EP0162954B1 - Process for obtaining a germanium concentrate - Google Patents

Process for obtaining a germanium concentrate Download PDF

Info

Publication number
EP0162954B1
EP0162954B1 EP84114333A EP84114333A EP0162954B1 EP 0162954 B1 EP0162954 B1 EP 0162954B1 EP 84114333 A EP84114333 A EP 84114333A EP 84114333 A EP84114333 A EP 84114333A EP 0162954 B1 EP0162954 B1 EP 0162954B1
Authority
EP
European Patent Office
Prior art keywords
germanium
sulfuric acid
concentrate
solution
sulphur
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
Application number
EP84114333A
Other languages
German (de)
French (fr)
Other versions
EP0162954A2 (en
EP0162954A3 (en
Inventor
Lothar Dipl.-Ing. Leder
Kunibert Dr.-Ing. Hanusch
Hans-Joachim Müller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Preussag AG Metall
Original Assignee
Preussag AG Metall
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Preussag AG Metall filed Critical Preussag AG Metall
Priority to AT84114333T priority Critical patent/ATE51898T1/en
Publication of EP0162954A2 publication Critical patent/EP0162954A2/en
Publication of EP0162954A3 publication Critical patent/EP0162954A3/en
Application granted granted Critical
Publication of EP0162954B1 publication Critical patent/EP0162954B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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. Argyrodite, canfieldite, germanite and renierite. During processing of the raw ores, the germanium minerals are concentrated 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 non-oxidizing 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. The germanium often accumulates in intermediate or waste products from the processes for extracting the main metals.
  • germanium in the flue dust contains e.g. Enriched 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 leaching with sulfuric or hydrochloric acid. The majority of the accompanying metals go with the solution. After prior separation of copper, arsenic and iron, the germanium can be removed from the solutions in a manner known per se by adding wood extracts, e.g. Tannin, to be felled.
  • wood extracts e.g. Tannin
  • the Ge concentrates produced in this way for example having a Ge content of 6 to 20%, are a common commercially available raw material.
  • GeC1 4 is distilled off from it and separated off, for example by chloride distillation.
  • the fly dusts generated also contain other volatile metal compounds, such as those of arsenic, antimony, cadmium and germanium. Such dusts are often used in addition to roasted zinc ores in hydrometallurgical-electrolytic zinc production. The dusts are leached with sulfuric acid and germanium is precipitated and enriched from the solutions.
  • Germanium When smelting Ge-containing lead concentrates, e.g. found in Tsumeb / Sun, 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 Germanium is then further concentrated, as already mentioned several times, by leaching with sulfuric acid and separating germanium by e.g. Wood extract precipitation.
  • Ge concentrate production is very often carried out via intermediate products of metal extraction. Their composition and ge content are only controllable to a limited extent. Many enrichment steps are necessary 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 oxidizing 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 to 370 K and the amount of sulfuric acid is such that after the leaching in the solution an H Z S0 4 concentration of at least 5 g / l of free H 2 S0 4 is contained.
  • the process would be approximately such that, for example, in copper concentrate with a certain low content of germanium, it is mixed with a quantity of soda 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 created, which in addition to the sulfur contains 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 precipitated from the solution produced in this way using a suitable precipitant, such as the frequently used tannin. 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 ash (Na 2 C0 3 ) 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 here. 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 contained. 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 toasted contained
  • Example 2 As in Example 1, very little germanium was volatilized. The roasted product produced was leached in a solid: water ratio of 1:10 after the addition of 40 ml concentrated sulfuric acid per 100 g roasted product.
  • a precipitate was produced from the clear solution in a manner known per se by adding a tannin solution contained.
  • This material corresponds to standard Ge concentrate qualities that can be further processed by chlorine distillation.

Landscapes

  • 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

1. Process for obtaining an upgradable germanium concentrate from sulphur-containing metal concentrates in which the sulphur-containing concentrate is treated with a quantity of soda such that the sulphur content is fixed as sulfate, and is subsequently roasted under oxidizing conditions, the product of roasting leached with sulfuric acid, and germanium precipitated from the solution.

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 Konzentration 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. Argyrodite, canfieldite, germanite and renierite. During processing of the raw ores, the germanium minerals are concentrated 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 0,4% 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 0.4% 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 non-oxidizing 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. The 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 Gehalt 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.For example, It is known that when Ge-containing copper concentrates are melted together in the flame furnace, germanium in the flue dust contains e.g. Enriched 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 leaching with sulfuric or hydrochloric acid. The majority of the accompanying metals go with the solution. After prior separation of copper, arsenic and iron, the germanium can be removed from the solutions in a manner known per se by adding wood extracts, e.g. Tannin, to be felled.

Die so erzeugten Ge-Konzentrate mit z.B. 6 bis 20% Ge-Gehalt stellen einen üblichen handelsfähigen Rohstoff dar. Aus ihm wird z.B. durch Chloriddestillation GeC14 abdestilliert und abgetrennt.The Ge concentrates produced in this way, for example having a Ge content of 6 to 20%, are a common commercially available raw material. GeC1 4 is distilled off from it and separated off, for example by chloride distillation.

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 z.B. solche des Arsens, Antimons, Cadmiums und Germaniums. Solche Flugstäube werden häufig neben geröstesten Zinkerzen bei der hydrometallurgisch-elektrolytischen Zinkgewinnung eingesetzt. Die Flugstäube werden schwefelsauer gelaugt und aus den Lösungen wird Germanium gefällt und angereichert.In addition to the main constituents of lead oxide and zinc oxide, the fly dusts generated also contain other volatile metal compounds, such as those of arsenic, antimony, cadmium and germanium. Such dusts are often used in addition to roasted zinc ores in hydrometallurgical-electrolytic zinc production. The dusts are 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, e.g. 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 Germanium is then further concentrated, as already mentioned several times, by leaching with sulfuric acid and separating germanium by e.g. 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 steuerbare. 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 are only controllable to a limited extent. Many enrichment steps are necessary 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 oxidierenden Bedingungen geröstet, das Röstgut mit Schwefelsäure 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 oxidizing 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 schwefelsauren Laugung einer Zerkleinerung unterworfen werden, und die schwefelsäure Laugung wird bei Temperaturen zwischen 313 bis 370 K durchgeführt und die Schwefelsäuremenge so bemessen, daß nach der Laugung in der Lösung eine HZS04-Konzentration von mindestens 5 g/I freier H2S04 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 to 370 K and the amount of sulfuric acid is such that after the leaching in the solution an H Z S0 4 concentration of at least 5 g / l of free H 2 S0 4 is contained.

In Verfolg des Erfindungsgedankens würde sich das Verfahren etwa so darstellen, daß man beispielsweise in 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 beakannter Weise durch Trocknen und Glühen.Following the idea of the invention, the process would be approximately such that, for example, in copper concentrate with a certain low content of germanium, it is mixed with a quantity of soda 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 created, which in addition to the sulfur contains 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 precipitated from the solution produced in this way using a suitable precipitant, such as the frequently used tannin. 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.

Beispiel 1example 1

100 Teile eines sulfidischen Kupferkonzentrats, etwa der folgenden Zusammensetzung

Figure imgb0001
werden mit einer für die Schwefelbindung ausreichenden Menge Soda (Na2C03) vermischt und danach unter Luftzufuhr geröstet.100 parts of a sulfidic copper concentrate, approximately the following composition
Figure imgb0001
 are mixed with a sufficient amount of soda ash (Na 2 C0 3 ) and then roasted with air.

Eine Analyse des Röstguts ergab, daß es von den wichtigen Elementen 99,4% Cu, 95% Ge und 100% Fe vom Einsatz enthielt.An analysis of the roast showed that it contained 99.4% Cu, 95% Ge and 100% Fe of the key elements.

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 enthieltThe leaching is preferably carried out at elevated temperatures, but can also be carried out at room temperature. After a solid / liquid separation, the filtrate, based on the amount used in the roasted material, contained 94% of the Ge of particular interest here. 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

Figure imgb0002
Durch Trocknen und Glühen des Tannats wurde ein Konzentrat erhalten, das
Figure imgb0003
enthielt. Dieses Material entspricht handelsüblichen Konzentraten.
Figure imgb0002
 A concentrate was obtained by drying and annealing the tannate, the
Figure imgb0003
 contained. This material corresponds to commercially available concentrates.

Beispiel 2Example 2

Dasselbe germaniumhaltige Kupferkonzentrat wie im Beispiel 1 wurde mit einer für die Schwefelbindung ausreichenden Sodamenge vermischt und danach unter Luftzufuhr geröstet. Das Röstgut enthieltThe 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 toasted contained

Figure imgb0004
Figure imgb0004

Wie in Beispiel 1 wurde auch hier nur sehr wenig Germanium verflüchtigt. Das erzeugte Röstgut wurde im Verhältnis Feststoff: Wasser wie 1:10 nach Zugabe von 40 ml konzentrierter Schwefelsäure je 100 g Röstgut gelaugt.As in Example 1, very little germanium was volatilized. The roasted product produced was leached in a solid: water ratio of 1:10 after the addition of 40 ml concentrated sulfuric acid per 100 g roasted product.

Die nach einer Fest-Flüssig-Trennung gewonnene Lösung enthielt, bezogen auf die Einsatzmengen im RöstgutThe solution obtained after a solid-liquid separation contained, based on the amounts used in the roasted material

Figure imgb0005
Das Gesamtausbringen in der Lösung betrug demnach
Figure imgb0006
Figure imgb0005
 The total output in the solution was therefore
Figure imgb0006

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 Fällprodukt erzeugt, das

Figure imgb0007
enthielt.A precipitate was produced from the clear solution in a manner known per se by adding a tannin solution
Figure imgb0007
 contained.

Nach Verglühen dieses Produkts reichern sich die Metalle an auf

Figure imgb0008
After this product has burned up, the metals accumulate
Figure imgb0008

Dieses Material entspricht handelsüblichen und durch Chlordestillation weiter verarbeitbaren Ge-Konzentrat-Qualitäten.This material corresponds to standard Ge concentrate qualities that can be further processed by chlorine distillation.

Claims (4)

1. Process for obtaining an upgradable germanium concentrate from sulphur-containing metal concentrates in which the sulphur-containing concentrate is treated with a quantity of soda such that the sulphur content is fixed as sulfate, and is subsequently roasted under oxidizing conditions, the product of roasting leached with sulfuric acid, and germanium precipitated from the solution.
2. Process according to claim 1, characterized by the fact that the roasting of the mixture is carried out with an adequate air supply in the temperature range between 850 deg K and 1200 deg K, preferably at 1000 deg K.
3. Process according to claims 1 and 2, characterized in that the product of roasting is leached with sulfuric acid after having been crushed.
4. Process according to claims 1 to 3, characterized in that the leaching with sulfuric acid is carried out at a temperature ranging from 313 deg K to 370 deg K and that the amount of sulfuric acid is calculated so that after the leaching the concentration in free H2S04 in the solution is at least 5 g/l.
EP84114333A 1984-05-23 1984-11-27 Process for obtaining a germanium concentrate Expired - Lifetime EP0162954B1 (en)

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
DE3419120A DE3419120C1 (en) 1984-05-23 1984-05-23 Process for obtaining a germanium concentrate that can be processed
DE3419120 1984-05-23

Publications (3)

Publication Number Publication Date
EP0162954A2 EP0162954A2 (en) 1985-12-04
EP0162954A3 EP0162954A3 (en) 1988-03-16
EP0162954B1 true 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 (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102191391A (en) * 2010-03-02 2011-09-21 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

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100750351B1 (en) * 2004-09-20 2007-08-17 승근구 Method of manufacturing germanium-containing water from yellow soil
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
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

Family Cites Families (6)

* Cited by examiner, † Cited by third party
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
DE1184088B (en) * 1964-03-10 1964-12-23 Stolberger Zink Ag Process for the extraction of non-ferrous heavy metals

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102191391A (en) * 2010-03-02 2011-09-21 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
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

Also Published As

Publication number Publication date
EP0162954A2 (en) 1985-12-04
ZA849151B (en) 1985-07-31
DE3481922D1 (en) 1990-05-17
DE3419120C1 (en) 1985-10-10
EP0162954A3 (en) 1988-03-16
ATE51898T1 (en) 1990-04-15

Similar Documents

Publication Publication Date Title
DE2540641C2 (en) Process for leaching residues containing zinc ferrite
DE69027437T2 (en) PREVENTION OF METALLURGICAL WASTE MATERIALS CONTAINING IRON COMPONENTS AND TOXIC ELEMENTS
DE2917751A1 (en) METHOD FOR THE EXTRACTION OF COPPER FROM HIGH-TOXIC, ARSEN-CONTAINING FLUE DUST FROM MELTING OVENS AND OR OR FROM REFINERY SLUDGE
DE2512180A1 (en) THERMAL PROCESSING PROCESS FOR LIQUID RESIDUE FROM WET METALLURGICAL ZINC EXTRACTION
EP0162954B1 (en) Process for obtaining a germanium concentrate
DE2038227C3 (en) Process for the preparation of ores and concentrates
DE3341154C2 (en)
DE2953802C1 (en) Process for the treatment of pyrite-containing polymetallic raw material
DE3402356C2 (en) Process for processing nickel-containing and vanadium-containing oil combustion residues
DE2707578A1 (en) Winning copper and other nonferrous metals from ores - using flame smelter followed by electric redn. furnace and converter
DE3615437C2 (en) Process for the production of high-purity molybdenum trioxide from contaminated raw materials
DE2000085C3 (en) Process for the gradual fluidized bed roasting of sulphidic iron materials
DE583380C (en) Process and device for pyrite melting
DE275904C (en)
DE836403C (en) Process and furnace for extracting lead
DE2023098A1 (en) Process for the selective separation and recovery of tin compounds
DE437891C (en) Process for separating pyrites containing zinc and iron into their constituent parts
DE3115272C2 (en) Process for the extraction of lead from concentrates containing lead sulphide
DE1792335C3 (en) Process for the preparation of iron sulphides
CH335859A (en) Process for the extraction of lead
DE463811C (en) Process for the direct production of brass from mixed copper-zinc-lead ores
DE3514717A1 (en) Process and apparatus for obtaining zinc oxides from fine granular sulphidic zinc concentrate by means of a pyrometallurgical smelting treatment
DE2618630A1 (en) Zinc extraction from zinc oxide and/or sulphide ores - by leaching and volatilising leach residue metals for max. recovery
DE310525C (en)
DE932521C (en) Process for the production of lead

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE DE FR IT NL

EL Fr: translation of claims filed
PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE DE FR IT NL

17P Request for examination filed

Effective date: 19880409

17Q First examination report despatched

Effective date: 19890626

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE FR IT NL

REF Corresponds to:

Ref document number: 51898

Country of ref document: AT

Date of ref document: 19900415

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3481922

Country of ref document: DE

Date of ref document: 19900517

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19931116

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19931125

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19931130

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19931206

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19941127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19941130

BERE Be: lapsed

Owner name: PREUSSAG A.G. METALL

Effective date: 19941130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19950601

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19950731

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20010921

Year of fee payment: 18

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030603