BE881273Q - LIQUID-LIQUID EXTRACTION PROCESS FOR GERMANIUM - Google Patents

LIQUID-LIQUID EXTRACTION PROCESS FOR GERMANIUM

Info

Publication number
BE881273Q
BE881273Q BE1/9688A BE1009688A BE881273Q BE 881273 Q BE881273 Q BE 881273Q BE 1/9688 A BE1/9688 A BE 1/9688A BE 1009688 A BE1009688 A BE 1009688A BE 881273 Q BE881273 Q BE 881273Q
Authority
BE
Belgium
Prior art keywords
emi
liquid
germanium
oxime
extraction
Prior art date
Application number
BE1/9688A
Other languages
French (fr)
Original Assignee
Metallurgie Hoboken
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 Metallurgie Hoboken filed Critical Metallurgie Hoboken
Priority to BE1/9688A priority Critical patent/BE881273Q/en
Application granted granted Critical
Publication of BE881273Q publication Critical patent/BE881273Q/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0492—Applications, solvents used
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G17/00—Compounds of germanium
    • C01G17/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/30—Oximes
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/40—Mixtures
    • C22B3/402—Mixtures of acyclic or carbocyclic compounds of different types
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Description

       

   <EMI ID=1.1> 

  
faible teneur en germanium. On obtient également des solutions de Ce impures partir des déchets de fabrications et sous-produits divers.

  
 <EMI ID=2.1> 

  
tions impures, consistant à précipiter le Ge sous forme de tannate ou

  
de sulfure au d'hydroxydes mixtes. Les précipités obtenus subissent

  
 <EMI ID=3.1> 

  
La présente invention décrit un procédé de séparation du Ge par extraction liquide-liquide, à partir de différentes solutions acides.

  
Il a, en effet, été trouvé que le Ge peut être extrait sélectivement en milieu acide au moyen d'un hydroxy-oxime et que la capacité d'extraction de cet extractant pour germanium augmente en fonction de l'acidité.

  
 <EMI ID=4.1> 

  
plus haute acidité leur pouvoir extractant pour cuivre est fortement réduit.

  
 <EMI ID=5.1> 

  
du Cu, peut donc être augmentée par le choix d'une acidité appropriée

  
de la solution aqueuse.

  
L'extractant a une très bonne sélectivité également par rapport à d'autres ions métalliques (seul le fer trivalent est partiellement

  
extrait en même temps).

  
Pour l'extraction du germanium à partir de solutions aqueuses

  
acides contenant des impuretés métalliques ou non métalliques on met

  
en contact, en co-courant ou en contre-courant, de manière répétitive

  
ou non, la solution aqueuse acide avec un liquide organique contenant

  
un hydroxy-oxime. 

  
 <EMI ID=6.1> 

  
d'acide fluorhydrique, ainsi que d'autres ions métalliques ou non-

  
 <EMI ID=7.1> 

  
ou par une solution d'un hydroxy-oxime dans un solvant aliphatique et ou un solvant aromatique, et éventuellement dans un alcool supérieur. 

  
 <EMI ID=8.1> 

  
oxime mis dans le commerce sous le nom déposé LIX-63 (fabrication de

  
 <EMI ID=9.1> 

  
particulièrement bien pour l'extraction de Ge.

  
Il a été constaté que des produits aliphatiques, tel que le kérozêne, sont bien indiqués comme solvants organiques pour diluer

  
 <EMI ID=10.1> 

Un alcool supérieur utilisé avantageusement est l'isodec&nol.

  
Les exemples cités plus loin indiquent que l'extraction simultanée du Cu est faible. Cependant, on peut éliminer au préalable le Cu, soit par cémentation sélective en milieu acide, soit par extraction sélective préalable, soit par toute autre méthode connue n'entraînant pas des pertes de Ce.

  
L'invention couvre également la ré-extraction du Ge à partir de la solution organique par de l'eau ou une solution acide ou alcaline. La précipitation directe du germanium dans la solution organique est également possible. On peut provoquer la précipitation du Ge par addi-

  
 <EMI ID=11.1> 

KOH. 

  
 <EMI ID=12.1> 

  
réutilisée pour une nouvelle extraction.

  
Au cas où l'on opère au déport avec des solutions contenant du Cu, ce dernier peut être réextrait après le germanium, au moyen d'une solution acide telle qu'une solution d'acide sulfuriqua.

  
La sélectivité de la séparation du Ge et du Cu peut donc être

  
 <EMI ID=13.1> 

  
qu'à la ré-extraction.

Exemple 1

  

 <EMI ID=14.1> 


  
Extraction :

  
 <EMI ID=15.1> 

  

 <EMI ID=16.1> 


  
Nombre d'étages d'extraction : 7. 

  

 <EMI ID=17.1> 


  
Rendement: d'extraction du Ge : 99,968 %

  
Elution en deux étapes :

  
 <EMI ID=18.1> 

  

 <EMI ID=19.1> 


  
nombre d'étages d'élution : 2

  

 <EMI ID=20.1> 
 

Exemple 2

  

 <EMI ID=21.1> 


  
Extraction .

  
 <EMI ID=22.1> 

  

 <EMI ID=23.1> 


  
Nombre d'étages : 7

  

 <EMI ID=24.1> 


  
 <EMI ID=25.1>  

Exemple 3

  

 <EMI ID=26.1> 


  
Extraction :

  
 <EMI ID=27.1> 

  

 <EMI ID=28.1> 


  
Nombre d'étages : 4

  

 <EMI ID=29.1> 


  
 <EMI ID=30.1>  

REVENDICATIONS

  
1. Procédé d'extraction liquide-liquide du germanium à partir d'une solution acide aqueuse, caractérisé en ce qu'on utilise comme extradant: un liquide organique contenant un hydroxy-oxime.



   <EMI ID = 1.1>

  
low germanium content. Solutions of this impure are also obtained from manufacturing wastes and various by-products.

  
 <EMI ID = 2.1>

  
impure tions, consisting of precipitating Ge in the form of tannate or

  
sulfide with mixed hydroxides. The precipitates obtained undergo

  
 <EMI ID = 3.1>

  
The present invention describes a process for the separation of Ge by liquid-liquid extraction, from different acid solutions.

  
It has in fact been found that Ge can be selectively extracted in an acid medium using a hydroxy-oxime and that the extraction capacity of this extractant for germanium increases as a function of the acidity.

  
 <EMI ID = 4.1>

  
higher acidity their extracting power for copper is greatly reduced.

  
 <EMI ID = 5.1>

  
Cu, can therefore be increased by choosing an appropriate acidity

  
of the aqueous solution.

  
The extractant also has very good selectivity compared to other metal ions (only trivalent iron is partially

  
extracted at the same time).

  
For the extraction of germanium from aqueous solutions

  
acids containing metallic or non-metallic impurities we put

  
in contact, co-current or counter-current, repeatedly

  
or not, the acidic aqueous solution with an organic liquid containing

  
a hydroxy oxime.

  
 <EMI ID = 6.1>

  
hydrofluoric acid, as well as other metal ions or not

  
 <EMI ID = 7.1>

  
or by a solution of a hydroxy-oxime in an aliphatic solvent and or an aromatic solvent, and optionally in a higher alcohol.

  
 <EMI ID = 8.1>

  
oxime put on the market under the registered name LIX-63 (manufacture of

  
 <EMI ID = 9.1>

  
particularly good for extracting Ge.

  
It has been found that aliphatic products, such as kerosene, are well indicated as organic solvents for diluting

  
 <EMI ID = 10.1>

A higher alcohol advantageously used is isodec & nol.

  
The examples cited below indicate that the simultaneous extraction of Cu is weak. However, the Cu can be eliminated beforehand, either by selective carburizing in an acid medium, or by prior selective extraction, or by any other known method which does not cause losses of Ce.

  
The invention also covers the re-extraction of Ge from the organic solution with water or an acid or alkaline solution. Direct precipitation of germanium in the organic solution is also possible. We can cause the precipitation of Ge by addi-

  
 <EMI ID = 11.1>

KOH.

  
 <EMI ID = 12.1>

  
reused for a new extraction.

  
If the operation is carried out with solutions containing Cu, the latter can be re-extracted after the germanium, by means of an acid solution such as a sulfuric acid solution.

  
The selectivity of the separation of Ge and Cu can therefore be

  
 <EMI ID = 13.1>

  
than re-extraction.

Example 1

  

 <EMI ID = 14.1>


  
Extraction:

  
 <EMI ID = 15.1>

  

 <EMI ID = 16.1>


  
Number of extraction stages: 7.

  

 <EMI ID = 17.1>


  
Yield: Ge extraction: 99.968%

  
Elution in two stages:

  
 <EMI ID = 18.1>

  

 <EMI ID = 19.1>


  
number of elution stages: 2

  

 <EMI ID = 20.1>
 

Example 2

  

 <EMI ID = 21.1>


  
Extraction.

  
 <EMI ID = 22.1>

  

 <EMI ID = 23.1>


  
Number of floors: 7

  

 <EMI ID = 24.1>


  
 <EMI ID = 25.1>

Example 3

  

 <EMI ID = 26.1>


  
Extraction:

  
 <EMI ID = 27.1>

  

 <EMI ID = 28.1>


  
Number of floors: 4

  

 <EMI ID = 29.1>


  
 <EMI ID = 30.1>

CLAIMS

  
1. A liquid-liquid extraction process for germanium from an aqueous acid solution, characterized in that an organic liquid containing a hydroxy-oxime is used as the extradant.

Claims (1)

2. Procédé selon la revendication 1, caractérisé en ce que la solution aqueuse contient de 10 à 500 g/1 d'acide sulfurique et/ou chlorhydrique. <EMI ID=31.1> 2. Method according to claim 1, characterized in that the aqueous solution contains from 10 to 500 g / 1 of sulfuric and / or hydrochloric acid. <EMI ID = 31.1> solution aqueuse contient de 10 à 100 g/1 d'acide fluorhydrique. aqueous solution contains 10 to 100 g / 1 hydrofluoric acid. 4. Procédé selon la revendication 1, caractérisé en ce qu'on 4. Method according to claim 1, characterized in that <EMI ID=32.1> <EMI ID = 32.1> 5. Procédé selon la revendication 1, caractérisé en ce qu'on utilise comme liquide organique une solution d'un hydroxy-oxime dans un solvant aliphatique et ou un solvant aromatique. 5. Method according to claim 1, characterized in that an organic solution is a solution of a hydroxy-oxime in an aliphatic solvent and or an aromatic solvent. 6. Procède selon la revendication 5, caractérise en ce qu'on 6. Method according to claim 5, characterized in that <EMI ID=33.1> <EMI ID = 33.1> 7. Procédé selon les revendications 5 ou 6, caractérisé en ce que 7. Method according to claims 5 or 6, characterized in that <EMI ID=34.1> <EMI ID = 34.1> oxime. oxime. 8. Procédé selon la revendication 6, caractérisé en ce que le liquide organique contient jusqu'à 10 % en volume d'un alcool supérieur. 8. Method according to claim 6, characterized in that the organic liquid contains up to 10% by volume of a higher alcohol. 9. Procédé selon la revendication 1, caractérisé en ce qu'on utilise comme hydroxy-oxime le 19-hydroxyhexatriaconta-9,28-diène-18oxime. 9. Method according to claim 1, characterized in that 19-hydroxyhexatriaconta-9,28-diene-18oxime is used as hydroxy-oxime. 10. Procédé selon la revendication 5, caractérise en ce qu'on utilise comme solvant aliphatique du kérosène. 11. Procédé selon la revendication 6, caractérisé en ce qu'on 10. Method according to claim 5, characterized in that kerosene is used as the aliphatic solvent. 11. Method according to claim 6, characterized in that <EMI ID=35.1> <EMI ID = 35.1> 12. Procédé selon la revendication 1, caractérisé en ce que la phase organique est régénérée par contact avec une base et réutilisée pour une nouvelle extraction. 12. Method according to claim 1, characterized in that the organic phase is regenerated by contact with a base and reused for a new extraction. 13. Procédé selon la revendication 12, caractérisé en ce qu'on 13. Method according to claim 12, characterized in that <EMI ID=36.1> <EMI ID = 36.1> chaux ou de magnésie, ou de 1* ammoniaque. lime or magnesia, or ammonia. 14. Procédé selon-la revendication 1, caractérisé en ce que la solution aqueuse contient du cuivre. 14. Method according to claim 1, characterized in that the aqueous solution contains copper. 15. Procédé selon la revendication 14, caractérisé en ce que la phase organique est régénérée d'abord par contact avec une base en vue d'en séparer le germanium et ensuite par contact avec une solution acide en vue d'en séparer le cuivre, et réutilisée pour une nouvelle extraction. 15. The method of claim 14, characterized in that the organic phase is regenerated first by contact with a base in order to separate the germanium therefrom and then by contact with an acid solution in order to separate the copper therefrom, and reused for a new extraction.
BE1/9688A 1980-01-22 1980-01-22 LIQUID-LIQUID EXTRACTION PROCESS FOR GERMANIUM BE881273Q (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
BE1/9688A BE881273Q (en) 1980-01-22 1980-01-22 LIQUID-LIQUID EXTRACTION PROCESS FOR GERMANIUM

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE881273 1980-01-22
BE1/9688A BE881273Q (en) 1980-01-22 1980-01-22 LIQUID-LIQUID EXTRACTION PROCESS FOR GERMANIUM

Publications (1)

Publication Number Publication Date
BE881273Q true BE881273Q (en) 1980-05-16

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ID=25659079

Family Applications (1)

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Country Status (1)

Country Link
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0046437A1 (en) * 1980-08-15 1982-02-24 SOCIETE MINIERE ET METALLURGIQUE DE PENARROYA Société anonyme dite: Process for the selective extraction of germanium
EP0068540A1 (en) * 1981-06-22 1983-01-05 METALLURGIE HOBOKEN-OVERPELT Société anonyme dite: Process for the recovery of germanium from an aqueous solution using an alpha-hydroxyoxime
EP0202833A3 (en) * 1985-05-16 1989-03-15 Imperial Chemical Industries Plc Composition and use of the composition for the extraction of metals from aqueous solutions
US6277300B1 (en) 1985-05-16 2001-08-21 Zeneca Limited Composition and use of composition for the extraction of metal values

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0046437A1 (en) * 1980-08-15 1982-02-24 SOCIETE MINIERE ET METALLURGIQUE DE PENARROYA Société anonyme dite: Process for the selective extraction of germanium
WO1982000664A1 (en) * 1980-08-15 1982-03-04 Miniere Metall Penarroya Process for selective extraction of germanium
EP0167414A1 (en) * 1980-08-15 1986-01-08 SOCIETE MINIERE ET METALLURGIQUE DE PENARROYA Société anonyme dite: Process for the selective extraction of germanium
EP0068540A1 (en) * 1981-06-22 1983-01-05 METALLURGIE HOBOKEN-OVERPELT Société anonyme dite: Process for the recovery of germanium from an aqueous solution using an alpha-hydroxyoxime
EP0202833A3 (en) * 1985-05-16 1989-03-15 Imperial Chemical Industries Plc Composition and use of the composition for the extraction of metals from aqueous solutions
US4978788A (en) * 1985-05-16 1990-12-18 Imperial Chemical Industries Plc Composition and use of the composition for the extraction of metals from aqueous solution
US6277300B1 (en) 1985-05-16 2001-08-21 Zeneca Limited Composition and use of composition for the extraction of metal values

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Legal Events

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RE Patent lapsed

Owner name: S.A. ACEC-UNION MINIERE N.V.

Effective date: 19930131