JPH0463014B2 - - 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. As an industrial production method for indium, for example, lead blast furnace slag is leached with sulfuric acid, separated into a residue containing indium, lead, etc., and a solution containing components such as zinc, copper, cadmium, etc., and then the above residue is further processed. 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. The impurities are dissolved and removed, the residual indium is leached with sulfuric acid again, and the impurities are precipitated and removed by hydrogen sulfide treatment, and then replaced with aluminum.
A method of obtaining metallic indium by electrolysis is known. 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, in the method using a chelate resin having an iminodiacetic acid type functional group, the indium adsorption capacity of the resin is small, so the amount of indium recovered per resin used is not industrially sufficient, or the selective adsorption of indium is difficult. However, it has the drawback that its properties are not necessarily high, and it has not yet been industrially satisfied. In view of these circumstances, the present inventors conducted intensive research to overcome the above-mentioned disadvantages and to find a method for recovering indium that particularly improved the recovery amount. It was discovered that it has a very large adsorption capacity for indium, and the method of the present invention was completed. That is, the present invention provides at least one type selected from a phosphine group, a phosphonium base, a phosphinate group, a phosphinate group, a phosphonic acid group, a phosphonate group, an aminoalkylene phosphate group, and a metal salt of the above functional group in the molecule. The present invention provides a method for recovering indium contained in a solution, which comprises contacting a chelate resin having a functional group with a solution containing indium. The chelate resin used in the present invention has the general formula -P(R) ₂ , -P(R) ₃ (wherein R is the same or different hydrogen atom, alkyl group, phenyl group, or substituted phenyl group) in the molecule. Phosphine group, phosphonium base, general formula -
Phosphonic acid group represented by PO(OH) ₂ , general formula −
PO(OR) ₂ (wherein R is the same or different hydrogen atom,
a phosphonic acid ester group represented by an alkyl group, a phenyl group, or a substituted phenyl group, at least one of which represents an alkyl group, a phenyl group, or a substituted phenyl group), a phosphonic acid represented by the general formula -PO(OH)H group, general formula -PO(OR)H (in the formula R
is an alkyl group, phenyl group or substituted phenyl group), a phosphinate group represented by the general formula

[expression] and/or

[Formula] (wherein X is an aminoalkylene group, a polyalkylene polyaminoalkylene group, R
is not particularly limited as long as it is a chelate resin having an aminoalkylene phosphate group represented by (alkyl group, phenyl group, or substituted phenyl group) or a metal salt of the above functional group. The chelate resin having a metal salt of the above-mentioned functional group of the present invention is a metal salt between a phosphine group, a phosphonium base, a phosphonic acid group, a phosphonic acid ester group, a phosphonic acid group, a phosphonic acid ester group, or an aminoalkylene phosphate ester group. There is no particular restriction as long as the metal salt is a metal salt formed by a chelate bond or a complex bond, and the bonding force of the metal salt formed by these salts is weaker than the bonding force between the functional group and indium. The metal of the metal salt generally includes sodium, potassium, calcium,
Alkali metals and alkaline earth metals such as magnesium are used. Examples of chelate resins having a phosphine group or a phosphonium group include styrene-divinylbenzene copolymers containing halogenated alkyl groups such as chloromethyl groups and bromomethyl groups, and halogen atoms such as bromine and iodine, phenolic resins, polyethylene, polypropylene, etc. A phosphine group or phosphonium base was produced by reacting the polymer with a phosphine compound such as lithium diphenylphosphine, sodium diphenylphosphine, lithium phenylphosphine, tricresylphosphine, or a mixture of the above compounds. Examples include resin. Examples of chelate resins having phosphonic acid ester groups include styrene-divinylbenzene copolymers containing halogenated alkyl groups such as chloromethyl groups and bromomethyl groups, phenol resins, aniline resins, and m-phenylene polymers (hereinafter referred to as halogenated alkyl groups). phosphorous acid derivatives such as triethyl phosphite, triphenyl phosphite, and trimethyl phosphite, and a mixture of the above phosphorous acid derivatives (hereinafter referred to as phosphorous acid derivatives). and other resins. The chelate resin having a phosphonic acid group is a resin obtained by subjecting the chelate resin having a phosphonic acid ester group to an ester hydrolysis reaction under an acid or alkali catalyst; a polymer such as polystyrene, phenol resin, polyethylene, polypropylene, etc. Examples include resins that are reacted with phosphorus trichloride, then reacted with chlorine or oxygen, and then subjected to a hydrolysis reaction in the presence of an alkali or acid. The chelate resin having a phosphinate group may be a mixture of the resin having a halogenated alkyl group, a hypophosphorous acid derivative such as diethyl hypophosphite or diphenyl hypophosphite, or a mixture of the above hypophosphorous acid derivatives (hereinafter referred to as hypophosphorous acid derivative). Examples include resins made by reacting phosphoric acid derivatives). The chelate resin having a phosphinate group includes a resin obtained by subjecting the chelate resin having a phosphinate group to an ester hydrolysis reaction under an acid or alkali catalyst; polystyrene;
Examples include resins in which a polymer such as a phenol resin, polyethylene, or polypropylene is reacted with phosphorus trichloride and then subjected to a hydrolysis reaction. Examples of the chelate resin having an aminoalkylene phosphate group include the halogenated alkyl group, sulfonyl chloride group, carbonyl chloride group, isocyanate group, nitrile group, chlorine atom, bromine atom, iodine atom, epoxy group, aldehyde group, ketone group, etc. Polymers such as styrene-divinylbenzene copolymers, phenolic resins, polyethylene, polypropylene, polyvinyl chloride, polyacrylonitrile, polyvinylidene cyanide, polymethacrylonitrile, poly-α-chloroacrylonitrile, etc. having amine-reactive groups (hereinafter referred to as (referred to as a resin having an amine-reactive group) with an amino compound such as ammonia, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, guanidine, or hydrazine. resin (hereinafter referred to as aminated resin),
A resin in which the phosphorous acid derivative is reacted with an aldehyde or ketone such as acetaldehyde, formaldehyde, acetone, acetylacetone, and a mixture of the aldehydes and ketones; a resin in which the phosphorous acid derivative is reacted with the aminated resin; A resin obtained by reacting a methylenating agent such as , paraformaldehyde, or trioxysan with the above-mentioned phosphorous acid derivative; diethyl chloromethylphosphonate, ethyl chloromethylphosphonate, diphenyl chloromethylphosphonate, or chloromethyl in the aminated resin. Examples include halogenated alkyl phosphates such as dicresyl phosphonate and ethyl chloromethylphosphinate, and resins made by reacting mixtures of the halogenated alkyl phosphates. However, it was completely unexpected that the chelate resin limited to the present invention would have an adsorption capacity six times or more than the conventionally known iminodiacetic acid type chelate resin. In 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,
Of course, other indium-containing solutions can also be used. 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 point of view of processing operations, into a column filled with chelate resin,
A method of passing an indium-containing solution 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. Particulate or spherical resins are preferably used, but resins in crushed, 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 six times or more than that of the known iminodiacetic acid type chelate resin, 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 A resin having a phosphonate group obtained by reacting 200 parts by weight of chloromethylated polystyrene with 500 parts by weight of triethyl phosphite in a toluene solvent (hereinafter, this polymer is referred to as chelate resin A).
A column with an inner diameter of 12 m/mφ was filled with 10 c.c. of the sulfuric acid leachate of PH1.0 zinc ore smelting sludge containing 102.2 ppm of indium from the top of the column. An analysis of 8.3
mg of indium was adsorbed. Examples 2 to 9 Chelate resin B; Commercially available resin having a phosphonic acid group [Duolite ES-63 (manufactured by Diamond Shamlok Co., Ltd.)]. Chelate resin C: Aminated polyacrylonitrile obtained by reacting 60 parts by weight of polyacrylonitrile with 103 parts by weight of diethylenetriamine in an aqueous solvent was further reacted with 281 parts by weight of formalin aqueous solution and 498 parts by weight of triethyl phosphite in the presence of 36% hydrochloric acid. A resin having an aminoalkylene phosphate ester group obtained by Chelate resin D: A resin containing a phosphonium base obtained by reacting 200 parts by weight of chloromethylated polystyrene and 200 parts by weight of tributylphosphine in a dimethylformamide solvent. Chelate resin E: A resin containing a phosphonium base obtained by reacting 200 parts by weight of chloromethylated polystyrene and 260 parts by weight of triphenylphosphine in a dimethylformamide solvent. Chelate resin F: 150 parts by weight of brominated polystyrene in tetrahydrofuran solvent, 1.6 mol% n-butyllithium
Lithium polystyrene was obtained by reacting with 64 parts by weight of hexane solution. A resin having a phosphine group obtained by reacting this with 300 parts by weight of chlordiphenylphosphine in a tetrahydrofuran solvent and further oxidizing with 371 parts by weight of 40% peracetic acid in a methylene chloride solvent. Chelate resin G: A resin containing a sodium salt of phosphonic acid obtained by hydrolyzing chelate resin D in a 20% aqueous solution of caustic soda. Chelate resin H: 100 parts by weight of polystyrene in chloroform solvent,
A resin containing phosphinic acid groups obtained by reacting with 150 parts by weight of phosphorus trichloride and then hydrolyzing it. Chelate Resin I: A resin having a phosphinate group obtained by reacting 100 parts by weight of aminated polystyrene with 120 parts by weight of cresyl chloromethylphosphinate in a 1,2-dichloroethane solvent. Using each of the above chelate resins, 100 c.c. of sulfuric acid leachate from zinc ore smelting sludge with a pH of 1.0 containing 102.2 ppm of indium was passed through the solution for 2 hours and analyzed for indium in the same manner as in Example 1. The results shown in Table 1 were obtained.

【table】

[Table] Examples 10 to 18 A, B, C, D, E, FG, H,
After adding 0.05 g of each of the resins of I and carrying out a stirring contact treatment at room temperature for 3 hours, filtration was performed, and the concentration of indium remaining in the filtrate was analyzed to determine the amount of indium adsorbed. 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 10 to 18.
KA850, Sumikylate CR-1 (manufactured by Sumitomo Chemical), iminodiacetic acid type chelate resin Duolite ES466
Example 10 using (manufactured by Diamond Shamrock)
Indium was adsorbed in the same manner as in ~18.
The results are shown in Table 3.

[Table] As shown in Examples 1 to 18 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 At least one member selected from a phosphine group, a phosphonium base, a phosphinate group, a phosphinate group, a phosphonic acid group, a phosphonate group, an aminoalkylene phosphate group, and a metal salt of the above functional group. A method for recovering indium, which comprises bringing a chelate resin having a functional group into contact with a solution containing indium. 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 indium recovery method 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.