JPS60260423A - Method for recovering germanium - Google Patents

Abstract

PURPOSE:To recover Ge from a soln. contg. Ge in a high yield by bringing the soln. into contact with a special chelate resin contg. specified functional groups so as to adsorb selectively Ge on the chelate resin. CONSTITUTION:Ash produced by smelting copper ore or zinc ore contains Ge. This Ge is extracted and dissolved in sulfuric acid or the like. The resulting strongly acidic aqueous soln. of 1-3pH is optionally adjusted to >=8.5pH by adding ammonia. The acidic or basic soln. is brought into contact with a chelate resin contg. =NOH (functional group A) in the molecule as an essential functional group and further contg. a functional group B capable of forming a chelate bond with =NOH through Ge such as a functional group represented by formula 1 (where each of R1 and R2 is H or an org. group) or a polyethylenepolyamino group. Polyacrylonitrile or the like is used as the chelate resin. Since Ge in the soln. is selectively adsorbed on the chelate resin, it is separated and recovered at a high rate of recovery.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for recovering germanium from germanium-containing solutions. − High in germanium (minerals containing arcitromite,
Germanite, Rainierite, Studite, Fleischite, and Itouite are known, but these are produced in small amounts, and for the commercial production of germanium, smelting smoke from copper and zinc ores is used as the raw material for germanium. Mainly used □.

As a method for recovering 'germanium' from such germanium raw materials, the germanium raw materials are leached with sulfuric acid, etc., arsenic, copper, zinc, etc. contained in large amounts in the leachate are precipitated and removed by chemical treatment, and magnesium oxide etc. are added. The germanium compound is converted into a hydroxide, C is precipitated, and the resulting germanium compound is dried and roasted to obtain a calcined product containing about 10% by weight of C germanium. A known method is to perform chlorination treatment and then distillation to recover germanium chloride, followed by hydrolysis, filtration, drying, and other treatments to recover C1 crude germanium oxide. Crude germanium oxide is further purified if necessary. Afterwards, it is subjected to hydrogen reduction,
It is recovered as metal germanium by methods such as electrolysis.

In this known method, the sulfuric acid leaching solution of the germanium raw material usually contains metal elements other than germanium such as copper, zinc, lead, arsenic, iron, etc.
Since there are 00 times as many germanium compounds, in order to separate germanium and other metal elements from the sulfuric acid leachate, chemical treatment with alkali, sulfide, etc. is performed, and the difference in solubility between germanium compounds and other metal compounds is utilized. Although the germanium component is separated and concentrated, it is not possible to efficiently separate germanium from other metal elements using a single separation and concentration process, and purification cannot be achieved unless it is subjected to repeated separation and concentration processes. The problem is that there is no. Furthermore, since the entrainment loss of germanium to other metal elements cannot be avoided during the separation and concentration operation, the germanium raw material used for commercial production contains at least several hundreds of germanium/e/e or more in the sulfuric acid leachate. The drawback is that you cannot use it unless you have something to do with it.

For this reason, the present inventors solved the above problem,
Germanium can be efficiently extracted from germanium-containing solutions containing large amounts of other metals, such as smelting smoke of copper and zinc ores using sulfuric acid, etc., with simple operations and without being affected by the germanium concentration. As a result of studies to recover germanium, it was discovered that a special chelate resin having a specific functional group can adsorb and recover germanium in a solution with high selectivity, leading to the completion of the present invention.

That is, the present invention uses a germanium-containing solution with a chelate resin having -NOH (to a functional group) in the molecule and a functional group (functional group B) capable of forming a C chelate bond with the layer through germanium, or a chelate resin containing a germanium-containing solution. The present invention provides a method for recovering germanium from a germanium-containing solution, which comprises contacting with a chelate resin containing a metal salt to cause germanium to be adsorbed onto the resin.

The chelate resin used in the present invention has a =NOH group as an essential functional group in the molecule, and the chelate resin has a functional group capable of forming a chelate bond with the layer through germanium, or It is a KIRE-1 resin having a metal salt of a functional group.

Here, = a functional group (functional group 13) capable of forming a C chelate bond via an NOH group and germanium -OH, -3H,
=NOH,)C=O, -NHOH, -NH-NH2, -
C52H, -COOH, -5O3H,)C=S.

-CHO, -0-, -S-, -P(OR), -PO(
OR),.

-PH(OR)s (In the above formula, R3 and R2 are a hydrogen atom or an organic group (usually an alkyl group, an aryle group, or an arykylene group in which R3 and R2 are bonded, particularly an alkyl group having 1 to 20 carbon atoms) ), R represents a hydrogen atom, an aryl group, an alkyl group, or an amino group] and a polyethylene polyamino group, with particular preference being given to a>C-0,=NOH, and a polyethylene polyamino group.

In the chelate resin of the present invention, the above functional groups A and B
A chelate resin in which both are bonded to the same carbon is particularly preferably used from the viewpoint of adsorption of germanium.

In addition, in the chelate resin having a metal salt of a functional group of the present invention, the metal salt and the V layer are the functional group (A) and/or (
There are no particular restrictions on the strength of the metal salt B) as long as it is weaker than the metal salt strength or the chelate bond between the functional groups (A) and (B).

The metals in such metal salts generally include sodium,
Alkali metals and alkaline earth metals such as potassium, calcium, and magnesium are used.

Such chelate resins include acrylonitrile and copolymerization with vinyl cyanide monomers or vinyl cyanide monomers such as α-chloro-reaacrylonitrile, vinylidene cyanide, and methacrylonitrile. Acrylonitri! is a resin made by reacting hydroxylamine or a derivative of hydroxylamine with a copolymer with other ethylenically unsaturated monomers to have an amidoxime group; acrylonitri! Homopolymerization or ζ2
Polymerized with other copolymerizable ethylenically unsaturated monomers; having amine-reactive groups such as chloromethyl group, sulfonitochloride group, carbonyl chloride group, isocyanate group, epoxy group, aldehyde group, etc. Styrene
Polymers such as divinylbenzene copolymer, phenol resin, polyethylene, polypropylene, and polyvinyl chloride (hereinafter referred to as resins with amine-reactive groups), aminoacetonitrile, aminomalonitrile, diaminomaleonitrile 1, dicyandiamide, imino Diacetonitrile, 1-amino-2-cyanoethane, 4-aminobenzonitrile is reacted with a nitrile compound having an amino group or an imino group such as l-amino-8-cyanopropane, and then hydroxyl A resin that has been reacted with an amine or a hydroxylamine derivative; Reacted resin: A halogenated resin such as a styrene-divinylbenzene copolymer or phenol resin having sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, dithi, ocarboxylic acid groups, alkylamino groups, etc. A resin obtained by reacting a product obtained by reacting a nitrile compound having an amino group or a domino group with hydroxylamine or a hydroxylamine derivative; benzamidoxime, benzylamino-N-methanediamide dioxime, benzylamino-N- Ethanediamide dioxime, (2-benzimidazolylthio)acetamidoxime, (2-penzimidazolylthio)ethylamideoxime, (2-penzimidazolylthio)propylamidoxime, l, 2-benzisoxacy+1/-9-
At least acetamidoxime, 5-fluoro-1,2-benzisoxazole-8-decetamidoxime, phenylsulfinylacetamidoxime, (8-chlorophenylsurilefinyl)-acetamidoxime, etc. A compound having one amidoxime group, a mixture of the above compounds, or the above compound and aniline, resorcinol,
Condensation or addition polymerization reaction of a mixture of 8-aminopyridine, 4-aminopyridine, 4-aminobenzenesulfonic acid, and 4-aminobenzenecarboxylic acid with formalin, epichlorohydrin, epibromohydrin, etc. Resin: aldehyde group, ketone A resin obtained by reacting hydroxylamine with a polymer such as a styrene-divinylebenzene copolymer, phenol resin, polyethylene, or polypropylene that has a group; chloromethyl group, sulfonyl chloride group, carbonyl chloride group, isocyanate group, epoxy group, Polymers such as styrene-divinylbenzene copolymer, phenol resin 1, polyethylene, polypropylene, polyvinyl chloride, etc. (hereinafter referred to as resins having amine-reactive groups) having amine-reactive groups such as aldehyde groups, etc. Acetaldoxime, iminodiacetaldoxime, aminobenzaldoxime, aminoalkylbenzaldoxime, aminobenzhydroxamic acid, aminoalkylbenzhydroxamic acid, etc. 7iino group, imino group and at least one -NOH group in the molecule A compound having the following, a resin reacted with a mixture of the above compounds; alkylaminobenzaldoxime, formylbenzaldoxime, benzaldoxime,
Benzhydroxamic acid, alkylaminobenzaldoxime, alkylaminobenzhydroxamic acid, alkylaminomethane benzaldoxime, alkylaminomethane benzhydroxamic acid, alkylaminoethane benzaldoxime, alkylaminoethane benzhydroxamic acid, formylbenzaldoxime , foleremyl benzacetaldoxime, benzisoxazole acetaldoxime, penzisoxazole-reacetohydroxamic acid oxime, benzisoxazole acetohydroxamic acid, phenylsulfinyl-acetohydroxamic acid,
Alkylaminophenylsulfinyl acetaldoxime, allelekylaminophenyl remethylesulfinylacetaledoxime, acylaminophenyl ethylsulfinyl acetaldoxime, alkylaminophenylcareponylacetaldoxime, alkylaminomethyl phenylcarbonylacetaldoxime,
Compounds having at least one =NOH group in the molecule, such as benzyldioxime, benzyloxime, benzimidazoylthioacetaldoxime, mixtures of the above compounds, or the above compounds and aniline, resorcinol, 8-aminopyridine, 4 - Condensation reaction resin with mixtures of aminopyridine, 4-aminobenzenesulfonic acid, 4-aminobenzenecarboxylic acid, toforunrin, epichlorohydrin, epibromohydrin, etc.; and sodium of these resins,
Examples include alkali metals such as potassium, calcium, and magnesium, and 4-salts of alkaline earth metals.

In implementing the method of the present invention, the germanium-containing solution to be brought into contact with the chelate resin is usually basic (preferably pH 7.5 or higher) or acidic (preferably pH 7.5 or higher) or acidic (preferably pH
Although germanium-containing aqueous solutions 1 to 8) are applied, other germanium-containing solutions can also be applied.

Specifically, such germanium-containing solutions include copper and zinc ore smelting smoke ash, coal smoke ash, or germanium-containing scrap, an aqueous mineral acid solution such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, etc. at a concentration of 1 to 8 moe/l, or ammonia, diethylamine. Generally, a leachate obtained by contacting an aqueous solution of amines such as ethylenediamine, diethylenetriamine, etc. at room temperature to IOO°C under normal pressure or pressure to elute metal elements such as getaremanium is applied, but an aqueous solution containing germanium is used. If so, there are no particular restrictions.

In particular, a basic aqueous solution with a pH of 7.5 or higher is preferred, as it increases the amount of germanium adsorbed and recovered on the chelate resin.

In carrying out the method of the present invention, the method of contacting the chelate resin with the germanium-containing solution is not particularly limited, and examples include a method of immersing the chelate resin in a germanium-containing solution, A method of passing a hegermanium-containing solution through a column is generally employed, but a method of passing a hegermanium-containing solution through a column packed with a chelate resin is preferred from the viewpoint of processing operations.

The amount of chelate resin used is not particularly limited;
Although it varies depending on the germanium concentration in the germanium-containing solution to be treated, the type of chelate tree 1117 used, etc., this can be set by appropriately conducting preliminary experiments.

The contact temperature between the chelate resin and the germanium-containing solution is not particularly limited, but it is usually carried out at a temperature of 10 to 100°C. The contact time is also not particularly limited, and is determined as appropriate depending on the conditions of each il.

Thus, according to the method of the present invention, germanium is efficiently adsorbed onto the chelate resin from a germanium-containing solution, but in particular, germanium can be efficiently adsorbed onto the chelate resin from a germanium-containing solution. It has not been known in the past that germanium can be highly selectively adsorbed and recovered by a chelate resin from an aqueous solution containing a large amount of impurities such as copper, zinc, cadmium, and iron in addition to germanium. It was completely unexpected that the resin would be extremely effective in recovering germanium from an aqueous solution containing a large amount of impurity elements, such as the above-mentioned smoke ash leachate.

The chelate resin adsorbing and collecting germanium by the method of the present invention can then be eluted with hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sodium sulfide, iminodiacetic acid, ethylenediamine, tetraacetic acid, etc., or heated to separate the germanium. can be separated from the chelate resin.

The germanium separated and recovered in the above manner is neutralized, dried, recovered as germanium oxide, and further subjected to C reduction treatment as necessary to form germanium metal, or subjected to hydrochloric acid or chlorination treatment. It can be recovered as germanium chloride.

Thus, according to the method of the present invention, germanium can be efficiently recovered with simple operations without performing complicated treatments compared to known methods, and its industrial value is extremely large.

The present invention will be explained below with reference to examples, but the present invention is not limited by the following examples unless the gist of the invention is exceeded.

Example 1 p) containing vinylamidoxime and FFe107pP obtained by the reaction of polyacrylonitrile fibers, hydroxylamine hydrochloride and aqueous sodium hydroxide solution
(50% sulfuric acid leachate of zinc ore smelting smoke adjusted to t, a)
1g, 1! The solution was added to the solution, shaken for 8 hours, subjected to contact treatment, and the treated solution was analyzed for Ge, Zn, and Fe, and the results shown in Table 1 were obtained.

Table 1 Examples 2 to 13 Chelate Resin B; Vinylsulfonic acid divinylbenzene copolymer resin was chlorinated in the presence of carbon tetrachloride solvent and sulfur, then reacted with aminomalone nitrile, and then reacted with hydroxylamine. Vinyl sulfonamide methanediamide oxime resin obtained by

Chelate Resin C: A vinylcarboxylic acid amide acetamidoxime-divinylbenzene copolymer resin obtained by halogenating an acrylic acid-divinylbenzene copolymer resin with phosgene in an N,N-dimethylformamide solvent and then reacting it with aminoacetamidoxime. Chelate resin D; =NOH group, NH obtained by reacting benzamidoxime, resorcinol, and 4c lumin.

- and 10H groups.

Chelate resin E; Vinyl amidoxime obtained by reacting hydroxylamine with acrylonitrile and divinylbenzene copolymer.
Divinylbenzene copolymer resin.

Chelate Resin F: A vinyl diamide dioxime-divinylbenzene-acrylic acid copolymer resin obtained by reacting a copolymerization method of vinylidene cyanide, divinylbenzene, and methylated acrylic acid with hydroxylamine.

Chelate Resin G: A vinylamidoxime-acrylic acid copolymer resin obtained by copolymerizing a reaction product of acrylonitrile and hydroxylamine with ethyl acrylate, followed by hydrolysis treatment.

Chelate Resin H: A resin obtained by reacting a chloromethylated styrene divinylbenzene resin with diaminomaleonitrile and further reacting with hydroxylamine.

Chelate resin processing: Strongly basic ion exchange resin Duolite-161 (manufactured by Diamond Jamrock Co., Ltd.) was mixed with 1,2-dichloro-1,
A resin obtained by chlorination over 2-difluoroethane solvent, then reaction with iminodiacetonitrile, and further reaction with hydroxylamine.

Chelate resin J: styrene divinylbenzene resin with sulfonic acid group [
Duolite C-26 (Diamond Jamrock Co. 1
&l)]] A resin obtained by carrying out a chlorination reaction with phosgene in an N,N-dimethylformamide solvent and further reacting with aminoacetamidoxime.

A resin obtained by reacting 1.2-benzisoxazole-8-acetamidoxime, resorcinol, and formalin with the chelate resin.

Chelate resin L: A resin obtained by reacting 5-fluoro-1,2-benzisoxazole-3-acetamidoxime, phenol, and formalin.

Chelate resin M: Commercially available chelate resin having an amidoxime group [Duolite C5-846<Diamond Jamrock a[)]
.

Chelate resin N; Amidoxime group N obtained by reacting acrylonitrile-tetraethylene glycol dimethacrylate (molar ratio 1:0.2) with hydroxylamine in a fatty toluene solvent and alkali-treated with an aqueous sodium hydroxide solution.
Resin with a salt.

Chelate resin O: A resin obtained by reacting acrylonitrile-ethylene glycol dimethacrylate (molar ratio t:o, 15) with hydroxylamine in a carbon tetrachloride solvent.

Chelate resin P: A resin obtained by reacting an acrylonitrile-ethylene glycol monomethacrylate (molar ratio 1:0.25) resin with hydroxylamine in a xylene solvent.

Using each of the above chelate resins, contact treatment was performed with the sulfuric acid leachate of zinc ore smelting smoke in the same manner as in Example 1, and the treated solution was analyzed for Ge, Zn, and Fe.
The results shown in Table 2 were obtained.

Table 2 Example 1'! The chelate resin A 0.1 f used in Example 1 was prepared using a sulfuric acid leachate of coal smoke ash which was adjusted to pH 9 with ammonia.
Liquid 5' containing t'yppm and As6701)pm
When added to Ogl, shaken and contacted for 8 hours, and analyzed for Ge and As in the treated solution, the results shown in Table 8 were obtained.

Table 8 Examples 18 to 22 Chelate resin Q Obtained by reacting 2-aminomethylbenzaldoxime, resorcinol, and formalin = N OH group, -NH,
Resin chelate resin R having 1.2-benzisoxazole-8-acetohydroxamic acid oxime, reso I resin, and formalin = N Of A resin having 1 group, =N group and 10×1 group.

Chelate resin S: 5-Fluoro-1,2-Pencilzuki "Zaburu 8-"
A resin having =NOH, -NHOH, 100N, and 10H groups obtained by reacting oxime acetohydroxamic acid, phenol, and foralemarin.

Chelate resin T: =NOH group and -C5,H group c7) obtained by reacting vinylamidoxime-divinylbenzene copolymer with carbon disulfide and then treating with alkali with an aqueous sodium hydroxide solution
Resin with N a Silkworm salt.

Pachylate resin U: A polycondensation resin of benzoylimino-ethanediamide dioxime, aniline, and nermarin is reacted with monochloroacetic acid, and then treated with alkali with an aqueous calcium hydroxide solution to form =NOH group and -C00H group c7) Ca metal salt A resin with

Using each of the above chelate resins, in the same manner as in Example 17, the sulfuric acid leachate of C1 coal smoke was diluted with ammonia to pH 9.
When the treated solution was analyzed for Ge and As, the results shown in Table 4 were obtained.

Table 4 Example 28 Chelate resin A0.1f used in Example 1 was Ge 67
”ppm, F-8220ppm was added to semiconductor factory wastewater with a pH of 8 to 50°C, shaken for 8 hours, and subjected to contact treatment.
Analysis of Ge in the treatment solution revealed that it was 7.8 ppm, and the amount of Ge adsorbed per unit resin was 809-Ge/f-
It was resin.

Examples 24 to 28 Chelate resin ■; 1.2-penzisoxazo=y-reacted with =NOH group, -NH2 group, =N group and 〇Resin with H group.

Chelate Resin W: A resin having =NOH and /N groups obtained by reacting 8-formylquinoline, benzaldehyde, and formalin to form a resin, and then reacting with hydroxylamine.

Chelate resin

Chelate resin Y; C obtained by reacting a copolymer of acrylonitrile and divinylbenzene with hydroxylamine sulfate and an aqueous hydrazine solution =NOH group, -NH group, -NH, group and -NHNH
, a resin having a group.

Kyrenide resin Z; resin having =NOH group, =NH group, -NH, group and -NHCH, CH, NHCH, CM2NH2 group obtained by reacting a copolymer of acrylonitrile and divinylbenzene with hydroxylamine hydrochloride and diethylenetriamine aqueous solution .

Using each of the above chelate resins, contact treatment was performed with semiconductor factory wastewater in the same manner as in Example 28, and the treated solution was analyzed for Ge, and the results shown in Table 5 were obtained.

Table 5 Comparative Examples 1 to 8 Polyacrylonitrile used to synthesize chelate resin instead of A=late resin used in the method of Example 1, strong basic ion exchange resin Duoly I-A -161 (manufactured by Diamond Jamrock Co., Ltd.) and dithiocarbamate type chelate resin Sumichelate Q-10 (manufactured by Sumitomo Chemical Co., Ltd.) were used to adsorb germanium in the same manner as in Examples 28 to 28. went. The results are shown in Table 6.

Table 6

Claims (1)

[Claims] (1) A germanium-containing solution is contained in the molecule = N OH
(Functional group A) and a chelate resin having a functional group (Functional group B) that can form a chelate bond with the group via germanium, or a chelate resin having a metal salt of the functional group. A method for recovering germanium from a germanium-containing solution, which comprises adsorbing germanium. =NOH,)C=0. -NHOH, -NH-NH,L-
The method according to claim 1, which is C52H, -Cool(, -3o, H, >C=S (in the above formula, R1 and R2 represent a hydrogen atom or an organic group) or a polyethylene polyamino group. (8) The method according to claim 1 or 2, which is a chelate resin in which the functional groups A and B are bonded to the same carbon atom. (4) The germanium-containing solution has a pH of 7.5 or higher. The method according to claim 1, wherein the germanium-containing solution is a basic or acidic aqueous solution with a pH of 1 to B. (6) The germanium-containing solution is an acid or base leachate of copper and zinc ore smelting smoke, coal smoke, or germanium scrap. The method according to claim 1 or 4.