JPH0555452B2 - - Google Patents
Info
- Publication number
- JPH0555452B2 JPH0555452B2 JP15704788A JP15704788A JPH0555452B2 JP H0555452 B2 JPH0555452 B2 JP H0555452B2 JP 15704788 A JP15704788 A JP 15704788A JP 15704788 A JP15704788 A JP 15704788A JP H0555452 B2 JPH0555452 B2 JP H0555452B2
- Authority
- JP
- Japan
- Prior art keywords
- germanium
- ethylene glycol
- glycol solution
- hydrochloric acid
- dioxide
- 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 - Lifetime
Links
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 99
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- 229910052732 germanium Inorganic materials 0.000 claims description 29
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 29
- 229940119177 germanium dioxide Drugs 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 15
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 description 10
- 238000004821 distillation Methods 0.000 description 9
- 150000002291 germanium compounds Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 229910005793 GeO 2 Inorganic materials 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はポリエステル製造工程等で発生するゲ
ルマニウムを含有するエチレングリコール溶液か
らゲルマニウムを、塩酸蒸留および加水分解の処
理を経て二酸化ゲルマニウムとして回収する方法
に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a method for recovering germanium from an ethylene glycol solution containing germanium generated in a polyester manufacturing process, etc., as germanium dioxide through hydrochloric acid distillation and hydrolysis treatment. Regarding.
［従来の技術］
一般にポリエステルを製造する場合、エステル
化反応及び重縮合反応の際に、過剰に加えたエチ
レングリコール及び重縮合で副生したエチレング
リコールが留出し回収されている。重縮合触媒と
してゲルマニウム化合物を使用する場合、ゲルマ
ニウムの一部もエチレングリコールに同伴する。
このエチレングリコール中にはゲルマニウムの他
に水、ジエチレングリコール、ポリエステルの低
重合体も含まれている。[Prior Art] Generally, when producing polyester, ethylene glycol added in excess and ethylene glycol by-produced during the polycondensation are distilled and recovered during the esterification reaction and polycondensation reaction. When a germanium compound is used as a polycondensation catalyst, a portion of the germanium is also entrained in the ethylene glycol.
In addition to germanium, this ethylene glycol also contains water, diethylene glycol, and a polyester low polymer.
そこでゲルマニウムをエチレングリコール溶液
より回収することが試みられている。例えば特公
昭48−6395号には、留出エチレングリコール溶液
を濃縮することによりゲルマニウム化合物濃度を
二酸化ゲルマニウムとして２重量％以上に高めた
濃厚溶液に水を添加して高温度に適当時間保持す
ることによつてゲルマニウム化合物を二酸化ゲル
マニウムに加水分解してエチレングリコール溶液
から分離する方法が開示されている。しかし該方
法ではゲルマニウムを含有するエチレングリコー
ル溶液を２〜100倍濃縮しなければならず、また
ゲルマニウム回収率が低く実用的でないとい問題
点がある。 Therefore, attempts have been made to recover germanium from an ethylene glycol solution. For example, Japanese Patent Publication No. 48-6395 discloses that water is added to a concentrated solution in which the germanium compound concentration is increased to 2% by weight or more as germanium dioxide by concentrating a distilled ethylene glycol solution, and the solution is maintained at a high temperature for an appropriate period of time. discloses a method for hydrolyzing a germanium compound to germanium dioxide and separating it from an ethylene glycol solution. However, this method has the problem that the ethylene glycol solution containing germanium must be concentrated 2 to 100 times, and that the germanium recovery rate is low and impractical.
また、特公昭63−69711号には留出したエチレ
ングリコール溶液に水及び塩基を加えて溶液のPH
を3.0〜9.0に調整した状態で加水分解して、該溶
液に含まれるゲルマニウム化合物を二酸化ゲルマ
ニウムとして析出させて分離する方法が開示され
ている。しかし該方法ではPH調整に使用した塩基
成分が回収された二酸化ゲルマニウムに残存し、
そのまま触媒用二酸化ゲルマニウムとしては使用
できず、精製等の後操作が必要となるという問題
点がある。 In addition, in Japanese Patent Publication No. 63-69711, water and a base were added to the distilled ethylene glycol solution to increase the pH of the solution.
A method is disclosed in which a germanium compound contained in the solution is hydrolyzed in a state in which it is adjusted to 3.0 to 9.0, and a germanium compound contained in the solution is precipitated and separated as germanium dioxide. However, in this method, the base component used for pH adjustment remains in the recovered germanium dioxide,
There is a problem in that it cannot be used as it is as germanium dioxide for catalysts, and post-operations such as purification are required.
［発明が解決しようとする課題］
エチレングリコール溶液からゲルマニウムを、
加水分解および中和等の工程を経て二酸化ゲルマ
ニウムとして回収する従来法には上述のごとき問
題点があることに鑑み、低濃度のエチレングリコ
ール溶液を特に濃厚に濃縮することを要せずに従
来法に比べて高い回収率で容易にゲルマニウムを
回収でき、しかも触媒用に使用可能な高純度の二
酸化ゲルマニウムとして回収できる方法を開発す
ることが課題であつた。[Problem to be solved by the invention] Germanium from ethylene glycol solution,
Considering that the conventional method of recovering germanium dioxide through steps such as hydrolysis and neutralization has the above-mentioned problems, the conventional method does not require particularly concentrated concentration of a low-concentration ethylene glycol solution. The challenge was to develop a method that could easily recover germanium at a higher recovery rate than conventional methods, and that could also be recovered as high-purity germanium dioxide that could be used as a catalyst.
［課題を解決するための手段］
本発明者等は種々検討の結果、下記方法を採用
することにより前記課題を解決できることを見出
し本発明を完成するに到つた。[Means for Solving the Problems] As a result of various studies, the present inventors have found that the above problems can be solved by employing the following method, and have completed the present invention.
すなわち、本発明により、ポリエステル製造工
程等で発生するゲルマニウムを含有するエチレン
グリコール溶液に塩酸を加えて蒸留することによ
り得らえるゲルマニウム塩化物を加水分解して、
二酸化ゲルマニウムとして分離することを特徴と
する二酸化ゲルマニウムの回収方法が提供され
る。 That is, according to the present invention, germanium chloride obtained by adding hydrochloric acid to an ethylene glycol solution containing germanium generated in a polyester manufacturing process and the like and distilling the mixture is hydrolyzed.
A method for recovering germanium dioxide is provided, which is characterized in that germanium dioxide is separated as germanium dioxide.
［作用］
芳香族ジカルボン酸とエチレングリコールを反
応させポリエステルを製造する具体例の一つとし
て、ポリエチレンテレフタレート（PET）の製
造がある。ポリエチレンテレフタレートを製造す
る場合、触媒としてのゲルマニウム化合物の使用
割合は通常PETに対して0.001〜0.1重量％であ
る。[Function] One specific example of producing polyester by reacting aromatic dicarboxylic acid and ethylene glycol is the production of polyethylene terephthalate (PET). When producing polyethylene terephthalate, the proportion of germanium compound used as a catalyst is usually 0.001 to 0.1% by weight based on PET.
本発明の方法ではポリエステルの製造工程等で
発生するゲルマニウムを含むエチレングリコール
溶液を塩酸蒸留するが、そのようなエチレングリ
コール溶液の具体例には、通常大気圧下で芳香族
ジカルボン酸とエチレングリコールを反応させて
エステル化する場合にエステル化反応部より留出
するエチレングリコール溶液及び／又はそれによ
り得られたエステル化物を通常減圧下で一段又は
多段で重縮合させてポリエステル化するときに重
縮合反応部より留出するエチレングリコール溶液
がある。通常エステル化反応部から留出するエチ
レングリコール溶液中にゲルマニウムはGeO2と
して0.05重量％以下含まれており、重縮合反応部
から留出するエチレングリコール溶液中には
GeO2として0.05〜1.0重量％含まれている。 In the method of the present invention, an ethylene glycol solution containing germanium, which is generated in the polyester manufacturing process, is distilled with hydrochloric acid. Polycondensation reaction occurs when the ethylene glycol solution distilled out from the esterification reaction part and/or the esterified product obtained therefrom is polycondensed in one or multiple stages under reduced pressure to form a polyester. There is an ethylene glycol solution that is distilled out. Usually, the ethylene glycol solution distilled from the esterification reaction section contains germanium in the form of GeO 2 at 0.05% by weight or less, and the ethylene glycol solution distilled from the polycondensation reaction section contains germanium.
Contains 0.05-1.0% by weight as GeO2 .
本発明の方法は、前記のゲルマニウムを含むエ
チレングリコール溶液に塩酸を加えて蒸留するこ
とによりゲルマニウム塩化物をつくる工程を含む
が、この場合のエチレングリコール溶液中のゲル
マニム濃度はGeO2換算で通常0.1重量％以上にす
ることがゲルマニウム回収率を高める点及び塩酸
使用量を減らせる点から好ましい。ゲルマニウム
濃度を上述の濃度範囲にするためには、ポリエス
テル製造工程で発生する留出エチレングリコール
溶液を必要に応じて蒸留により濃縮する方法を用
いることができる。 The method of the present invention includes the step of adding hydrochloric acid to the ethylene glycol solution containing germanium and distilling it to produce germanium chloride. In this case, the germanium concentration in the ethylene glycol solution is usually 0.1 in terms of GeO 2 It is preferable to increase the amount by weight % or more from the viewpoint of increasing the germanium recovery rate and reducing the amount of hydrochloric acid used. In order to bring the germanium concentration within the above concentration range, a method may be used in which the distilled ethylene glycol solution generated in the polyester manufacturing process is concentrated by distillation, if necessary.
本発明の方法によつて、前記エチレングリコー
ル溶液に塩酸を加えて蒸留する場合、塩酸濃度は
５〜12規定、好ましくは６〜10規定の範囲にあ
り、塩酸量としてはエチレングリコール溶液量の
0.5倍以上、好ましくは１〜３倍の範囲である。
蒸留温度は70〜130℃、好ましくは79〜120℃の範
囲であり、ゲルマニウム塩化物の留出が終了する
までの適当時間加熱されることが好ましい。本発
明の方法における上記塩酸蒸留工程ではエチレン
グリコール溶液中のゲルマニウム化合物は塩酸に
溶解され、四塩化ゲルマニウムとして留出され
る。この場合塩酸も共に留出するが、四塩化ゲル
マニウムの塩酸への溶解度が小さいので、留出凝
縮された塩酸及び四塩化ゲルマニウムは２層とな
り、比重の大きい四塩化ゲルマニウムはその下層
となるので、容易に塩酸相からの分離が可能であ
る。 When hydrochloric acid is added to the ethylene glycol solution and distilled according to the method of the present invention, the concentration of hydrochloric acid is in the range of 5 to 12N, preferably 6 to 10N, and the amount of hydrochloric acid is the amount of ethylene glycol solution.
It is 0.5 times or more, preferably 1 to 3 times.
The distillation temperature is in the range of 70 to 130°C, preferably 79 to 120°C, and heating is preferably carried out for an appropriate time until the distillation of germanium chloride is completed. In the hydrochloric acid distillation step in the method of the present invention, the germanium compound in the ethylene glycol solution is dissolved in hydrochloric acid and distilled out as germanium tetrachloride. In this case, hydrochloric acid is also distilled out, but since the solubility of germanium tetrachloride in hydrochloric acid is low, the distilled and condensed hydrochloric acid and germanium tetrachloride form two layers, and germanium tetrachloride, which has a high specific gravity, forms the lower layer. It can be easily separated from the hydrochloric acid phase.
本発明の方法によれば、ゲルマニウムを含むエ
チレングリコール溶液を上記方法で直接塩酸蒸留
して沸点が84℃という低い値である四塩化ゲルマ
ニウムを留出されることにより、エチレングリコ
ール溶液中の沸点が高い塩化物をつくる他の無機
不純物からゲルマニウムを選択的に分離すること
ができ、したがつて純度の高い四塩化ゲルマニウ
ムを得ることができる。 According to the method of the present invention, an ethylene glycol solution containing germanium is directly distilled with hydrochloric acid using the above method to distill germanium tetrachloride, which has a boiling point as low as 84°C, thereby lowering the boiling point in the ethylene glycol solution. Germanium can be selectively separated from other inorganic impurities that create high chloride levels, and thus highly pure germanium tetrachloride can be obtained.
純度の高い四塩化ゲルマニウムは純水中に滴下
することで加水分解を受け二酸化ゲルマニウムと
なる。本発明の方法で得られた二酸化ゲルマニウ
ムはポリエステル製造の触媒用として再度利用す
ることが可能である。 When highly pure germanium tetrachloride is dropped into pure water, it undergoes hydrolysis and becomes germanium dioxide. The germanium dioxide obtained by the method of the present invention can be reused as a catalyst for polyester production.
以下実施例により説明する。 This will be explained below using examples.
実施例 １
蒸留装置にゲルマニウムをGeO2換算で0.83重
量％含むエチレングリコール溶液１Kgと8N塩酸
２Kgとを添加し、118℃まで加熱しながら３時間
攪拌を行つた。Example 1 1 kg of an ethylene glycol solution containing 0.83% by weight of germanium in terms of GeO 2 and 2 kg of 8N hydrochloric acid were added to a distillation apparatus, and stirred for 3 hours while heating to 118°C.
留出し得られた四塩化ゲルマニウムは7.8mlで
ゲルマニウム回収率としては83％であつた。この
四塩化ゲルマニウムを120mlの純水中に滴下し、
6.5ｇの二酸化ゲルマニウムを得た。この二酸化
ゲルマニウム中の鉄、銅、鉛、ナトリウム品位は
1ppm以下であつた。 The germanium tetrachloride obtained by distillation was 7.8 ml, and the germanium recovery rate was 83%. Drop this germanium tetrachloride into 120ml of pure water,
6.5 g of germanium dioxide was obtained. The iron, copper, lead, and sodium grades in this germanium dioxide are
It was less than 1 ppm.
実施例 ２
蒸留装置にゲルマニウムをGeO2換算で0.12重
量％を含むエチレングリコール溶液１Kgと6N塩
酸３Kgとを添加し、108℃まで加熱しながら３時
間攪拌を行つた。留出し得られた四塩化ゲルマニ
ウムは0.96mlでゲルマニウム回収率としては70％
であつた。Example 2 1 kg of an ethylene glycol solution containing 0.12% by weight of germanium in terms of GeO 2 and 3 kg of 6N hydrochloric acid were added to a distillation apparatus, and the mixture was stirred for 3 hours while heating to 108°C. The germanium tetrachloride obtained by distillation was 0.96ml, and the germanium recovery rate was 70%.
It was hot.
［比較例］
ゲルマニウムをGeO2換算で0.83重量％含むエ
チレングリコール溶液１Kgに純水を35ml添加し、
PHが7.0になるようにNaOHを添加した。この溶
液を170℃に1.5時間保持後90℃まで冷却し、ろ過
した。ろ紙上に残つた白色固体をメタノールで洗
浄し、乾燥することにより4.58ｇの二酸化ゲルマ
ニウムを得た。ゲルマニウムの回収率は55％であ
つたが、ナトリウム品位が2320ppmと高く、直接
触媒用としてリサイクルはできないものであつ
た。[Comparative example] 35 ml of pure water was added to 1 kg of ethylene glycol solution containing 0.83% by weight of germanium in terms of GeO2 ,
NaOH was added so that the pH was 7.0. This solution was maintained at 170°C for 1.5 hours, cooled to 90°C, and filtered. The white solid remaining on the filter paper was washed with methanol and dried to obtain 4.58 g of germanium dioxide. The recovery rate of germanium was 55%, but the sodium content was as high as 2320 ppm, and it could not be directly recycled for use as a catalyst.
［発明の効果］
本発明方法に従い、ゲルマニウムを含有するエ
チレングリコール溶液に塩酸を加えて蒸留するこ
とにより得られるゲルマニウム塩化物を加水分解
して、ゲルマニウムを回収する場合には、従来法
に比べて工程がより簡単であるにもかかわらず、
直接純度の高い二酸化ゲルマニウムを高回収率で
得ることができる。したがつて、これによりポリ
エステル製造工程で発生するエチレングリコール
溶液からゲルマニウムを容易に回収し、再利用す
ることが可能となり、その経済的意義は大きい。[Effects of the Invention] According to the method of the present invention, germanium is recovered by hydrolyzing germanium chloride obtained by adding hydrochloric acid to an ethylene glycol solution containing germanium and distilling it, compared to the conventional method. Although the process is simpler,
High purity germanium dioxide can be obtained directly with high recovery rate. Therefore, this makes it possible to easily recover and reuse germanium from the ethylene glycol solution generated in the polyester manufacturing process, which has great economic significance.
Claims (1)
溶液に塩酸を加えて蒸留することによりゲルマニ
ウム塩化物を生成せしめ、該塩化物を加水分解し
て二酸化ゲルマニウムを得ることからなる、二酸
化ゲルマニウムの回収方法。1. A method for recovering germanium dioxide, which comprises adding hydrochloric acid to an ethylene glycol solution containing germanium and distilling it to generate germanium chloride, and hydrolyzing the chloride to obtain germanium dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15704788A JPH026331A (en) | 1988-06-25 | 1988-06-25 | Method for recovering germanium dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15704788A JPH026331A (en) | 1988-06-25 | 1988-06-25 | Method for recovering germanium dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH026331A JPH026331A (en) | 1990-01-10 |
| JPH0555452B2 true JPH0555452B2 (en) | 1993-08-17 |
Family
ID=15641034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15704788A Granted JPH026331A (en) | 1988-06-25 | 1988-06-25 | Method for recovering germanium dioxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH026331A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100340472C (en) * | 2005-12-27 | 2007-10-03 | 云南冶金集团总公司技术中心 | Process for recovering hydrochloride from leached germanium residu acid |
| KR100836569B1 (en) * | 2006-08-25 | 2008-06-10 | 경남대학교 산학협력단 | Pharmaceutical Compositions and Food Additives Containing the Extracts of Medullus as Active Ingredients |
| CN102892907A (en) * | 2010-02-18 | 2013-01-23 | 尼欧麦特科技公司 | Process for the recovery of metals and hydrochloric acid |
| CN104073636B (en) * | 2014-06-23 | 2016-05-25 | 贵州宏达环保科技有限公司 | A kind of method of extracting germanium concentrate from germanic back extraction alkali lye |
| CN116623018B (en) * | 2023-06-27 | 2024-09-20 | 昆明冶金研究院有限公司 | Method for extracting germanium by acid burning |
-
1988
- 1988-06-25 JP JP15704788A patent/JPH026331A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH026331A (en) | 1990-01-10 |
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