JPS60145914A - Recovery of germanium - Google Patents

Abstract

PURPOSE:To recover Ge effectively from a mineral containing large amount of metal salts other than Ge salt and containing trace amount of Ge, by leaching the mineral with an acid, separating the leaching residue, and contacting the leachate with a chelating ion exchange resin. CONSTITUTION:A substance containing trace Ge and a large amount of the salt of other metals, e.g. the refinery intermediate (or refinery residue) produced by the refinery of non-ferrous metals, e.g. refinery of zinc, etc., is leached with an acid using a mineral acid such as sulfuric acid, and the leaching residue is separated from the leachate. The obtained leachate is made to contact with a chelating ion exchange resin, e.g. a resin having aminocarboxylic acid group as functional group, to effect the selective adsorption of Ge to the resin. The adsorbed Ge is recovered effectively by elution.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a Ge
The present invention relates to a method for effectively recovering Ge from materials containing large amounts of salts of other metals, such as smelting intermediates.

For example, in a nonferrous smelting process such as zinc smelting, a trace amount of Ge contained in the processed ore becomes concentrated in the smelting residue. In addition to Ge, such smelting residue contains
Salts such as zinc, aluminum, iron and arsenic are usually present in large amounts, and these metal salts are much larger than the Ge content.

Conventionally, the most common method for recovering Ge from materials such as smelting intermediates (smelting residues) is the following.

First, this smelting residue is leached using mineral acid, hydrogen sulfide or tannic acid is added to the leaching solution to generate a precipitate containing Ge, and this precipitate is normally used in the subsequent Ge extraction process. Ta. However, in the treatment of precipitation by sulfides such as hydrogen sulfide.

Although approximately 100% of Ge is precipitated, a large amount of arsenic is also precipitated, and the precipitate usually contains several tens of times as much arsenic as Ge. Therefore, a dry or wet dearsenization process is required, and even if this dearsenization process is carried out, As contamination cannot be avoided in the subsequent distillation step of germanium chloride using a conventional method, and repeated purification is required. This required a lot of man-hours, leading to high costs. Further, in the method of forming a precipitate of germanium tannate using tannic acid, it is difficult to set one condition, and the actual yield of Ge decreases, so it cannot necessarily be said to be a good method.

Also, MgJ? There is also a method of generating a precipitate using 3Ba salt, etc., but this method can be used for analysis etc.
This is not suitable as an industrial method for recovery.

Furthermore, in addition to the formulation that generates a precipitate as described above, extraction of Ge by solvent extraction has also been reported as a method for collecting Ge in a liquid. When targeting a liquid containing Ge, it is difficult to efficiently and selectively extract only Ge.

The present inventors have conducted intensive research aimed at selectively and efficiently recovering Ge directly from a leachate in which other metals coexist in excess, without using the method of precipitation formation as described above. The inventors have discovered that all of the above objects can be achieved by bringing the leachate into contact with a chelating ion exchange resin to adsorb germanium and eluting the adsorbed germanium, and have completed the present invention. That is, the present invention subjects a substance containing a small amount of germanium and a large amount of salts of metals other than germanium to acid leaching treatment using a mineral acid,
After separating the leaching residue from the leaching solution, the leaching solution is brought into contact with a chelating ion exchange resin to selectively adsorb germanium onto the resin.

The present invention provides a method for recovering germanium, which is characterized in that the adsorbed germanium is then separated by /8.

The method of the present invention will be specifically explained below. Examples of substances targeted by the present invention that contain a trace amount of germanium and a large amount of salts of metals other than germanium include substances such as smelting intermediates. These smelting intermediates and other substances are
These include various smelting residues that contain a small amount of Ge, and specifically include residues after leaching zinc from burnt ore in zinc smelting. Such smelting intermediates are
Although it is accompanied by a small amount of Ge, it contains a large amount of salts of various metals other than Ge. In the present invention, first, a leaching treatment is carried out using such a trace amount of Ge compound substance mineral acid 1, for example, sulfuric acid. In this case, the free sulfuric acid concentration of the leachate is 20 to 1
00 (g#).

Residues that are not dissolved by this leaching process are filtered out, and a leaching solution containing various metal ions is collected. This leachate can dissolve the substantial amount of Ge present in the smelting intermediate, but it also contains ions of other metals in a much larger amount than the Gc.

If trivalent iron ions are present in this leachate, it is preferable to perform a treatment to reduce them to divalent iron ions using a reducing agent such as sulfur dioxide gas or sodium bisulfite.

Next, this leachate is brought into contact with a chelating ion exchange resin, but in this case, it is desirable to appropriately adjust the acid concentration of this liquid. When the leachate is an acidic sulfuric acid solution, the free sulfuric acid concentration is preferably 20 to 1100 (/β). It is advantageous in actual operation that a leachate having such a free sulfuric acid concentration is obtained in the previous leaching treatment of the smelting intermediate.

Examples of chelating ion exchange resins that can be used in the present invention include the following commercially available resins. For example, a chelating ion exchange resin having an aminocarboxylic acid group as a functional group (M in the formula represents an alkali metal atom or a hydrogen atom, and R1 and R2 each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) It is obtained by three-dimensionally crosslinking the compound, phenol and aldehyde. According to Japanese Patent Application Laid-Open No. 54-121241, this resin is known to be able to reduce the iron ion concentration in an @-type electrogalvanizing bath. Commercially available chelating ion exchange resins having aminocarboxylic acid groups that can be used in the present invention include Unitika@
Manufactured by UNISERESOKU R-10, UR-20',
UR-30, UR-40, and 0R-50i Sumikilate ■Q-10HR and MC-30 manufactured by Sumitomo Chemical Co., Ltd.; Amberlight ■ manufactured by Organo 01
Examples include IRC-718i and Mitsubishi Chemical Industries side dam's Diamond Ion CR-10. Also, as a chelating ion exchange resin with aminoalkyl phosphate group as a functional group, 2
For example, the commercially available Unitika side-cleft Unicelesoku ■UR330
0T and Sumikylate ES-4 manufactured by Sumiya Kagaku Kogyo ■
67, 9 as a chelating ion exchange resin having a polyamino group as a functional group, for example, commercially available Sumikylate ■8-850 manufactured by Sumiya Chemical Co., Ltd. and Diaion ■CR-20 manufactured by Mitsubishi Chemical Al, and furthermore, As a chelating ion exchange resin having a pyridine group as a functional group, commercially available Sumikylate ■CR-2 manufactured by Susumu Kagaku Kogyo Co., Ltd. can also be used in the practice of the present invention.

A convenient method for bringing such a chelating ion exchange resin into contact with the leachate is to pass the leachate through a column filled with resin. At that time, it is preferable to pass the liquid so that the three liquid passing speeds (space velocities S, V) are 5.0 or less. Further, the temperature at which the leachate contacts the resin is suitably 10 to 50°C. As a result, only Gd in the leachate can be selectively adsorbed to the resin while substantially all of the elements other than Ge remain in the leachate.

Figure 1 shows that zinc, iron, aluminum and arsenic are
After reducing trivalent iron ions to divalent ones by blowing sulfite residue into an acidic sulfuric acid solution (free sulfuric acid concentration about 50 g/ff) containing 0 (g/I2) and a trace amount of Ge, S, V = 2. 1 when the liquid was passed through a column packed with the chelating ion exchange resin of UNISERENOKU UR-50 at a space velocity.
This shows the relationship between the flow rate and the flow point, and from this,
It can be seen that only Ge is selectively adsorbed onto the resin from this solution under the given conditions.

In order to elute the Ge adsorbed on the resin, it is preferable to use an alkaline aqueous solution such as caustic soda.

The substantial hold of Ge adsorbed on the resin can be easily eluted by caustic soda at a concentration of 80 to 160 g/β. FIG. 2 shows a /8 separation curve when Ge adsorbed on the resin was eluted with 160 g/β of caustic soda.

In this way, alkali/8 syneresis containing Ge (4
If y, add hydrochloric acid to this /8 synerte to neutralize the pH.
(approximately 9), thereby forming a precipitate of sodium germanate, and this precipitate was filtered off.

Hydrochloric acid is added to this precipitate again and leaching distillation is performed to obtain highly pure germanium chloride as a distillate. In addition, highly pure germanium oxide can be obtained by hydrolyzing this germanium chloride. The alkaline eluent is neutralized with acid, and a precipitating agent such as a sulfiding agent is added to precipitate it again. The precipitate is then filtered, hydrochloric acid is added again, leaching distillation is carried out, and highly pure germanium chloride is obtained as a distillate. You can also get Also in this case, highly pure germanium oxide can be obtained by hydrolyzing the obtained germanium chloride.

According to the method of the present invention, zinc and iron are used as smelting intermediates.

Even if aluminum or the like is accompanied, especially arsenic, germanium can be selectively recovered from these. In particular, even if arsenic is present (even if arsenic is dissolved in the leachate), a germanium concentrate from which this arsenic is separated can be obtained, so when sodium germanate is precipitated from this concentrate, arsenic contamination is reduced. When this is leached and distilled using hydrochloric acid, it is possible to recover highly pure germanium chloride without arsenic contamination, so it can be said that this method is industrially very advantageous compared to the conventional direct precipitation method from the leachate.

Next, the present invention will be specifically explained using examples.

Example 1 A zinc smelting intermediate whose composition is shown in Table 1 is used as a raw material, and the concentration of free sulfuric acid in the solution after leaching is 50 g /
Sulfuric acid was added so that the leachate had a composition shown in Table 2.

After reducing the iron by blowing sulfur dioxide gas into the leachate shown in Table 2,
This solution was passed through a column filled with a chelating ion exchange resin (resin base: phenol, formalin resin, chelate group: iminodiacetic acid) at S, v-2. When the passed-through liquid was analyzed, the concentrations of Zn, AI, Fe, and As in the first-passed liquid hardly changed, and Ge was not detected. That is, almost 100% of only Ge was adsorbed on this resin.

Next, add 160 g/1 of this Ge-adsorbed resin.
Eluted with Na0t+ of 2. The composition of the obtained eluent is shown in Table 3.

By elution with this 160 g/E-NaOH,
Almost 100% of the Ge adsorbed on the resin could be recovered.

Hydrochloric acid was added to the eluent in Table 3 to adjust the pH to approximately 9,
The generated precipitate was separated and collected from the liquid. This precipitate is essentially sodium germanate. At this time, the recovery rate of germanium from the raw materials shown in Table 1 was 95% or more.

Next, this precipitate was subjected to hydrochloric acid leaching and distillation, and a 1M germanium chloride distillate was hydrolyzed to recover germanium oxide. This germanium oxide was pure containing almost no impurities, and the recovery rate of germanium Tota 1 from the raw materials in Table 1 recovered as germanium oxide was 90% or more.

[Brief explanation of the drawing]

Figure 1 shows the flow rate and flow point when a dilute germanium solution containing high concentrations of zinc, iron, aluminum, and arsenic is passed through a chelating ion exchange resin after maintaining its reducing properties. Relationship diagram. FIG. 2 is a diagram showing the relationship between the amount of Ge/8 released in the elution curve and the Ge concentration when a chelating ion exchange resin adsorbing germanium is eluted at 160 g/β-Na011. Applicant Dowa Mining Co., Ltd. 1 Unitika Co., Ltd. Agent Patent attorney Kenji Wada Procedural amendment (spontaneous) February 10, 1980 Commissioner of the Patent Office Kazuo Wakasugi 2. Name of the invention Germanium recovery method 3. Amends. Relationship with the patent case 1tM person Address 8-2 Marunouchi-chome, Chiyoda-ku, Tokyo Name Dowa Mining Co., Ltd. (1 person) Representative Nishi 1) Taka 4, Agent 162 Address Ichigaya, Shinjuku-ku, Tokyo 83 Yakuojicho (1), Claims column (2) of the specification, 9 Drawings 6, Contents of amendment (J), Claims are amended as shown in the attached sheet. (2) 1st of 6 drawings The figure is as shown in the attached figure. (Attachment) 2. Claim (1): Acid leaching treatment of a substance containing a trace amount of germanium and a large amount of salts of metals other than germanium using a mineral acid. After separating the leaching residue from the leaching solution, the leaching solution is brought into contact with a chelating ion exchange resin to selectively adsorb germanium to the resin, and the U-treated ``U'' is treated with an alkali 7'-'-r'. --tq-. (2) The germanium recovery method according to claim 1, wherein the alkaline aqueous solution is caustic soda water/8 liquid.

Claims (1)

[Claims] A substance containing a small amount of germanium and a large amount of salts of metals other than germanium is subjected to acid leaching treatment using a mineral acid, and the leaching residue is separated from the leachate. A method for recovering germanium, which comprises bringing a leachate into contact with a chelating ion exchange resin and selectively adsorbing germanium onto the resin.