JPS60103029A - Method for recovering germanium - Google Patents

Abstract

PURPOSE:To recover Ge especially from a strongly acidic leaching soln. in a high yield by bringing a chelate resin having specified functional groups into contact with a soln. contg. Ge to allow Ge to be adsorbed on the resin and by eluting the adsorbed Ge. CONSTITUTION:A chelate resin having oxine ligands in the molecule such as a resin prepd. by reacting a styrene-divinylbenzene copolymer with halomethylated oxine is brought into contact with a soln. contg. Ge such as a leaching soln. of <=2pH after the treatment of zinc ore with sulfuric acid to allow Ge to be adsorbed on the chelate resin. The chelate resin is then treated with an aqueous soln. of NaOH or the like to elute the adsorbed Ge. The chelate resin is much superior to a conventional known ion exchange resin or iminodiacetic acid type chelate resin in power of selectively adsorbing Ge in an acidic aqueous soln. of <=2pH. It has physical, chemical and mechanical stabilities and can be repeatedly used by regeneration.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for recovering germanium from a solution containing germanium, and more specifically, the present invention relates to a method for recovering germanium from a solution containing germanium. This is a method for recovering germanium.

Germanium is currently used in many fields, such as semiconductors and infrared optics.

It is used in the fields of fiber optics, T-ray particle detection, catalysis, medicine and polymer chemistry.

However, high-grade germanium ores are extremely rare, and most of the germanium recovered in the 11M field is as a by-product from 12L copper+f+i. Particularly in the production of electrolyte (1:j), the concentration of germanium is relatively high, and if germanium is not removed from the electrolyte, the current mobility in the subsequent electrodes will be significantly reduced. Depending on the process, it is usual to carry out degermanization treatment in advance (11).

Conventionally, a method for recovering germanium from a sulfuric acid acidic lu effluent of 2I; A method has been adopted to recover 1.1 rumanium as rumanium.However, this method requires a lot of operations, and the loss of kermanila and /A C) lil associated with the process is large. Therefore, in recent years.

One method for liquid-liquid extraction has attracted attention and has been widely studied. For example, tributyl phosphate Nagahora alkyl
Methods have been proposed for separating and recovering germanium using solvent extractants such as amine, alkyl phosphoric acid, sulfinic acid, hydroxamic acid, hydroxyoxime, alkyl pyrocatechol, and oxine derivatives (for example,
B-9134, JP-A-9817, JP-A-58-31048, etc.). Although these methods are very interesting, they have problems such as poor selectivity of the extractant for germanium, decomposition of substituents during repeated use over a long period of time, resulting in a decrease in extraction ability, or their price is low. Due to reasons 111 such as being extremely expensive, it has not yet been industrially satisfied.

In view of these circumstances, the present inventor has conducted intensive research with the aim of providing a method for recovering germanium that overcomes the disadvantages mentioned in 2. As a result, the present inventor has developed a Kir-1-resin having a specific functional group. It has been found that germanium, especially from acidic leachate, can be recovered very efficiently by using this method, and the present invention has been completed.

That is, the present invention uses a ``1-1/-'' resin containing oxine as a ligand in the molecule and a germanium content j.
The gel is adsorbed onto the resin by contacting with the gel mani.
gelmer-1″r, characterized in that it elutes horns;
This is a method of collecting l.

The chelate resins used in the present invention include:

It is a Kir-1 resin having oxine in the ligand, Shishi, -(UtJ', and (I, B) is not particularly limited.

1. As the resin, for example, styrene is reacted with a cross-linked vinyl aromatic copolymer typified by the -Rhenzene copolymer with halomethylated A-1. resin, cross-bonded vinyl, name 'N'+/
IS: (^1 fatty acid, chloromethyl group, sulfonyl chloride), (carbonyl chloride group) obtained by diazotizing or halomethylating a copolymer and then reacting it with oxine.

Isocyanana 1. Styrene-divinyl-1:n J': ilr combination with amines such as J, I;, epoxy group, aldehyde group, etc., Iy', Ili;,
Phenolic resin.

A resin obtained by reacting an aminated oxine with a polymer such as polyethylene, polyvinyl chloride, or polymethacrylic acid (hereinafter referred to as a polymer having an amine-reactive group), or a polymer having an amine-reactive group, ammonia , reacting amine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, and guanidine to form f! ? /:: Chloromethyl group, sulfonyl chloride group, carboerc l:1 to the aminated polymer that whitens the primary or secondary amino group in the polymer.
Lido group.

A resin obtained by reacting an oxine derivative having a group that reacts with an amine such as a sardine-1 group, an epoxy group, an aldehyde group, an acrylic acid-divinylbenzene copolymer,
A resin obtained by diazotizing a methacrylic-divinylbenzene copolymer and then reacting it with oxine, a resin obtained by copolymerizing vinyloxine and an ethylenically unsaturated compound 2 such as styrene, divinylbenzene, acrylic ester, or ethylene glycol dimethacrylate. Examples include resins obtained by combining oxine or me;1-syn derivatives with flit, which is obtained by polycondensation with fluorols and pol Jz 'J' aldehydes.

As the above-mentioned oni 1 vinyl or its derivatives.

For example, 8-1=, lII xyquinoline (oxine).

2-Methyl 811.1koxyquinoline (2-methyloxone), 2-ethyl-8-hydroxyquinoline, 2-
rI-propyl-8-hydroxyquinoline, 2-iso-
Propyl-8-hydroxyquinoline, 2-n-butyl-
8-Hydroxyginoline, 2 LarL-butyl-8-
! Nido-1koxyquinoline, 5-chloro-8-hydroxyquinoline, 5-bromo-8-hydroxyquinoline, 2-
Examples include methyl-5-chloro-8-hydroxyquinoline, among which 8-hyI:1:I xyquinoline, 2
-Methyl-8-hydroxyquinoline is preferred, especially 8-hydroxyquinoline.
- Human+SlSl xylin is preferred.

To produce a resin that removes this oxine, for example, Journal of Organic Che.
mis-try, volume 43, pages 3151-3157,
1978, PolymerScience, U.
S, S, R, 20 volumes +, 53'2, 54Q Uj'
, .

Follow the method described in 1978 (
Usually, it can be produced by swelling an appropriately crosslinked three-dimensional resin in an organic solvent and then reacting it with oxine or a derivative thereof in the presence of a catalyst or a deoxidizing agent.

The germanium-containing solution that is the object of the present invention is usually an acidic solution with a pH of 2 or less, but of course other germanium-containing solutions can also be used. Specific examples of such solutions include acidic leachates of zinc castings or acidic leachates of zinc smelting residues; these solutions are usually acidic sulfuric acid solutions with a p112 or lower content containing a large amount of zinc.

To carry out the method of the present invention, first, the above chelate resin is brought into contact with a solution containing germanium to adsorb germanium onto the chelate resin. For this purpose, the hatch method and the column method are usually used as well as the method using an ion exchange resin, but the column method is more advantageous in terms of monolithic production. When using the column method.

Fill the column with the resin and heat the germanium-containing solution at a continuous rate (indicating how many times the volume of the resin is processed per hour) for 0.5 to 5 hours, warm for 1 morning. l
';'I '1 item or 60' (Set 4 items, downflow Q, 2 twists 1 (1).

Next, from the chelate resin that has adsorbed germanium, germanium ``Tsum'k?'' 6X [For example, 9.

The chelate resin is treated with an aqueous potash metal hydroxide solution at i'/l.
1. Rooster 1.1. <1 to 4 mol/β An alkaline aqueous solution such as caustic soda, kase, and inonori is used as a dissolving agent.
(Used.

11. explained above. (1) Since the present invention uses method C using a chelate resin, gel-lium can be recovered efficiently with simple operations. In addition, the chelate resin used in the present invention has significantly superior 1) absorption and 17 properties for germanium in an acidic aqueous solution with a pH of 2 or less compared to conventionally known ion exchange resins and iminodiacetic acid type chelate resins. Therefore, Gel Manila J is required for example zinc, cadmium, and cobalt.

It also has the effect of being able to selectively recover germanium even from M('L) solutions in which iron, arsenic, nickel, etc. coexist.

It has excellent chemical and mechanical stability, and can be used many times by regenerating the resin, so its industrial value is great.

The present invention will be explained in more detail with reference to Examples below. In addition, % in Reference Examples and Examples indicates weight % in total.

Reference Example 1 Commercially available styrene-divinylbenzene composite (divinylbenzene/3 mol θ%) 10. (After adding 150ml of nitrohenzene to 11! and swelling -Vk.

Next, thread 1: Tsujj [aluminum chloride hydrate 1.3 g
and 5-ri 101 me-1-ru 8-hydroxyquinoline hydrochloride 23, 01! ,! : was added and reacted at 80°C for 24 hours.

Reaction path J'ik, lJ: Jj, separated and washed with water and methanol'), 4% caustic soda water? ' By neutralizing with liquid 8 and then washing with water for 1 minute.

The desired l'i-1 resin was obtained.

Reference Example 2 10.0 g of commercially available non-divinylbenzene copolymer (divinyl, 3 mole%) was added to 50 m1
of concentrated sulfuric acid, 2':'; ) 25
m1 was added dropwise over a period of 1 hour to form 21-1I. After the reaction was completed, the mixture was poured into ice water (the product was isolated). The temperature was gradually raised, and the reaction was finally carried out for 3 hours at 5+1"c for amination. At the end of the reaction, the mixture was poured into ice water to isolate the product. I let go. After washing thoroughly with water,
After drying, 1.7 g of styrene-divinylhensenno I and polymer aminated product 1 were obtained.

To this aminated product, add dimethylborumamyl 5 (iml
After adding and swelling, 5-chlor I, 1]f-ru 8
- Adding 23.014 hydroxyquinoline hydrochloride groups, 9
The reaction was carried out at 0°C for 5 hours. After the reaction was completed, it was isolated in the same manner as in Reference Example 1 to obtain a desired chelate resin.

Reference Example 3 Commercially available styrene-divinylbenzene co-iF combination (divinylbenzene 3 mole%)1. After adding 30 g of chloromethyl ether to O. After gradually adding the mixture without exceeding the temperature, the mixture was reacted at 0 to 5°C for 2 hours to effect chloromethylation. After the reaction is complete, add the reactant to ice water and soak until the black resin sphere turns yellow, then rinse thoroughly with water and acetone.

It was dried under reduced pressure to obtain a resin of 'i-,I(i,OR).

Consolidation IIJ l:I) I-dylated styrene disilane and nilhenzen covalent t,-dimethylborumamide 5Qm 1
-1) These were swollen by adding 15.6 g of b-amino-8-hydroxytonolin and 5.3 g of soda carbonate.
and 8! The reaction was allowed to proceed for 4 hours with i' (:). After the reaction was completed, the same procedure as in Example 1 was carried out.

Reference Example 4 8-H-1-roxyquinoline 14.5 was added to 75 g of 8.0% hydroxide solution and 32.4 g of 37% formalin was heated at 25 to 30°C. When added dropwise, a homogeneous solution was obtained at i:1, so the
Stirring was continued for 10 minutes at 0.degree. C. to remove the initial product. To this initial product, 11.0 g of resorcin was 8.0% hydroxylated.
An aqueous solution dissolved in Heliu J.Aqueous 11-75H.

Add 3.6 g of polyethyleneimine (molecular weight 1,800) and 32.4 g of a 37% Polmarine aqueous solution and heat at 30°C.
The reaction mixture was stirred for 20 minutes at 1'l' L, and the reaction solution was cooled down. When this reaction solution was subjected to pearl polycondensation using perchloromethane as a solvent and water was distilled off while water was being distilled off, the product was crosslinked into small spheres in three-dimensional form. A resin was obtained.

After washing this resin with water, it was treated with 4.0% hydrochloric acid, and after washing with water, it was neutralized with an aqueous solution containing 4.0% tritonium hydroxide.
Next, the desired chelate resin was obtained by sufficiently washing with water.

Example 1 Germanium, i2! loOmg/j of JL copper, Ninogel 2 gel and arsenic ion, respectively! Whitening p++ 0
．． Add 1.0 ml each of the chelate resins produced in Reference Examples 1 and 4 to 50 ml of the sulfuric acid acidic solution of No. 5 in a wet state,
After contacting the two resins for 1 hour at 25"C without shaking, the temperature of various metal ions in the treatment solution was measured by atomic absorption spectrophotometry.

As a result, the concentrations of ferric iron, copper, Conogel 2 bent lead, and arsenic ions were almost the same as before treatment5) from 0 to 100 ml/
However, the germanium ion concentration was less than 5 mg/β and the recovery rate was 9 when using any resin.
It was 5%.

For comparison, commercially available iminodiacetic acid type chelate resin (resin 1), styrene-divinylhenzen 11
1. was processed in the same manner using The concentration of remaining germanium ions was 40% X/C, and the recovery rate was 60 cases.

From this, the chelate resin used for A and 2 Ming has a low p
It is clear that only kermanium ions can be selectively recovered in the H region b(c, -, -).

Example 2 Reference Example 14 Earth horns] (11 dirt horns) (30 + nl of t'J 9 mm of force were filled in the column, each 10 (1 m +; / 7! glue) Rumanium, Ferric iron, copper, near wool, jJ14] 1) J pot):
pHO17nosulfur containing arsenic ions ((J, ('+
Qt'l? 'j1? I'j-(Time &: 60m
1 (7) Speed (Sv211r-1)
'& did.

As a result, ferric, copper, nickel, zinc and arsenic ions 4.1. ．． The leakage concentration was defined as 1 to 5 times 9 to 1A + fat volume (InIIX/'E).

On the other hand, germanium ions did not leak when the resin volume was 4 (+'i m, 31:).

Next, Kirei-L 4A4 fli which adsorbed germanium
t was washed with water, and a 1696 (4 mol) aqueous solution of caustic soda of 3 times the volume of the resin was passed through the resin at SV21+r-,', thereby obtaining an aqueous solution of caustic soda containing 1.3 g of germanium.

Example 3 Chelate 4R1 fat obtained in Reference Example 2: t (1 ml
was packed into a glass column with an inner diameter of 9 mm, and a sulfuric acid acidic/8 solution of pif-0,5 containing germanium was added at 6 times per hour.
The solution was passed at a rate of 0 ml (SV 2 hr-').

As a result, the germanium ions in the effluent were less than 50 m+H/Il even after each treatment with M of 60 times the resin volume.

The composition of the germanium-containing solution was as follows (Ge(IV) 500mg/(1,Zn5
00mg/12, pH 0.5) Next, the germanium-adsorbed Kire-+1Δ1 fat was washed with water, and a 12% (3 mol) caustic soda aqueous solution was added in an amount 4 times the resin volume by SV.
When I poured 1 ffl solution in 2 hours, I found that the caustic soda water containing 5 g of germanium l'i'W< is j:/
It was done.

Real h1! i Example 4 Kiri-1 resin 20m with j and strI applied to Reference Example I
A glass column with an inner diameter of 1) m...φ is filled with C++(lν) 211f HII+! from the top of the column. /β, Zn33
．． 000mg/(ptlo including l, +jiL of 5
f'IQ Acidic 78 liquid at a rate of 50 ml per hour (S
V 2.5br") -(:'>U&Sita.

As a result, even after treatment in an amount 20 times the volume of 1δI fat, the concentration of 1 (·(1ν)) in the outflow lt' was less than 5 mg/β.

Next, wash the Kirei-1 resin that has adsorbed Gelmar'/Jz with water, and add 3 times the amount of 12
% (3 moles) of toy soda water solution SV21+r″1
When the solution was passed through the solution, 11 liquids containing 1.4 g of germanium were obtained.

Claims (1)

[Claims] (1) The process of contacting a chelate resin having oxine as a ligand in its molecule with a solution having a germanium content j, adsorbing germanium onto the chelate resin, and then melting the adsorbed germanium. A method for recovering germanium.