperature for 3 hours, filtration was performed, and the concentration of indium remaining in the filtrate was analyzed to determine the indium adsorption capacity. The results are shown in Table 2.

[Table] Comparative Examples 1 to 3 Commercially available ion exchange resin Sumikaion was used instead of the chelate resin used in Examples 8 to 12.
KA850, Sumikylate CR-1 (manufactured by Sumitomo Chemical), iminodiacetic acid type chelate resin Duolite ES466
Example 7 using (manufactured by Diamond Shamrock)
Indium was adsorbed in the same manner as in ~10.
The results are shown in Table 3.

[Table] As shown in Examples 1 to 12 and Comparative Examples 1 to 3, it is clear that the chelate resin of the present invention has an excellent ability to selectively adsorb and remove indium from an aqueous solution containing indium.

Claims (1)

[Scope of Claims] 1. A chelate resin having at least one functional group selected from an oxime group, an aminoalkylene phosphate group, an oxine group, a dithiocarbamate group, and a metal salt of the functional group is brought into contact with a solution containing indium. A method for recovering indium, characterized by: 2. The method for recovering indium according to claim 1, wherein the indium-containing solution is an aqueous solution with a pH of 8.5 or less. 3. The method for recovering indium according to claim 1, wherein the indium-containing solution is seawater or a sulfuric acid leachate, which is a by-product of smelting zinc and lead.