EP0162954A2 - Process for obtaining a germanium concentrate - Google Patents
Process for obtaining a germanium concentrate Download PDFInfo
- Publication number
- EP0162954A2 EP0162954A2 EP84114333A EP84114333A EP0162954A2 EP 0162954 A2 EP0162954 A2 EP 0162954A2 EP 84114333 A EP84114333 A EP 84114333A EP 84114333 A EP84114333 A EP 84114333A EP 0162954 A2 EP0162954 A2 EP 0162954A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- germanium
- concentrate
- sulfuric acid
- leaching
- solution
- 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.)
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
Definitions
- the invention relates to a method for obtaining a processable germanium concentrate.
- Germanium occurs as an accompanying element in concentrations of a few ppm in some deposits of sulfidic ores of the metals lead, copper and zinc.
- Known Ge minerals are e.g. B. argyrodite, canfieldite, germanite and renierite. When processing the raw ores, the germanium minerals are concentrated in concentrates together with the sulfides of the main metals lead, zinc and copper.
- the concentration of germanium only reaches such high values in the concentrates in a few particularly rich crude ores that a direct separation of the ge from the concentrates is technically possible and economically justifiable.
- Germanium is also sulfidically condensed and separated from the exhaust gas in a nonoxidizing atmosphere. Together with the germanium sulfide, arsenic compounds and, depending on the temperature used, PbS are also sublimed. In most lead, zinc and copper concentrates, however, the germanium contents are so low that Ge enrichment and separation from the concentrate are out of the question. Germanium often accumulates in intermediate or Waste products from the processes for extracting the main metals.
- the fly ash generated in addition to the main components of lead oxide and zinc oxide are other volatilizable metal compounds such as i - for example, those of arsenic, antimony, cadmium and Germaniums_
- Such flue dusts are next geröstesten zinc ores in hydronteta turgisch-e often Ektro used ytician zinc recovery! .
- the dust is leached with sulfuric acid, and germanium is precipitated and enriched from the solutions.
- Germanium goes into the final slags of lead reduction. Germanium, together with lead and zinc, can be evaporated from them by a slag blowing process and, after oxidation and condensation, enriched and separated in a flying dust. The further concentration of germanium then takes place, as already mentioned several times, by leaching with sulfuric acid and germanium separation by z. B. Wood extract precipitation.
- Ge concentrate production is very often carried out via intermediate products of metal extraction. Their composition and ge content can only be controlled to a limited extent. Many enrichment steps are required to produce a Ge concentrate with 10 to 20% Ge.
- the object of the present invention is to propose a method which, in a very simple and direct manner, makes it possible to extract germanium from sulfidic concentrates.
- germanium-containing sulfidic concentrate is mixed with such an amount of soda that the sulfur content is bound as sulfate and then the concentrate is roasted under oxidic conditions, the roasted material is leached with sulfuric acid and germanium is precipitated from the solution.
- the mixture is roasted with sufficient air supply in the temperature range between 850 K and 1200 K, preferably at 1000 K.
- the roasted material can be subjected to comminution before the sulfuric acid leaching, and the sulfuric acid leaching is carried out at temperatures between 313 and 370 K and the amount of sulfuric acid is such that an H 2 to 4 concentration in the solution after the leaching at least 5 g / t is included.
- the process would be such that, for example, a copper concentrate with a certain low content of germanium is mixed with a soda amount sufficient to bind the sulfur of the concentrate as sulfate and this mixture is then roasted under oxidizing conditions , whereby the metal sulfides pass into the oxides.
- a roasted product is formed which contains not only the sulfur but also the metals of the concentrate. This roasted material is leached with sulfuric acid, and so much sulfuric acid is added that a pH of approx. 1 is reached.
- Germanium goes into solution. Germanium can be obtained from the solution thus produced by a suitable precipitant, such as. B. the frequently used tannin can be precipitated. Small amounts of copper, arsenic, iron and zinc are also precipitated.
- the precipitation product is further processed into the actual germanium concentrate in a manner known per se by drying and annealing.
- sulfidic copper concentrate 100 parts of a sulfidic copper concentrate, approximately the following composition are mixed with a sufficient amount of soda (Na-CO-) and then roasted with air.
- the example shows that very little Ge was evaporated in this way of working.
- the roasted product thus produced is then leached in a ratio of solid: water like 1:10 after comminution and so much concentrated sulfuric acid is added that a pH of less than 1 is established at the end of the leaching.
- the leaching is preferably carried out at elevated temperatures, but can also be carried out at room temperature.
- the filtrate based on the amount used in the roasted material, contained 94% of the Ge of particular interest. The total yield of the solution was therefore 89% Ge.
- Ge is precipitated from this solution by adding a tannin solution.
- the precipitated tannate contained
- a concentrate was obtained by drying and annealing the tannate, the enthieit ⁇ This material corresponds to commercially available concentrates.
- Example 2 The same germanium-containing copper concentrate as in Example 1 was mixed with an amount of soda sufficient for binding sulfur and then roasted with air.
- the roast contained well As in Example 1, very little germanium was volatilized.
- the roasted product produced became a 1:10 ratio of solid: water after adding 40 ml of concentrated sulfuric acid per 100 g of roasted product.
- a fat product was produced from the clear solution in a manner known per se by adding a tannin solution contained.
- This material corresponds to commercially available Ge concentrate qualities that can be further processed using chlorine style tatton.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Gewinnung eines weiterverarbeitbaren Germaniumkonzentrats.The invention relates to a method for obtaining a processable germanium concentrate.
Germanium kommt als Begleitelement in Konzentrationen von wenigen ppm in einigen Lagerstätten sulfidischer Erze der Metalle Blei, Kupfer und Zink vor. Bekannte Ge-Mineralien sind z. B. Argyrodit, Canfieldit, Germanit und Renierit. Bei der Aufarbeitung der Roherze werden die Germaniumminerale zusammen mit den Sulfiden der Hauptmetalle Blei, Zink und Kupfer in Konzentraten angereichert.Germanium occurs as an accompanying element in concentrations of a few ppm in some deposits of sulfidic ores of the metals lead, copper and zinc. Known Ge minerals are e.g. B. argyrodite, canfieldite, germanite and renierite. When processing the raw ores, the germanium minerals are concentrated in concentrates together with the sulfides of the main metals lead, zinc and copper.
Die Anreicherung des Germaniums erreicht nur bei einigen wenigen besonders Ge-reichen Roherzen so hohe Werte in den Konzentraten, daß eine direkte Ge-Abtrennung aus den Konzentraten technisch möglich und wirtschaftlich vertretbar ist.The concentration of germanium only reaches such high values in the concentrates in a few particularly rich crude ores that a direct separation of the ge from the concentrates is technically possible and economically justifiable.
So sind Verfahren bekannt, aus sulfidischen Blei- und/oder Kupferkonzentraten mit Ge-Gehalten von 0,2 bis 0, % das Germanium als Sulfid unter neutralen oder schwach reduzierenden Bedingungen bei Atmosphärendruck zu sublimieren.Methods are known for subliming the germanium as sulfide from sulfidic lead and / or copper concentrates with Ge contents of 0.2 to 0% under neutral or weakly reducing conditions at atmospheric pressure.
Aus dem Abgas wird Germanium sulfidisch ebenfalls in nicht oxidierender Atmosphäre kondensiert und abgeschieden. Zusammen mit dem Germaniumsulfid werden Arsenverbindungen und je nach angewandter Temperatur auch PbS mit sublimiert. In den meisten Blei-, Zink- und Kupferkonzentraten sind die Germaniumgehalte jedoch so niedrig, daß eine Ge-Anreicherung und Abtrennung aus dem Konzentrat heraus nicht in Frage kommt. Häufig reichert sich das Germanium in Zwischen- oder Abfallprodukten der Prozesse zur Gewinnung der Hauptmetalle an.Germanium is also sulfidically condensed and separated from the exhaust gas in a nonoxidizing atmosphere. Together with the germanium sulfide, arsenic compounds and, depending on the temperature used, PbS are also sublimed. In most lead, zinc and copper concentrates, however, the germanium contents are so low that Ge enrichment and separation from the concentrate are out of the question. Germanium often accumulates in intermediate or Waste products from the processes for extracting the main metals.
So ist z. B. bekannt, daß beim Verschmelzen Ge-haltiger Kupferkonzentrate im Flammofen sich Germanium in den Flugstäuben auf Gehalte von z_ B. 0,2 bis 0,4 % anreichert. In diesen Flugstäuben sind daneben noch die Elemente Kupfer, Arsen, Eisen, Zink, Blei, Schwefel und andere enthalten. Aus solchen Flugstäuben kann Germanium dann durch schwefelsaures oder salzsaures Laugen herausgelöst werden= Mit in Lösung gehen ein Großteil der Begleitmetalle. Aus den Lösungen kann nach eventuell vorheriger Abtrennung von Kupfer, Arsen und Eisen das Germanium in an sich bekannter Weise durch Zugabe von Holzextrakten, wie z. B. Tannin, gefällt werden.So z. For example, it is known that when Ge-containing copper concentrates are melted in the flame furnace, germanium accumulates in the flue dust to contents of, for example, 0.2 to 0.4%. These flue dusts also contain the elements copper, arsenic, iron, zinc, lead, sulfur and others. Germanium can then be removed from such dusts by sulfuric acid or hydrochloric acid lye = a large part of the accompanying metals also go into solution. After any previous separation of copper, arsenic and iron, the germanium can be removed from the solutions in a manner known per se by adding wood extracts, such as. B. tannin.
Die so erzeugten Ge-Konzentrate mit z. B. 6 bis 20 % Ge-Gehalt steHen:einen üblichen handelsfähigen Rohstoff dar. Aus ihm wird z. B. durch ChtoriddestHtation CeCL abdestilliert und abgetrennt.The Ge concentrates so produced with z. B. 6 to 20% Ge content: a common tradable raw material. B. distilled and separated by ChtoriddestHtation CeCL.
Bei dem heute am stärksten verbreiteten Verfahren der hydrometallurgisch-elektrolytischen Zinkgewinnung bleibt das Germanium, wie man festgestellt hat, zu über 90 % im Laugungsrückstand. In einigen Hütten werden diese Rückstände thermisch aufgearbeitet und bevorzugt Blei und Zink, sofern interessant, auch das Germanium verflüchtigt und in einem Flugstaub angereichert.In the most widespread method of hydrometallurgical-electrolytic zinc production today, more than 90% of the germanium remains in the leaching residue. In some smelters, these residues are thermally processed and lead and zinc, if interesting, also volatilize the germanium and accumulate in a dust.
Die erzeugten Flugstäube enthalten neben den Hauptbestandteilen Bleioxid und Zinkoxid noch andere leicht verflüchtigbare Metallverbindungen, wie i- B. solche des Arsens, Antimons, Cadmiums und Germaniums_ Solche Flugstäube werden häufig neben geröstesten Zinkerzen bei der hydronteta!turgisch-e!ektro!ytischen Zinkgewinnung eingesetzt. Die Ftugstäube werden schwefelsauer gelaugt und aus den Lösungen wird Germanium gefällt und angereichert.The fly ash generated in addition to the main components of lead oxide and zinc oxide are other volatilizable metal compounds such as i - for example, those of arsenic, antimony, cadmium and Germaniums_ Such flue dusts are next geröstesten zinc ores in hydronteta turgisch-e often Ektro used ytischen zinc recovery! . The dust is leached with sulfuric acid, and germanium is precipitated and enriched from the solutions.
Beim Verhütten Ge-haltiger Bleikonzentrate, wie sie z. B. in Tsumeb/Namibia gefunden werden, geht Germanium in die Endschlacken der Bleireduktion. Aus ihnen kann Germanium, zusammen mit Blei und Zink, durch einen Schlackeverblaseprozeß verflüchtigt und nach Oxidation und Kondensation in einem Flugstaub angereichert und abgetrennt werden. Die weitere Aufkonzentrierung des Germaniums erfolgt dann, wie bereits mehrfach erwähnt, durch Laugung mit Schwefelsäure und Germaniumabtrennung durch z. B. Holzextraktfällung.When smelting Ge-containing lead concentrates such as z. B. found in Tsumeb / Namibia, Germanium goes into the final slags of lead reduction. Germanium, together with lead and zinc, can be evaporated from them by a slag blowing process and, after oxidation and condensation, enriched and separated in a flying dust. The further concentration of germanium then takes place, as already mentioned several times, by leaching with sulfuric acid and germanium separation by z. B. Wood extract precipitation.
Wie aus dieser kurzen Beschreibung der angewandten Technik: zu ersehen ist, erfolgt die Ge-Konzentraterzeugung sehr häufig über Zwischenprodukte der Metallgewinnung. Deren Zusammensetzung und Ge-Inhalte sind nur begrenzt steuerbar. Es sind viele Anreicherungsschritte zur Erzeugung eines Ge-Konzentrats mit 10 bis 20 % Ge notwendig.As can be seen from this brief description of the technology used: Ge concentrate production is very often carried out via intermediate products of metal extraction. Their composition and ge content can only be controlled to a limited extent. Many enrichment steps are required to produce a Ge concentrate with 10 to 20% Ge.
Aufgabe der vorliegenden Erfindung ist es nun, demgegenüber ein Verfahren vorzuschlagen, welches in einer sehr einfachen und direkten Weise ermöglicht, Germanium aus sulfidischen Konzentraten zu erschließen.The object of the present invention is to propose a method which, in a very simple and direct manner, makes it possible to extract germanium from sulfidic concentrates.
Gelöst wird diese Aufgabe dadurch, daß das germaniumhaltige sulfidische Konzentrat mit einer solchen Menge Soda versetzt wird, daß der Schwefelinhalt als Sulfat gebunden wird und anschließend das Konzentrat unter oxidischen Bedingungen geröstet, das Röstgut schwefelsauer gelaugt und Germanium aus der Lösung gefällt wird.This object is achieved in that the germanium-containing sulfidic concentrate is mixed with such an amount of soda that the sulfur content is bound as sulfate and then the concentrate is roasted under oxidic conditions, the roasted material is leached with sulfuric acid and germanium is precipitated from the solution.
Die Röstung des Gemisches erfolgt bei ausreichender Luftzufuhr im Temperaturbereich zwischen 850 K und 1200 K, vorzugsweise bei 1000 K.The mixture is roasted with sufficient air supply in the temperature range between 850 K and 1200 K, preferably at 1000 K.
In Verfolg des Erfindungsgedankens kann das Röstgut vor der schwefefsauren Laugung einer Zerkleinerung unterworfen werden, und die schwefelsaure Laugung wird bei Temperaturen zwischen 313 bis 370 K durchgeführt und die Schwefelsäuremenge so bemessen, daß nach der Laugung in der Lösung eine H 2so 4-Konzentration von mindestens 5 g/t enthalten ist.Following the concept of the invention, the roasted material can be subjected to comminution before the sulfuric acid leaching, and the sulfuric acid leaching is carried out at temperatures between 313 and 370 K and the amount of sulfuric acid is such that an H 2 to 4 concentration in the solution after the leaching at least 5 g / t is included.
In Verfolg des Erfindungsgedankens würde sich das Verfahren etwa so darstellen, daß man beispielsweise ein Kupferkonzentrat mit einem bestimmten geringen Gehalt an Germanium mit einer Sodamenge vermischt, die ausreichend ist, um den Schwefel des Konzentrats als Sulfat zu binden und dieses Gemisch anschließend unter oxidierenden Bedingungen röstet, wobei die Metallsulfide in die Oxide übergehen. Es entsteht ein Röstgut, welches neben dem Schwefel auch die Metalle des Konzentrats enthält. Dieses Röstgut wird schwefelsauer gelaugt, und mit so viel Schwefelsäure versetzt, daß ein pH-Wert von ca. 1 erreicht wird. Dabei geht Germanium in Lösung. Aus der so erzeugten Lösung kann Germanium durch ein geeignetes Fällmittel, wie z. B. das häufig angewandte Tannin, ausgefällt werden. Dabei werden auch geringe Mengen von Kupfer, Arsen, Eisen und Zink mit gefällt. Die Weiterverarbeitung des Fällprodukts zum eigentlichen Germaniumkonzentrat erfolgt in an sich bekannter Weise durch Trocknen und Glühen.Following the idea of the invention, the process would be such that, for example, a copper concentrate with a certain low content of germanium is mixed with a soda amount sufficient to bind the sulfur of the concentrate as sulfate and this mixture is then roasted under oxidizing conditions , whereby the metal sulfides pass into the oxides. A roasted product is formed which contains not only the sulfur but also the metals of the concentrate. This roasted material is leached with sulfuric acid, and so much sulfuric acid is added that a pH of approx. 1 is reached. Germanium goes into solution. Germanium can be obtained from the solution thus produced by a suitable precipitant, such as. B. the frequently used tannin can be precipitated. Small amounts of copper, arsenic, iron and zinc are also precipitated. The precipitation product is further processed into the actual germanium concentrate in a manner known per se by drying and annealing.
Das Verfahren wird nun anhand zweier Beispiele ausführlicher beschrieben.The method will now be described in more detail using two examples.
100 Teile eines sulfidischen Kupferkonzentrats, etwa der folgenden Zusammensetzung
Eine Analyse des Röstguts ergab, daß es von den wichtigen Elementen 99, % Cu, 95 % Ge und 100 % Fe vom Einsatz enthielt.Analysis of the roast showed that it contained 99% of the important elements, Cu, 95% Ge and 100% Fe from use.
Das Beispiel zeigt, daß bei dieser Arbeitsweise nur sehr wenig Ge verflüchtigt wurde. Das so erzeugte Röstgut wird nun im Verhältnis Feststoff : Wasser wie 1 : 10 nach einer Zerkleinerung gelaugt und dabei so viel konzentrierte Schwefelsäure zugesetzt, daß sich am Ende der Laugung ein pH-Wert von kleiner als 1 einstellt.The example shows that very little Ge was evaporated in this way of working. The roasted product thus produced is then leached in a ratio of solid: water like 1:10 after comminution and so much concentrated sulfuric acid is added that a pH of less than 1 is established at the end of the leaching.
Die Laugung erfolgt vorzugsweise bei erhöhten Temperaturen, kann aber auch bei Raumtemperatur vorgenommen werden. Nach einer Fest/Flüssig-Trennung enthielt das Filtrat, bezogen auf die Einsatzmenge im Röstgut, an dem hier besonders interessierenden Ge 94 %. Die Gesamtausbringung der Lösung betrug demnach 89 % Ge. Aus dieser Lösung wird Ge durch Zugabe einer Tanninlösung ausgefällt. Das ausgefällte Tannat enthielt
Durch Trocknen und Glühen des Tannats wurde ein Konzentrat erhalten, das
Dasselbe germaniumhaltige Kupferkonzentrat wie im Beispiel 1 wurde mit einer für die Schwefelbindung ausreichenden Sodamenge vermischt und danach unter Luftzufuhr geröstet.The same germanium-containing copper concentrate as in Example 1 was mixed with an amount of soda sufficient for binding sulfur and then roasted with air.
Das Röst gut enthielt
Die nach einer Fest-Flüssig-Trennung gewonnene Lösung enthielt, bezogen auf die Einsatzmengen im Röstgut
- 91 % Ge. Das Gesamtausbringen in der Lösung betrug demnach ca. 89 % Ge.
- 91% Ge. The total yield in the solution was therefore about 89% Ge.
Das im Vergleich zu Beispiel 1 geringere Kupferausbringen wird auf den vergleichsweise niedrigeren Schwefelsäureeinsatz beim Laugen zurückgeführt.The lower copper yield compared to example 1 is attributed to the comparatively lower use of sulfuric acid in the lye.
Aus der klaren Lösung wurde in an sich bekannter Weise durch Zugabe einer Tanninlösung ein Fätfprodukt erzeugt, das
Nach Verglühen dieses Produkts reichern sich die Metalle an auf
Dieses Material entspricht handelsüblichen und durch Chlordestiltatton weiter verarbeitbaren Ge-Konzentrat-Qualitäten.This material corresponds to commercially available Ge concentrate qualities that can be further processed using chlorine style tatton.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT84114333T ATE51898T1 (en) | 1984-05-23 | 1984-11-27 | PROCESS FOR OBTAINING A PROCESSABLE GERMANIUM CONCENTRATE. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3419120 | 1984-05-23 | ||
| DE3419120A DE3419120C1 (en) | 1984-05-23 | 1984-05-23 | Process for obtaining a germanium concentrate that can be processed |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0162954A2 true EP0162954A2 (en) | 1985-12-04 |
| EP0162954A3 EP0162954A3 (en) | 1988-03-16 |
| EP0162954B1 EP0162954B1 (en) | 1990-04-11 |
Family
ID=6236589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84114333A Expired - Lifetime EP0162954B1 (en) | 1984-05-23 | 1984-11-27 | Process for obtaining a germanium concentrate |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0162954B1 (en) |
| AT (1) | ATE51898T1 (en) |
| DE (2) | DE3419120C1 (en) |
| ZA (1) | ZA849151B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006033535A1 (en) * | 2004-09-20 | 2006-03-30 | Seung, Keun Ku | Method of manufacturing germanium-containing solution from yellow soil |
| CN101638725A (en) * | 2009-08-14 | 2010-02-03 | 扬州宁达贵金属有限公司 | Method for enriching germanium concentrates from low-germanium coal dust |
| CN116875826A (en) * | 2023-09-07 | 2023-10-13 | 昆明理工大学 | Method for extracting germanium by zinc oxide smoke depth and short process |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102191391B (en) * | 2010-03-02 | 2013-08-21 | 南华茂森综合利用有限责任公司 | Method for extracting germanium from high-impurity low-grade complex zinc oxide powder |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1082311A (en) * | 1952-08-18 | 1954-12-28 | Zh Sekitan Sogo Kenkyujo | Germanium recovery process |
| US2827369A (en) * | 1953-12-23 | 1958-03-18 | Metallurg De Hoboken Soc Gen | Method of separating germanium from primary materials containing germanium and other, less volatile, elements |
| DE1067221B (en) * | 1959-10-15 | Siemens & Halske Aktiengesellschaft, Berlin und München | Process for the production of germanium for directional conductors, transistors or the like | |
| GB865306A (en) * | 1959-06-25 | 1961-04-12 | Charles Lilley Horn | Metal recovery process |
| DE1163787B (en) * | 1960-01-16 | 1964-02-27 | Ledoga Spa | Process for the production of germanium from its acidic solutions |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1184088B (en) * | 1964-03-10 | 1964-12-23 | Stolberger Zink Ag | Process for the extraction of non-ferrous heavy metals |
-
1984
- 1984-05-23 DE DE3419120A patent/DE3419120C1/en not_active Expired
- 1984-11-23 ZA ZA849151A patent/ZA849151B/en unknown
- 1984-11-27 AT AT84114333T patent/ATE51898T1/en not_active IP Right Cessation
- 1984-11-27 EP EP84114333A patent/EP0162954B1/en not_active Expired - Lifetime
- 1984-11-27 DE DE8484114333T patent/DE3481922D1/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1067221B (en) * | 1959-10-15 | Siemens & Halske Aktiengesellschaft, Berlin und München | Process for the production of germanium for directional conductors, transistors or the like | |
| FR1082311A (en) * | 1952-08-18 | 1954-12-28 | Zh Sekitan Sogo Kenkyujo | Germanium recovery process |
| US2827369A (en) * | 1953-12-23 | 1958-03-18 | Metallurg De Hoboken Soc Gen | Method of separating germanium from primary materials containing germanium and other, less volatile, elements |
| GB865306A (en) * | 1959-06-25 | 1961-04-12 | Charles Lilley Horn | Metal recovery process |
| DE1163787B (en) * | 1960-01-16 | 1964-02-27 | Ledoga Spa | Process for the production of germanium from its acidic solutions |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006033535A1 (en) * | 2004-09-20 | 2006-03-30 | Seung, Keun Ku | Method of manufacturing germanium-containing solution from yellow soil |
| CN101638725A (en) * | 2009-08-14 | 2010-02-03 | 扬州宁达贵金属有限公司 | Method for enriching germanium concentrates from low-germanium coal dust |
| CN101638725B (en) * | 2009-08-14 | 2014-05-07 | 扬州宁达贵金属有限公司 | Method for enriching germanium concentrates from low-germanium coal dust |
| CN116875826A (en) * | 2023-09-07 | 2023-10-13 | 昆明理工大学 | Method for extracting germanium by zinc oxide smoke depth and short process |
| CN116875826B (en) * | 2023-09-07 | 2023-11-14 | 昆明理工大学 | Method for extracting germanium by zinc oxide smoke depth and short process |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3481922D1 (en) | 1990-05-17 |
| EP0162954B1 (en) | 1990-04-11 |
| ATE51898T1 (en) | 1990-04-15 |
| ZA849151B (en) | 1985-07-31 |
| DE3419120C1 (en) | 1985-10-10 |
| EP0162954A3 (en) | 1988-03-16 |
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