EP0000457B1 - Verfahren zur Gewinnung von Gallium mittels flüssig-flüssig Extraktion aus stark basischen Lösungen - Google Patents

Verfahren zur Gewinnung von Gallium mittels flüssig-flüssig Extraktion aus stark basischen Lösungen Download PDF

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Publication number
EP0000457B1
EP0000457B1 EP78400035A EP78400035A EP0000457B1 EP 0000457 B1 EP0000457 B1 EP 0000457B1 EP 78400035 A EP78400035 A EP 78400035A EP 78400035 A EP78400035 A EP 78400035A EP 0000457 B1 EP0000457 B1 EP 0000457B1
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Prior art keywords
organic phase
phase
gallium
aqueous
acid
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French (fr)
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EP0000457A1 (de
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Jacques Helgorsky
Alain Leveque
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Rhone Poulenc Specialites Chimiques
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Rhone Poulenc Specialites Chimiques
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • C01G15/003—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
    • C22B3/36—Heterocyclic compounds
    • C22B3/362—Heterocyclic compounds of a single type
    • C22B3/364—Quinoline
    • 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

Definitions

  • the present invention relates to an improvement to the liquid / liquid extraction process of gallium contained in basic aqueous solutions, in particular as described in French patent application No. 2,277,897 and its additions numbers 2,307,047, 2,307,882 and 2,365,641.
  • the acids used are preferably hydrochloric acid, sulfuric acid and nitric acid.
  • the concentration of the dilute aqueous acid solution is preferably between 0.2 M and 0.5 M.
  • the concentration of the more concentrated aqueous acid solution is generally preferably greater than 1.6 M; but, in the case where hydrochloric acid is used, the latter is preferably between 1.3 M and 2.2 M and more especially between 1.6 M and 1.8 M.
  • the acids used are preferably hydrochloric acid and hydrobromic acid.
  • the concentration of the concentrated solution is preferably between 5 M and 8 M and those of the diluted solution between 1.3 M and 2.2 M.
  • the acids used are preferably either sulfuric acid or nitric acid at a concentration greater than 1.6 M, or hydrochloric acid or hydrobromic acid at a concentration between 1.3 M and 2.2 Mr.
  • the organic solvents used in particular in these variants are the diluents used in liquid / liquid extraction. They can be used alone or as a mixture. Among these, there may be mentioned: aliphatic compounds such as for example heptane and petroleum fractions of the kerosene type; aromatic compounds such as, for example, benzene, toluene, xylene and cuts of the Solvesso type (trademark registered by the company Exxon) and finally the halogenated derivatives of these compounds such as, for example, chloroform and carbon tetrachloride.
  • aliphatic compounds such as for example heptane and petroleum fractions of the kerosene type
  • aromatic compounds such as, for example, benzene, toluene, xylene and cuts of the Solvesso type (trademark registered by the company Exxon)
  • the halogenated derivatives of these compounds such as, for example, chloroform and carbon tetrachloride.
  • the substituted hydroxyquinolines used are those which can extract the gallium by complexation, they must moreover be more soluble in the organic phase than in the aqueous phase.
  • Suitable substituted hydroxyquinolines are in particular those of general formula wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 identical or different are chosen from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, cycloaliphatic, aromatic radicals; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 cannot simultaneously represent H.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 cannot simultaneously represent H.
  • the preferred ⁇ -8-alkenyl hydroxy-quinolines have the general formula in which R 1 , R 2 , R 3 represent a hydrogen or an optionally substituted hydrocarbon group. Among these, we will use in particular those of general formula
  • the preferred 8-alkenyl hydroxy-8 quinolines have the general formula in which R 1 , R 2 , R 3 , R 4 , R 5 represent a hydrogen or an optionally substituted hydrocarbon group.
  • the hydroxyquinolines can be used alone or as a mixture.
  • the proportion of hydroxyquinoline substituted in the organic phase is not critical and can vary within wide limits. However, a proportion of between 1 and 50% by volume based on the organic phase is generally suitable, a proportion of between 6 and 12% being economically favorable.
  • the temperature is not a critical parameter, in order to obtain good results according to the method described in these applications, it is advantageous for the extraction step to be carried out at a fairly high temperature practically below 100 ° C. and preferably between 50 and 80 ° C.
  • the solutions generally treated are aluminate solutions of the Bayer process and particularly the so-called "decomposed" solutions which have a temperature close to 50 ° C. It turns out that this temperature, although less favorable than a higher temperature, is however sufficient to ensure satisfactory extraction yields; in addition, the solvent regeneration and gallium recovery step is carried out in such a way that the organic phase is treated in order to recover the gallium with an acid solution at a temperature lower than that of step d extraction and preferably near room temperature.
  • the sodium aluminate detergents of the Bayer process preferably treated according to this process generally have compositions corresponding to: so-called "decomposed" detergents generally having compositions such as:
  • the installations used according to this process are presented as follows: in a first extraction device, the sodium aluminate solution depleted in alumina is sent following its "decomposition" and the organic phase consisting of chosen complexing agent, of a solvent and optionally of bodies with an alcohol function and other solvating compounds; the gallium then passes for a large fraction in the organic phase, which fraction depends on the respective flow rates of the two liquids. Aluminum, sodium and certain impurities also pass into the organic phase.
  • the organic phase thus charged is brought into contact in a second extraction device with a first regeneration solution constituted by a strong dilute acid or by a strong concentrated complexing acid which in both cases leaves practically in this organic phase only the gallium; this organic phase is then treated in a third counter-current extraction device where the wire is brought into contact with a strong acid for the purpose of recovering the gallium, then undergoes washing with water before being recycled into the first extraction device; the steel solution having recovered the gallium is then treated in order to perfect its purification, then the gallium is extracted therefrom.
  • a first regeneration solution constituted by a strong dilute acid or by a strong concentrated complexing acid which in both cases leaves practically in this organic phase only the gallium
  • this organic phase is then treated in a third counter-current extraction device where the wire is brought into contact with a strong acid for the purpose of recovering the gallium, then undergoes washing with water before being recycled into the first extraction device; the steel solution having recovered the gallium is then treated in order to perfect its purification, then the gallium is extracted therefrom
  • One can also envisage a simpler industrial device but leading to a less purified gallium; such a type of device comprises a first extraction apparatus as described above, at the outlet of which a second regeneration is carried out in a second apparatus operating against the current, with a solution of strong acid, aluminum, sodium and gallium contained in the organic phase.
  • the alkyl radical R n comprises, in a preferred embodiment, from 5 to 20 carbon atoms.
  • the radical R is located in position 7 on the 8-hydroxy-quinoline ring and the preferred products used correspond to the general formula: in which n is preferably between 5 and 20.
  • the hydroxyquinolines according to this process allow an almost total and lossless extraction over time of the gallium present in very basic aqueous solutions and in particular sodium aluminate detergents of the Bayer process.
  • the Applicant has found that, although the essential cause of the degradation of the 8-hydroxy-quinolines is the very basic nature of the medium, the oxidation of these products by the oxygen in the air also leads to a certain degradation during prolonged use; this latter degradation affecting to various degrees the different types of hydroxy-8 quinolines that can be used.
  • the object of the present invention is to obviate this drawback.
  • the present invention relates to a liquid / liquid extraction process of the gallium contained in basic aqueous solutions by bringing the aqueous solution into contact with an organic phase mainly containing an organic solvent and at least one substituted hydroxyquinoline, characterized in that one operates under an inert atmosphere.
  • the inert atmosphere may in particular consist of an argon or nitrogen atmosphere.
  • the organic solvent used according to the method of the invention is chosen from the group consisting of aromatic and aliphatic hydrocarbons, halogenated or not.
  • the substituted hydroxyquinoline used according to the process of the invention extracts the gallium by complexation and is more soluble in the organic phase than in the aqueous phase.
  • the suitable substituted hydroxyquinolines are in particular those of general formula wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 identical or different are chosen from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, cycloaliphatic, aromatic radicals; R 1 , R 2 , R 3 , R 4 , R s , R 6 cannot simultaneously represent H.
  • R 1 , R 2 , R 3 , R 4 , R s , R 6 cannot simultaneously represent H.
  • the preferred ⁇ -alkenyl hydroxy-8 quinolines have the general formula: in which R 1 , R 2 , R 3 represent a hydrogen or an optionally substituted hydrocarbon group.
  • the preferred 8 hydroxy alkyl quinolines have the general formula
  • the preferred 8-alkenyl hydroxy-8 quinolines have the general formula in which R ,, R 2 , R 3 , R 4 , R s represent a hydrogen or an optionally substituted hydrocarbon group.
  • the hydroxyquinolines can be used alone or as a mixture.
  • the proportion of hydroxyquinoline substituted in the organic phase is not critical and can vary within wide limits. However, a proportion of between 1 and 50% by volume based on the organic phase is generally suitable, a proportion of between 6 and 12% being economically favorable.
  • a modifying agent chosen from the group comprising bodies with alcohol function and phosphoric esters.
  • the present invention also relates to a process for recovering gallium contained in basic aqueous solutions by liquid / liquid extraction, characterized in that the aqueous solution is brought into contact, under an inert atmosphere, with an organic phase containing mainly an organic solvent and at least one substituted hydroxyquinoline, the organic phase is separated from the aqueous phase, that at least once, on the one hand, the organic phase is brought into contact with a strong acid solution, and, on the other hand, the remaining organic phase is separated from the aqueous phase and then the gallium is recovered from the aqueous phase.
  • the present invention also relates to the recovery of gallium contained in basic aqueous solutions by liquid / liquid extraction by contacting the aqueous solution with an organic phase containing mainly an organic solvent and a substituted hydroxyquinoline, characterized in that the separation of the phase organic phase, and / or contacting the organic phase with a strong acid solution, and / or separating the remaining organic phase from the aqueous phase, and / or recovering gallium from the phase aqueous are carried out under an inert atmosphere.
  • the acid used is chosen from the group comprising hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid; its concentration in the regeneration step or steps of the gallium-laden solvent is that which has been noted above for the different variants of implementation of the process according to French patent applications numbers 2.277.897, 2.307.047, 2.307. 882 and 2.365.641.
  • a Bayer detergent of composition AI 2 0 3 : 82 g / I, Na 2 O: 185 g / I, Ga: 240 mg / I is stirred with an organic phase consisting of hydroxyquinoline in 10% solution in a mixture 90 -10 kerosene-decanol, the operation being carried out at 50 ° C in the open air or in a nitrogen atmosphere.
  • the hydroxyquinoline titer is analyzed by gas chromatography. in the organic phase. The results obtained are recorded in the following table which expresses the percentage loss of hydroxyquinoline.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (9)

1. Verfahren zur Flüssig-Flüssig-Extraktion von in wässrigen basischen Lösungen enthaltenem Gallium, bei dem die wässrige Lösung mit einer organischen Phase in Kontakt gebracht wird, die hauptsächlich ein orgaisches Lösungsmittel und mindestens ein substituiertes Hydroxychinolin der Formel
Figure imgb0019
enthält, in der R1, R2, R3, R4, R5 und R6 gleich oder unterschiedlich aus der Gruppe ausgewählt sind, die durch Wasserstoff und die Alkyl-, Alkenyl-, cycloaliphatischen und aromatischen Reste gebildet wird, wobei R,, R2, R3, R4, R5 und R, nicht gleichzeitig Wasserstoff darstellen können, dadurch gekennzeichnet, daß man unter einer inerten Atmosphäre arbeitet.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die inerte Atmosphäre durch Stickstoff oder Argon gebildet wird.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das organische Lösungsmittel aus der durch die aliphatischen und aromatischen, halogenierten oder nicht-halogenierten Kohlenwasserstoffe gebildeten Gruppe ausgewählt ist.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Hydroxychinolin aus der Gruppe ausgewählt ist, die die α-Alkenyl-8-hydroxychinoline der allgemeinen Formel
Figure imgb0020
in der R1, R2 und R3 Wasserstoff oder eine Kohlenwasserstoffgruppe darstellen, die β-Alkenyl-8-hydroxychinoline der Formel
Figure imgb0021
in der R1, R2, R3, R4 und R5 Wasserstoff oder eine Kohlenwasserstoffgruppe darstellen und die Alkyl-8-hydroxychinoline der Formel
Figure imgb0022
bei der n zwischen 5 und 20 liegt, umfasst.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Anteil des substituierten Hydroxychinolins in der organischen Phase zwischen 1 und 50 Vol%, bezogen auf die organische Phase, beträgt.
6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man der organischen Phase ein Modifizierungsmittel zugibt, das aus der Gruppe ausgewählt ist, die Verbindungen mit einer Alkoholfunktion und Phosphorsäureester umfasst.
7. Verfahren zur Rückgewinnung von Gallium, das in wässrigen basischen Lösungen enthalten ist durch eine Flüssig/Flüssig-Extraktion nach Anspruch 1, dadurch gekennzeichnet, daß man in einer inerten Atmosphäre die wässrige Lösung mit einer organischen Phase in Kontakt bringt, die hauptsächlich ein organisches Lösungsmittel und mindestens ein substituiertes Hydroxychinolin enthält, daß man die Trennung der organischen Phase von der wässrigen Lösung mindestens einmal durchführt, wobei man zum einen die organische Phase mit einer Lösung einer starken Säure in Kontakt bringt und zum anderen die restliche organische Phase von der wässrigen Phase trennt und anschließend das Gallium aus der wässrigen Phase zurückgewinnt.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß man die Trennung der organischen Phase von der wässrigen Phase und/oder das Inkontaktbringen der organischen Phase mit einer Lösung einer starken Säure und/oder die Trennung der restlichen organischen Phase von der wässrigen Lösung und/oder die Rückgewinnung des Galliums aus der wässrigen Phase unter inerter Atmosphäre durchführt.
9. Verfahren nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß die Säure aus der Salzsäure, Schwefelsäure, Salpetersäure und Bromwasserstoffsäure umfassenden Gruppe ausgewählt ist.
EP78400035A 1977-07-13 1978-06-27 Verfahren zur Gewinnung von Gallium mittels flüssig-flüssig Extraktion aus stark basischen Lösungen Expired EP0000457B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR7721607 1977-07-13
FR7721607A FR2397464A2 (fr) 1977-07-13 1977-07-13 Procede de recuperation du gallium de solutions tres basiques par extraction liquide/liquide
KR7803585A KR810001297B1 (ko) 1977-07-13 1978-12-07 갈륨 추출 방법

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EP0000457A1 EP0000457A1 (de) 1979-01-24
EP0000457B1 true EP0000457B1 (de) 1982-06-02

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EP (1) EP0000457B1 (de)
JP (1) JPS5440212A (de)
KR (1) KR810001297B1 (de)
AU (1) AU517726B2 (de)
CA (1) CA1117767A (de)
ES (3) ES471694A1 (de)
FI (1) FI68087C (de)
FR (1) FR2397464A2 (de)
GR (1) GR66020B (de)
IT (1) IT1105093B (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2460276A1 (fr) * 1979-07-03 1981-01-23 Rhone Poulenc Ind Procede de traitement de melanges d'oxydes de terres rares et de gallium
FR2532296B1 (fr) * 1982-08-26 1985-06-07 Rhone Poulenc Spec Chim Procede d'extraction du gallium a l'aide d'hydroxyquinoleines substituees et de composes organophosphores
SE8206377A0 (sv) * 1982-11-10 1984-05-11 Madan Khorshed Nya kelatbildande biskinolinföreningar
SE8206378L (sv) * 1982-11-10 1984-05-11 Sverker Hogberg Nya kelatbildande kinolinforeningar
CH655710A5 (de) * 1983-11-17 1986-05-15 Sulzer Ag Verfahren zur fluessig-fluessig-extraktion von gallium aus natriumaluminatloesung mit hilfe eines organischen extraktionsmittels.
CH656643A5 (de) * 1983-11-29 1986-07-15 Sulzer Ag Verfahren zur fluessig-fluessig-extraktion von gallium aus basischen, waessrigen loesungen mit hilfe eines organischen extraktionsmittels.
DE3508041A1 (de) * 1985-03-07 1986-09-11 Preussag Ag Metall, 3380 Goslar Verfahren zur fluessig-fluessig-extraktion von gallium, germanium oder indium aus waessrigen loesungen
NO158028C (no) * 1985-12-16 1988-06-29 Elkem As Utvinning av gallium.
JPH01117370U (de) * 1988-01-29 1989-08-08
US5016092A (en) * 1989-11-17 1991-05-14 Rca Licensing Corporation Control circuitry for an adaptive multistandard video comb filter
FR2670803B1 (fr) * 1990-12-19 1993-03-19 Rhone Poulenc Chimie Procede d'extraction de gallium avec de l'hydroxyquinoleine substituee.

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR952976A (fr) * 1947-08-25 1949-11-28 Alais & Froges & Camarque Cie Procédé d'extraction de la galline des produits alumineux
US3214239A (en) * 1962-07-02 1965-10-26 Kerr Mc Gee Oil Ind Inc Recovery of metal values from aqueous solution by solvent extraction with an organo phosphorus extractant
US3971843A (en) * 1974-07-12 1976-07-27 Rhone-Poulenc Industries Process for liquid/liquid extraction of gallium

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JPS5440212A (en) 1979-03-29
KR810001297B1 (ko) 1981-10-13
IT7850271A0 (it) 1978-07-12
IT1105093B (it) 1985-10-28
AU3796378A (en) 1980-01-17
AU517726B2 (en) 1981-08-20
FR2397464A2 (fr) 1979-02-09
FR2397464B2 (de) 1980-01-18
EP0000457A1 (de) 1979-01-24
FI68087B (fi) 1985-03-29
GR66020B (de) 1981-01-13
ES471694A1 (es) 1979-10-01
CA1117767A (fr) 1982-02-09
JPS6242851B2 (de) 1987-09-10
FI68087C (fi) 1985-07-10
FI782222A (fi) 1979-01-14
ES479023A1 (es) 1979-07-01
ES479022A1 (es) 1979-07-01

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