JPH026331A - Method for recovering germanium dioxide - Google Patents
Method for recovering germanium dioxideInfo
- Publication number
- JPH026331A JPH026331A JP15704788A JP15704788A JPH026331A JP H026331 A JPH026331 A JP H026331A JP 15704788 A JP15704788 A JP 15704788A JP 15704788 A JP15704788 A JP 15704788A JP H026331 A JPH026331 A JP H026331A
- Authority
- JP
- Japan
- Prior art keywords
- germanium
- ethylene glycol
- glycol solution
- hydrochloric acid
- distilled
- 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.)
- Granted
Links
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229940119177 germanium dioxide Drugs 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 110
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 34
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 34
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 229920000728 polyester Polymers 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 8
- 150000002291 germanium compounds Chemical class 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 229910006113 GeCl4 Inorganic materials 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000008213 purified water Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000004821 distillation Methods 0.000 description 9
- 238000011084 recovery Methods 0.000 description 7
- 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
- 238000007796 conventional method Methods 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
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-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
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 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)
Abstract
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
及び重縮合で副生じ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。[Prior Art] Generally, when producing polyester, ethylene glycol added in excess and ethylene glycol produced as a by-product 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.
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。In addition to germanium, this ethylene glycol contains water,
Also included are diethylene glycol and polyester low polymers.
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４８−８３９
５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っ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う問題点がある。Therefore, attempts have been made to recover germanium from an ethylene glycol solution. For example, Tokuko Sho 48-839
In No. 5, the germanium compound concentration is increased to 2% by weight or more as germanium dioxide by concentrating the distilled ethylene glycol solution, water is added to the concentrated solution, and the germanium compound is oxidized by maintaining it at a high temperature for an appropriate time. A method for hydrolyzing germanium and separating it from an ethylene glycol solution is disclosed. 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 is not practical.
また、特公昭８３−６９７１１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ｐｌ＋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. 83-69711, water and a base were added to a distilled ethylene glycol solution to adjust the pH of the solution to 3.
A method is disclosed in which a germanium compound contained in the solution is hydrolyzed in a state adjusted to 0 to 9.0, and a germanium compound contained in the solution is precipitated and separated as germanium dioxide. However, this method has the problem that the base component used for pl+ adjustment remains in the recovered germanium dioxide, and 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
ることが課題であった。[Problems to be Solved by the Invention] In view of the above-mentioned problems with the conventional method of recovering germanium from an ethylene glycol solution as germanium dioxide through steps such as hydrolysis and neutralization, we have developed a method to recover germanium from an ethylene glycol solution as germanium dioxide. To develop a method that can easily recover germanium at a higher recovery rate than conventional methods without particularly concentrating a glycol solution, and can also recover germanium dioxide of high purity that can be used as a catalyst. was the issue.
［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
するに到った。[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れるゲルマニウ
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, the present invention is characterized in that 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 and separated as germanium dioxide. A method for recovering germanium dioxide is provided.
［作 用コ
芳谷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０．００
１〜０．１重量％である。[Function] One specific example of producing polyester by reacting an aromatic dicarboxylic acid with ethylene glycol is the production of polyethylene terephthalate (PET). When producing polyethylene terephthalate, the ratio of germanium compound used as a catalyst is usually 0.00 to PET.
It is 1 to 0.1% by weight.
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、通常大気圧下で芳呑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Ｇ ｅ Ｏ２として０．０５重１％
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Ｇ ｅ Ｏ’２として０．０５〜
１２口重量％含まれている。In the method of the present invention, an ethylene glycol solution containing germanium generated in the polyester manufacturing process is distilled with hydrochloric acid. Polycondensation occurs when the ethylene glycol solution distilled from the esterification reaction section and/or the resulting esterified product is polycondensed in one or multiple stages under reduced pressure to form a polyester. There is an ethylene glycol solution distilled out from the reaction section. Usually, germanium is contained in the ethylene glycol solution distilled from the esterification reaction section at a concentration of 0.05% by weight as G e O2.
The ethylene glycol solution distilled from the polycondensation reaction section contains 0.05 to 0.05 to G e O'2.
Contains 12% by weight.
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ウム濃度はＧ ｅ Ｏ２
換算で通常０゜ｌ ！Ｉｉｍ％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 producing germanium chloride by adding hydrochloric acid to the ethylene glycol solution containing germanium and distilling it. In this case, the germanium concentration in the ethylene glycol solution is G e O2
Normally converted to 0゜l! It is preferable to make the amount more than Iim% 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.
本発明の方法において、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°Ｃ１
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。In the method of the present invention, when hydrochloric acid is added to the ethylene glycol solution and distilled, the hydrochloric acid concentration is 5 to 12N,
It is preferably in the range of 6 to 10 normal, and the amount of hydrochloric acid is 0.5 times or more, preferably 1 to 3 times the amount of the ethylene glycol solution. Distillation temperature is 70-130°C1
Preferably, the temperature is in the range of 79 to 120°C, and heating is preferably continued 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.
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、容易に塩酸量から
の分離が可能である。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 amount of hydrochloric acid.
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せる
ことにより、エチレングリコール溶液中の沸点か高い塩
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、したがっ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 reduce the boiling point to 84.
By distilling germanium tetrachloride, which has a low value of 100 °C, it is possible to selectively separate germanium from other inorganic impurities that create chlorides with high boiling points in ethylene glycol solutions, thus producing highly pure tetrachloride. Germanium 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
で加水分解を受は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か可能である。When highly purified 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Ｇ ｅ ０２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２
ｋｇとを添加し、１１８℃まで加熱しながら３時間撹拌
を行った。[Example: 1] Germanium was added to the distillation apparatus at a concentration of 0.83 in terms of Ge 02
1 kg of ethylene glycol solution containing % by weight and 2 kg of 8N hydrochloric acid
kg 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％であった。この四塩化ゲ
ルマニウムを１２０ｍ１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１ ｐｐｌＩ以下であ
った。The germanium tetrachloride obtained by distillation was 7.8 ml, and the germanium recovery rate was 83%. This germanium tetrachloride was dropped into 120 ml of pure water to obtain 6.5 g of germanium dioxide. The iron, copper, lead, and sodium contents in this germanium dioxide were 1 pplI or less.
［実施例：２］
蒸留装置にゲルマニウムをＧ ｅ Ｏ２換算で０．１２
２重丸を含むエチレングリコール溶液１ｋｇと６Ｎ塩酸
３ｋｇを添加し、１０８℃まで加熱しなから３時間撹拌
を行った。留出し得られた四塩化ゲルマニウムは０．９
６ｍ１でゲルマニウム回収率としては７０％であった。[Example: 2] Germanium was added to the distillation apparatus at a concentration of 0.12 in terms of G e O2.
1 kg of an ethylene glycol solution containing double circles and 3 kg of 6N hydrochloric acid were added, and the mixture was stirred for 3 hours without heating to 108°C. Germanium tetrachloride obtained by distillation is 0.9
The germanium recovery rate was 70% in 6 ml.
［比 較 例］
ゲルマニウムをＧ ｅ Ｏ２換算で０．８３％を含むエ
チレングリコール溶液１ ｋｇに純水を３５ｍ１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。ろ紙上に残っ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５５９６であったが
、ナトリウム品位が２３２０ｐｐＩｍ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った。[Comparative Example] 35 ml of pure water was added to 1 kg of an ethylene glycol solution containing 0.83% germanium in terms of GeO2, and NaOH was added to adjust the pH to 7.0. This solution was kept at 170°C for 1.5 hours and then cooled to 90°C.
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 5,596, but the sodium content was as high as 2,320 ppIm, 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かより簡単であ
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。したがって、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, germanium dioxide with high purity can be obtained directly with a 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.
特許出願人 同和鉱業株式会′ｆ１゜Patent applicant: Dowa Mining Co., Ltd.'f1゜
Claims (1)
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。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 true JPH026331A (en) | 1990-01-10 |
| JPH0555452B2 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) |
Cited By (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 | A pharmaceutical composition and food additive containing a extract of Styela clava |
| JP2013527307A (en) * | 2010-02-18 | 2013-06-27 | ネオメット テクノロジーズ インコーポレイテッド | Metal and hydrochloric acid recovery methods |
| CN104073636A (en) * | 2014-06-23 | 2014-10-01 | 贵州顶效开发区宏达金属综合回收有限公司 | Method for extracting germanium concentrate from germanium-containing reverse extraction alkaline liquor |
| CN116623018A (en) * | 2023-06-27 | 2023-08-22 | 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
Cited By (7)
| 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 | A pharmaceutical composition and food additive containing a extract of Styela clava |
| JP2013527307A (en) * | 2010-02-18 | 2013-06-27 | ネオメット テクノロジーズ インコーポレイテッド | Metal and hydrochloric acid recovery methods |
| US9889421B2 (en) | 2010-02-18 | 2018-02-13 | Brav Metal Technologies Inc. | Process for the recovery of metals and hydrochloric acid |
| CN104073636A (en) * | 2014-06-23 | 2014-10-01 | 贵州顶效开发区宏达金属综合回收有限公司 | Method for extracting germanium concentrate from germanium-containing reverse extraction alkaline liquor |
| 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 |
| CN116623018A (en) * | 2023-06-27 | 2023-08-22 | 昆明冶金研究院有限公司 | Method for extracting germanium by acid burning |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0555452B2 (en) | 1993-08-17 |
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