JPS6136059B2 - - Google Patents
Info
- Publication number
- JPS6136059B2 JPS6136059B2 JP9900181A JP9900181A JPS6136059B2 JP S6136059 B2 JPS6136059 B2 JP S6136059B2 JP 9900181 A JP9900181 A JP 9900181A JP 9900181 A JP9900181 A JP 9900181A JP S6136059 B2 JPS6136059 B2 JP S6136059B2
- Authority
- JP
- Japan
- Prior art keywords
- germanium
- sodium hydroxide
- hydroxide solution
- acid
- resin column
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 229910052732 germanium Inorganic materials 0.000 claims description 19
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 19
- 239000011435 rock Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003957 anion exchange resin Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 3
- 229910005793 GeO 2 Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- FNIHDXPFFIOGKL-UHFFFAOYSA-N disodium;dioxido(oxo)germane Chemical group [Na+].[Na+].[O-][Ge]([O-])=O FNIHDXPFFIOGKL-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Description
【発明の詳細な説明】
本発明は含ゲルマニウム岩石よりゲルマニウム
を効率よく回収する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for efficiently recovering germanium from germanium-containing rocks.
ゲルマニウムは火成岩中に存在し、平均／
ppm前後含まれているが、風化岩石中には0.5％
位のゲルマニウムを含むものも存在する。また石
灰，亜炭中にも微量含まれており、石炭灰中には
数％に達することもある。従来ゲルマニウムの製
錬法としては、四塩化ゲルマニウムとして蒸溜す
る方法が最良で一般に採用されている。適当な精
留塔を用い、塩素を通じながら蒸溜し、留出した
四塩化ゲルマニウムは冷水中に捕集する。 Germanium is present in igneous rocks and has an average
Contains around ppm, but 0.5% in weathered rocks
There are also some that contain germanium. It is also contained in trace amounts in lime and lignite, and can reach several percent in coal ash. Conventionally, as a method for smelting germanium, the method of distilling germanium tetrachloride is the best and generally adopted method. Distillation is carried out using a suitable rectification column while passing chlorine through, and the distilled germanium tetrachloride is collected in cold water.
本発明は風化岩石からゲルマニウムを純粋に回
収する方法を開発すべく鋭意研究を重ねた結果イ
オン交換法により岩石中よりゲルマニウムを高収
率で得られること見出し、本発明を完成するに至
つた。 The present invention was developed after intensive research to develop a method for recovering germanium from weathered rocks, and as a result, it was discovered that germanium can be obtained from rocks at a high yield using an ion exchange method, leading to the completion of the present invention.
すなわち、含ゲルマニウム岩石微粉砕物を硝
酸，フツ化水素酸および硫酸とともにおだやかに
加熱を行ないケイ酸を完全に除いた溶液に水酸化
ナトリウムを加えPH7.0に調製すると、鉄，アル
ミニウム等の水酸化物の沈澱を生ずる。この沈澱
を分離した液を陰イオン交換樹脂柱で処理した
後、水酸化ナトリウム溶液で溶離させることによ
り純粋なゲルマニウムを回収することができた。 In other words, by gently heating finely ground germanium-containing rock with nitric acid, hydrofluoric acid, and sulfuric acid to completely remove silicic acid and adjusting the pH to 7.0 by adding sodium hydroxide, the water content of iron, aluminum, etc. Produces oxide precipitation. Pure germanium could be recovered by treating the separated precipitate with an anion exchange resin column and eluting it with a sodium hydroxide solution.
本発明において鉄，アルミニウム等の水酸化物
の沈澱分離方法としては過または遠心分離など
が適宜用いられる。 In the present invention, filtration or centrifugation is appropriately used as a method for precipitating and separating hydroxides of iron, aluminum, etc.
本発明で用いられる陰イオン交換樹脂としては
アンバーライトIRA400（商品名，米国 ロー
ム・アンド・ハース社製）、ダウエツクス１−×
８（商品名，ダウケミカル社製）などが例として
あげられる。 Examples of anion exchange resins used in the present invention include Amberlite IRA400 (trade name, manufactured by Rohm and Haas, USA) and Dowex 1-X.
8 (trade name, manufactured by Dow Chemical Company) is an example.
上記陰イオン交換樹脂としてはCl型よりOH型
を用いるのが好ましい。OH型樹脂柱にはゲルマ
ニウムを完全に吸着できるが、Cl型では吸着が
不完全になる。溶離液としては水酸化ナトリウム
溶液でよいが、濃度により溶出状態が異なる。
GeO2として５mgを吸着させた樹脂の溶出実験の
結果を第１図および第２図に示した。溶出量はカ
ラム体積（CV）単位で表わしてある。この溶出
液はゲルマニウム酸ナトリウム（Na2GeO3）であ
る。 As the anion exchange resin, it is preferable to use an OH type rather than a Cl type. Germanium can be completely adsorbed on the OH type resin column, but adsorption is incomplete on the Cl type. A sodium hydroxide solution may be used as the eluent, but the elution state differs depending on the concentration.
The results of an elution experiment using a resin adsorbed with 5 mg of GeO 2 are shown in FIGS. 1 and 2. Elution volumes are expressed in column volume (CV). This eluent is sodium germanate (Na 2 GeO 3 ).
本発明によれば含ゲルマニウム岩石中よりゲル
マニウムを高純度でかつ高収率で回収することが
でき、また経済的であり、工業的回収方法として
好適である。 According to the present invention, germanium can be recovered from germanium-containing rocks with high purity and high yield, and is economical and suitable as an industrial recovery method.
次に本発明を実施例によりさらに詳細に説明す
る。 Next, the present invention will be explained in more detail with reference to Examples.
実施例
GeO20.44％含有の火成岩風化岩石１ｇを白金
蒸発皿に採取し、フツ化水素酸10ml、硝酸１mlお
よび硫酸１mlを加え、砂浴上でおだやかに加熱を
行ないケイ酸を完全に除去する。その溶液に水酸
化ナトリウム溶液を加えてPHを7.0に調製し、
鉄，アルミニウム等の水酸化物の沈澱を作り、沈
澱を分離する。沈澱分離した液を、あらかじめ
4N水酸化ナトリウム溶液および蒸留水で洗浄し
た陰イオン交換樹脂ダウエツクス１−×８（樹脂
量10ml）のOH型樹脂柱に流し、蒸留水100mlで
樹脂柱を洗浄後、2N水酸化ナトリウム溶液20ml
を流しゲルマニウムを溶出させた。Example 1 g of weathered igneous rock containing 0.44% GeO 2 was collected in a platinum evaporation dish, 10 ml of hydrofluoric acid, 1 ml of nitric acid and 1 ml of sulfuric acid were added, and the mixture was heated gently on a sand bath to completely remove silicic acid. . Add sodium hydroxide solution to the solution to adjust the pH to 7.0,
Precipitate hydroxides of iron, aluminum, etc. and separate the precipitates. Precipitate the precipitated liquid in advance.
Pour into an OH type resin column of anion exchange resin Dowex 1-x8 (resin amount 10ml) that has been washed with 4N sodium hydroxide solution and distilled water, wash the resin column with 100ml of distilled water, and then add 20ml of 2N sodium hydroxide solution.
was run to elute germanium.
溶離液としては0.5N水酸化ナトリウムでは120
ml、1N水酸化ナトリウムでは50ml、4N水酸化ナ
トリウム溶液では６mlで十分である。この際の回
収率は98％であつた。なお樹脂柱には交換能力一
杯までゲルマニウムを吸着させることができるの
で経済的である。 120 for 0.5N sodium hydroxide as eluent
ml, 50 ml for 1N sodium hydroxide solution and 6 ml for 4N sodium hydroxide solution is sufficient. The recovery rate at this time was 98%. Note that germanium can be adsorbed to the resin column up to its exchange capacity, which is economical.
第１図はOH型陰イオン交換樹脂柱ダウエツク
ス１−×８（樹脂量10ml）を用い、2N水酸化ナ
トリウム溶液で溶離した結果を、第２図は同上樹
脂柱を1N水酸化ナトリウム溶液で溶離した結果
を示し、横軸は溶出量、縦軸は溶出液の濃度であ
る。なお溶出量はカラム体積（CV）単位で、濃
度はppmGeO2で表わしてある。
Figure 1 shows the results of eluting with 2N sodium hydroxide solution using OH type anion exchange resin column Dowex 1-x8 (resin amount 10ml), and Figure 2 shows the results of elution of the same resin column with 1N sodium hydroxide solution. The horizontal axis is the elution amount, and the vertical axis is the eluate concentration. The elution amount is expressed in column volume (CV), and the concentration is expressed in ppmGeO 2 .
Claims (1)
水素酸および硫酸とともにおだやかに加熱を行な
いケイ酸を完全に除いた溶液に水酸化ナトリウム
を加えてPH7.0に調整後、沈澱を分離し液を陰
イオン交換樹脂柱に通した後、水酸化ナトリウム
溶液でゲルマニウムを溶出させることを特徴とす
る含ゲルマニウム岩石中よりゲルマニウムを回収
する方法。1 Gently heat the finely ground germanium-containing rock with nitric acid, hydrofluoric acid, and sulfuric acid to completely remove silicic acid. After adjusting the pH to 7.0 by adding sodium hydroxide, separate the precipitate and drain the liquid. A method for recovering germanium from germanium-containing rocks, which comprises passing the germanium through an anion exchange resin column and eluting the germanium with a sodium hydroxide solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9900181A JPS581031A (en) | 1981-06-25 | 1981-06-25 | Method for recovering germanium from germanium- containing rock |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9900181A JPS581031A (en) | 1981-06-25 | 1981-06-25 | Method for recovering germanium from germanium- containing rock |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS581031A JPS581031A (en) | 1983-01-06 |
| JPS6136059B2 true JPS6136059B2 (en) | 1986-08-16 |
Family
ID=14234741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9900181A Granted JPS581031A (en) | 1981-06-25 | 1981-06-25 | Method for recovering germanium from germanium- containing rock |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS581031A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104046801B (en) * | 2014-06-18 | 2016-11-02 | 贵州宏达环保科技有限公司 | A kind of method extracting germanium from germanium silicon raw material |
| CN107723467A (en) * | 2017-09-20 | 2018-02-23 | 郴州丰越环保科技有限公司 | A kind of method of high efficiente callback germanium |
-
1981
- 1981-06-25 JP JP9900181A patent/JPS581031A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS581031A (en) | 1983-01-06 |
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