EP0000457B1 - Process for the recovery of gallium from very basic solutions by liquid/liquid extraction. - Google Patents

Process for the recovery of gallium from very basic solutions by liquid/liquid extraction. 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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EP0000457A1 (en
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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.

Description

La présente invention concerne un perfectionnement au procédé d'extraction liquide/liquide du gallium contenu dans des solutions aqueuses basiques, en particulier tel que décrit dans la demande de brevet français n° 2.277.897 et ses additions numéros 2.307.047, 2.307.882 et 2.365.641.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.

Ces demandes décrivent notamment un procédé de récupération du gallium présent dans des solutions aqueuses alcalines qui contiennent aussi des composés de l'aluminium et du sodium, par extraction liquide/liquide au moyen d'hydroxyquinoléines substituées. Le procédé étant plus particulièrement appliqué à la récupération du gallium des lessives d'aluminate de sodium du procédé Bayer à l'aide d'hydroxy-8 quinoléines. Le procédé de récupération du gallium décrit dans ces demandes comporte une étape d'extraction proprement dite et une étape de régénération du solvant et de récupération du gallium au moyen d'acides forts. Il existe des variantes préférées de mise en oeuvre de ce procédé selon, d'une part, l'acide utilisé et sa concentration dans l'étape de régénération du solvant chargé en gallium et, d'autre part, selon la pureté du gallium que l'on désire recueillir. Selon une première variante, le procédé préféré de récupération du gallium présent dans des solutions aqueuses très basiques contenant aussi des composés de l'aluminium et du sodium comporte les phases suivantes:

  • - mise en contact de la solution aqueuse avec une hydroxyquinoléine substituée insoluble dans l'eau en solution dans un solvant organique insoluble dans l'eau pris dans le groupe contenant les hydrocarbures aliphatiques et aromatiques halogénés ou non, de telle façon que le gallium et une certaine quantité de sodium et d'aluminium passent de la phase aqueuse dans la phase organique,
  • - séparation de la phase'organique de la phase aqueuse,
  • - mise en contact de la phase organique avec une solution aqueuse diluée d'un acide pour extraire le sodium et l'aluminium de la phase organique, le gallium restant en solution dans ladite phase organique,
  • - séparation de la phase organique de la phase aqueuse et mise en contact de la phase organique restante avec une solution aqueuse d'acide plus concentrée afin d'extraire le gallium de la phase organique dans la phase aqueuse,
  • - séparation du gallium de la phase aqueuse.
These applications describe in particular a process for recovering gallium present in aqueous alkaline solutions which also contain aluminum and sodium compounds, by liquid / liquid extraction by means of substituted hydroxyquinolines. The process being more particularly applied to the recovery of gallium from the sodium aluminate washing liquors of the Bayer process using 8-hydroxyquinolines. The gallium recovery process described in these applications comprises an extraction step proper and a step of regenerating the solvent and recovering the gallium by means of strong acids. There are preferred variants of implementation of this process according, on the one hand, to the acid used and its concentration in the regeneration step of the solvent loaded with gallium, and, on the other hand, according to the purity of the gallium that we want to collect. According to a first variant, the preferred process for recovering gallium present in very basic aqueous solutions also containing aluminum and sodium compounds comprises the following phases:
  • - bringing the aqueous solution into contact with a substituted hydroxyquinoline insoluble in water in solution in an organic solvent insoluble in water taken from the group containing aliphatic and aromatic hydrocarbons, halogenated or not, so that gallium and a certain amount of sodium and aluminum pass from the aqueous phase into the organic phase,
  • - separation of the organic phase from the aqueous phase,
  • bringing the organic phase into contact with a dilute aqueous solution of an acid to extract the sodium and aluminum from the organic phase, the gallium remaining in solution in said organic phase,
  • separation of the organic phase from the aqueous phase and bringing the remaining organic phase into contact with a more concentrated aqueous acid solution in order to extract the gallium from the organic phase in the aqueous phase,
  • - separation of gallium from the aqueous phase.

Les acides utilisés sont de préférence l'acide chlorhydrique, l'acide sulfurique et l'acide nitrique. La concentration de la solution aqueuse diluée d'acide est de préférence comprise entre 0,2 M et 0,5 M. La concentration de la solution aqueuse d'acide plus concentrée est généralement de préférence supérieure à 1,6 M; mais, dans le cas où l'on met en oeuvre l'acide chlorhydrique, celle-ci est de préférence comprise entre 1,3 M et 2,2 M et plus spécialement entre 1,6 M et 1,8 M.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.

Selon une deuxième variante, le procédé préféré de récupération du gallium comporte les phases suivantes:

  • - mise en contact de la solution aqueuse avec une hydroxyquinoléine substituée insoluble dans l'eau en solution dans un solvant organique insoluble dans l'eau pris dans le groupe comprenant les hydrocarbures aliphatiques et aromatiques halogénés ou non de telle façon que le gallium et une certaine quantité de sodium et d'aluminium passent de la phase aqueuse dans la phase organique,
  • - séparation de la phase organique de la phase aqueuse,
  • - mise en contact de la phase organique avec une solution aqueuse concentrée d'un acide capable de complexer le gallium sous forme anionique, le gallium restant en solution dans la phase organique, tandis que le sodium et l'aluminium passent dans la phase aqueuse,
  • - séparation de la phase organique de la phase aqueuse et mise en contact de la phase organique restante avec une solution aqueuse diluée d'acide pour transférer le gallium de la phase organique dans la phase aqueuse,
  • - séparation du gallium de la phase aqueuse.
According to a second variant, the preferred process for recovering gallium comprises the following phases:
  • - bringing the aqueous solution into contact with a substituted hydroxyquinoline insoluble in water in solution in an organic solvent insoluble in water taken in the group comprising aliphatic and aromatic hydrocarbons halogenated or not in such a way that gallium and a certain amount of sodium and aluminum pass from the aqueous phase into the organic phase,
  • - separation of the organic phase from the aqueous phase,
  • bringing the organic phase into contact with a concentrated aqueous solution of an acid capable of complexing the gallium in anionic form, the gallium remaining in solution in the organic phase, while the sodium and the aluminum pass into the aqueous phase,
  • separation of the organic phase from the aqueous phase and bringing the remaining organic phase into contact with a dilute aqueous acid solution to transfer the gallium from the organic phase into the aqueous phase,
  • - separation of gallium from the aqueous phase.

Les acides utilisés sont de préférence l'acide chlorhydrique et l'acide bromhydrique. La concentration de la solution concentrée est de préférence comprise entre 5 M et 8 M et celles de la solution diluée entre 1,3 M et 2,2 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.

Par ailleurs, et selon une troisième variante, si l'on désire un gallium moins purifié, le procédé peut comporte les étapes suivantes:

  • - mise en contact de la solution aqueuse avec une hydroxyquinoléine substituée insoluble dans l'eau en solution dans un solvant organique insoluble dans l'eau pris dans le groupe comprenant les hydrocarbures aliphatiques et aromatiques halogénés ou non, de telle façon que le gallium et une certaine quantité de sodium et d'aluminium passent de la phase aqueuse dans la phase organique,
  • - séparation de la phase organique de la phase aqueuse,
  • - mise en contact de la phase organique avec une solution aqueuse d'un acide pour extraire le sodium, l'aluminium et le gallium de la phase organique,
  • - séparation de la phase aqueuse et organique,
  • - récupération du gallium, du sodium et de l'aluminium.
Furthermore, and according to a third variant, if a less purified gallium is desired, the process can include the following steps:
  • contacting the aqueous solution with a substituted hydroxyquinoline insoluble in water in solution in an organic solvent insoluble in water taken from the group comprising aliphatic and aromatic hydrocarbons, halogenated or not, in such a way that gallium and a certain amount of sodium and aluminum pass from the aqueous phase into the organic phase,
  • - separation of the organic phase from the aqueous phase,
  • - bringing the organic phase into contact with an aqueous solution of an acid to extract sodium, aluminum and gallium from the organic phase,
  • - separation of the aqueous and organic phase,
  • - recovery of gallium, sodium and aluminum.

Les acides utilisés sont de préférence soit de l'acide sulfurique ou l'acide nitrique à une concentration supérieure à 1,6 M, soit l'acide chlorhydrique ou l'acide bromhydrique à une concentration comprise entre 1,3 M et 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.

Les solvants organiques mis en oeuvre en particulier dans ces variantes sont les diluants utilisés en extraction liquide/liquide. Ils peuvent être utilisés seuls ou en mélange. Parmi ceux-ci, on peut citer: les composés aliphatiques comme par exemple l'heptane et les coupes pétrolières du type Kérosène; les composés aromatiques comme par exemple le benzène, le toluène, le xylène et les coupes du type Solvesso (marque déposée par la Société Exxon) et enfin les dérivés halogénés de ces composés comme par exemple le chloroforme et le tétrachlorure de carbone.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.

De manière connue, dans l'étape d'extraction du gallium décrite dans ces demandes, il peut être avantageux d'ajouter dans la phase organique d'extraction des corps à fonction alcool, tels que les alcools lourds comme le N-décanol et l'isodécanol et des phénols lourds divers, ainsi que divers autres composés solvatants tels que certains esters phosphoriques comme le tributyl phosphate.As is known, in the gallium extraction step described in these applications, it may be advantageous to add, in the organic phase of extraction, bodies with an alcohol function, such as heavy alcohols such as N-decanol and l isodecanol and various heavy phenols, as well as various other solvating compounds such as certain phosphoric esters such as tributyl phosphate.

Les hydroxyquinoléines substituées mises en oeuvre sont celles qui peuvent extraire le gallium par complexation, elles doivent de plus être plus solubles dans la phase organique que dans la phase aqueuse.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.

Les hydroxyquinoléines substituées convenant sont notamment celles de formule générale

Figure imgb0001
dans laquelle R1, R2, R3, R4, R5, R6 identiques ou différents sont choisis parmi le groupe constitué par l'hydrogène, les radicaux substitués ou non alkyles, alcényles, cycloaliphatiques, aromatiques; R1, R2, R3, R4, R5, R6 ne pouvant représenter simultanément H. Parmi ces hydroxyquinoléines substituées, celles convenant particulièrement bien sont notamment les α alcényl hydroxy-8 quinoléines, les β alcényl hydroxy-8 quinoléines et les alkyl hydroxy-8 quinoléines dans lesquelles Rn (n = 1,2,3,4,5,6) représente un hydrogène ou un radical alkyle.Suitable substituted hydroxyquinolines are in particular those of general formula
Figure imgb0001
 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. Among these substituted hydroxyquinolines, those which are particularly suitable are in particular the α alkenyl hydroxy-8 quinolines, the β alkenyl hydroxy-8 quinolines and alkyl hydroxy-8 quinolines in which R n (n = 1,2,3,4,5,6) represents a hydrogen or an alkyl radical.

Les α alcényl hydroxy-8 quinoléines préférées ont pour formule générale

Figure imgb0002
dans laquelle R1, R2, R3 représentent un hydrogène ou un groupement hydrocarboné éventuellement substitué. Parmi celles-ci, on utilisera notamment celles de formule générale
Figure imgb0003
 The preferred α-8-alkenyl hydroxy-quinolines have the general formula
Figure imgb0002
 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
Figure imgb0003

Les β alcényl hydroxy-8 quinoléines préférées ont pour formule générale

Figure imgb0004
dans laquelle R1, R2, R3, R4, R5 représentent un hydrogène ou un groupement hydrocarboné éventuellement substitué.The preferred 8-alkenyl hydroxy-8 quinolines have the general formula
Figure imgb0004
 in which R 1 , R 2 , R 3 , R 4 , R 5 represent a hydrogen or an optionally substituted hydrocarbon group.

Les hydroxyquinoléines peuvent être mises en oeuvre seules ou en mélange.The hydroxyquinolines can be used alone or as a mixture.

La proportion en hydroxyquinoléine substituée dans la phase organique n'est pas critique et peut varier dans de larges limites. Toutefois, une proportion comprise entre 1 et 50% en volume rapportée à la phase organique convient généralement, une proportion comprise entre 6 et 12% étant économiquement favorable.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.

Par ailleurs, bien que la température ne soit pas un paramètre critique, pour obtenir de bons résultats selon le procédé décrit dans ces demandes, il est avantageux que l'étape d'extraction soit effectuée à une température assez élevée pratiquement inférieure à 100°C et, de préférence, comprise entre 50 et 80°C. On peut ajouter qu'en pratique industrielle, les solutions généralement traitées sont des solutions d'aluminate du procédé Bayer et particulièrement les solutions dites "décomposées" qui ont une température voisine de 50°C. Il se trouve que cette température, bien que moins favorable qu'une température plus élevée, suffit cependant à assurer des rendements d'extraction satisfaisants; de plus, l'étape de régénération du solvant et de récupération du gallium est effectuée de telle façon que la phase organique est traitée afin d'en récupérer le gallium par une solution d'acide à une température inférieure à celle de l'étape d'extraction et de préférence au voisinage de la température ambiante.Furthermore, although 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. It can be added that in industrial practice, 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.

Les solutions très basiques traitées selon le procédé décrit dans ces demandes sont notamment celles dans lesquelles la concentration en OH- peut aller jusqu'à 13--14 ions g/I. Ainsi, les lessives d'aluminate de sodium du procédé Bayer traitées de préférence selon ce procédé ont généralement des compositions correspondant à:

Figure imgb0005
les lessives dites "décomposées" ayant généralement des compositions telles que:
Figure imgb0006
 The very basic solutions treated according to the process described in these applications are in particular those in which the concentration of OH- can range up to 13-14 g / I ions. Thus, the sodium aluminate detergents of the Bayer process preferably treated according to this process generally have compositions corresponding to:
Figure imgb0005
 so-called "decomposed" detergents generally having compositions such as:
Figure imgb0006

En pratique industrielle, les installations utilisées selon ce procédé se présentent de la manière suivante: dans un premier dispositif d'extraction on envoie la solution d'aluminate de sodium appauvrie en alumine à la suite de sa "décomposition" et la phase organique constituée du complexant choisi, d'un solvant et éventuellement de corps à fonction alcool et autres composés solvatants; le gallium passe alors pour une fraction importante dans la phase organique, laquelle fraction dépend des débits respectifs des deux liquides. Passent également dans la phase organique, de l'aluminium, du sodium et certaines impuretés. La phase organique ainsi chargée est mise en contact dans un deuxième dispositif d'extraction avec une première solution de régénération constituée par un acide fort dilué ou par un acide fort complexant concentré ce qui dans les deux cas ne laisse pratiquement dans cette phase organique que le gallium; cette phase organique est traitée ensuite dans un troisième dispositif d'extraction à contre-courant où éfle est mise en contact avec un acide-fort aux fins de récupération du gallium, puis subit un lavage à l'eau avant d'être recyclée dans le premier dispositif d'extraction; la solution acie ayant récupéré le gallium est ensuite traitée afin de parfaire sa purification puis le gallium en est extrait. On peut également envisager un dispositif industriel plus simple mais conduisant à un gallium moins purifié; un tel type de dispositif comporte un premier appareil d'extraction comme décrit précédemment à la sortie duquel on effectue dans un deuxième appareil fonctionnant à contre-courant, une seule régénération par une solution d'acide fort, de l'aluminium, du sodium et du gallium contenus dans la phase organique.In industrial practice, 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. 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.

Par ailleurs, selon la demande n° 2.365.641, il a été trouvé que l'utilisation prolongée d'alcényl hydroxy-8 quinoléine dans une unité d'extraction du gallium selon le procédé décrit dans la demande de brevet français n° 2.277.897 et ses deux additions numéros 2.307,047 et 2.307.882 conduit à leur dégradation progressive du fait de la basicité du milieu d'extraction ce qui se traduit par une baisse de leur pouvoir extractant. La demanderesse a été conduite à sélectionner, dans la classe des hydroxyquinoléines substituées, certaines d'entre elles qui s'avèrent présenter une stabilité accrue en milieu très basique et qui conservent les remarquables propriétés extractantes du gallium des lessives d'aluminate de sodium des alcényl hydroxy-8 quinoléines. Ainsi, la demanderesse a proposé dans sa demande numéro 2.365.641 des hydroxyquinoléines substituées choisies parmi le groupe constitué par les hydroxyquinoléines de formule générale:

Figure imgb0007
dans laquelle Rn (n = 1,2,3,4,5,6) est un radical alcoyl ou un hydrogène.Furthermore, according to application No. 2,365,641, it has been found that the prolonged use of alkenyl hydroxy-8 quinoline in a gallium extraction unit according to the process described in French patent application No. 2,277. 897 and its two additions numbers 2.307.047 and 2.307.882 leads to their gradual degradation due to the basicity of the extraction medium which results in a decrease in their extracting power. The Applicant has been led to select, from the class of substituted hydroxyquinolines, some of them which prove to have increased stability in very basic medium and which retain the remarkable extracting properties of gallium from the sodium aluminate alkenyl detergents. 8-hydroxyquinolines. Thus, the applicant proposed in its application number 2,365,641 substituted hydroxyquinolines chosen from the group consisting of hydroxyquinolines of general formula:
Figure imgb0007
 in which R n (n = 1,2,3,4,5,6) is an alkyl radical or a hydrogen.

Le radical alcoyl Rn comporte, dans un mode de réalisation préféré, de 5 à 20 atomes de carbone.The alkyl radical R n comprises, in a preferred embodiment, from 5 to 20 carbon atoms.

Selon un autre mode de réalisation préféré, le radical R est situé en position 7 sur le cycle hydroxy-8 quinoléine et les produits préféres utilisés répondent à la formule générale:

Figure imgb0008
dans laquelle n est de préférence compris entre 5 et 20.According to another preferred embodiment, the radical R is located in position 7 on the 8-hydroxy-quinoline ring and the preferred products used correspond to the general formula:
Figure imgb0008
 in which n is preferably between 5 and 20.

Les hydroxyquinoléines selon ce procédé permettent une extraction presque totale et sans perte au cours du temps du gallium présent dans des solutions aqueuses très basiques et en particulier des lessives d'aluminate de sodium du procédé Bayer.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.

Poursuivant ses travaux, la demanderesse a trouvé que, bien que la cause essentielle de la dégradation des hydroxy-8 quinoléines soit la nature très basique du milieu, l'oxydation de ces produits par l'oxygène de l'air conduisait également à une certaine dégradation au cours de leur utilisation prolongée; cette dernière dégradation affectant à des degrés divers les différents types d'hydroxy-8 quinoléines utilisables. La présente invention a pour but d'obvier à cet inconvénient.Continuing its work, 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.

La présente invention concerne un procédé d'extraction liquide/liquide du gallium contenu dans des solutions aqueuses basiques par mise en contact de la solution aqueuse avec une phase organique contentant principalement un solvant organique et au moins une hydroxyquinoléine substituée caractérisé en ce que l'on opère sous atmosphère inerte.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.

L'atmosphère inerte peut être constituée en particulier par une atmosphère d'argon ou d'azote.The inert atmosphere may in particular consist of an argon or nitrogen atmosphere.

Les différentes modalités de mise en oeuvre du procédé selon l'invention sont celles qui ont été rappelées ci-dessus. Toutes les phases du procédé peuvent être réalisées sous atmosphère inerte étant bien entendu que la phase d'extraction doit l'être obligatoirement.The various methods of implementing the method according to the invention are those which have been mentioned above. All the process phases can be carried out under an inert atmosphere, it being understood that the extraction phase must be carried out.

Bien que les différentes modalités de mise en oeuvre du procédé selon l'invention aient été décrites dans ce qui précède, notamment dans le rappel du procédé décrit dans les demandes de brevets français n° 2 277 897, 2 307 047, 2 307 882, 2 365 641, on en rappelle ci-après certains aspects.Although the various methods of implementing the method according to the invention have been described in the foregoing, in particular in the reminder of the method described in French patent applications No. 2,277,897, 2,307,047, 2,307,882, 2,365,641, certain aspects are recalled below.

Le solvant organique mis en oeuvre selon le procédé de l'invention est choisi parmi le groupe constitué par les hydrocarbures aromatiques et aliphatiques halogénés ou non.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.

L'hydroxyquinoléine substitué mise en oeuvre selon le procédé de l'invention extrait le gallium par complexation et est plus soluble dans la phase organique que dans la phase aqueuse.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.

Les hydroxyquinoléines substituées convenant sont notamment celles de formule générale

Figure imgb0009
dans laquelle R1, R2, R3, R4, R5, R6 identiques ou différents sont choisis parmi le groupe constitué par l'hydrogène, les radicaux substitués ou non alkyles, alcényles, cycloaliphatiques, aromatiques; R1,R2, R3, R4, Rs, R6 ne pouvant représenter simultanément H. Parmi ces hydroxyquinoléines substituées, celles convenant particulièrement bien sont notamment les a alcényl hydroxy-8 quinoléines, les β alcényl hydroxy-8 quinoléines et les alkyl hydroxy-8 quinoléines dans lesquelles Rn (n = 1,2,3,4,5,6) représente un hydrogène ou un radical alkyle.The suitable substituted hydroxyquinolines are in particular those of general formula
Figure imgb0009
 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. Among these substituted hydroxyquinolines, those which are particularly suitable are in particular the 8-alkenyl hydroxy-quinolines, the β-8-alkenyl hydroxy-quinolines and alkyl hydroxy-8 quinolines in which R n (n = 1,2,3,4,5,6) represents a hydrogen or an alkyl radical.

Les a alcényl hydroxy-8 quinoléines préférées ont pour formule générale:

Figure imgb0010
dans laquelle R1, R2, R3 représentent un hydrogène ou un groupement hydrocarboné éventuellement substitué.The preferred α-alkenyl hydroxy-8 quinolines have the general formula:
Figure imgb0010
 in which R 1 , R 2 , R 3 represent a hydrogen or an optionally substituted hydrocarbon group.

Les alkyl hydroxy-8 quinoléines préférées ont pour formule générale

Figure imgb0011
The preferred 8 hydroxy alkyl quinolines have the general formula
Figure imgb0011

Les f3 alcényl hydroxy-8 quinoléines préférés ont pour formule générale

Figure imgb0012
dans laquelle R,, R2, R3, R4, Rs représentent un hydrogène ou un groupement hydrocarboné éventuellement substitué.The preferred 8-alkenyl hydroxy-8 quinolines have the general formula
Figure imgb0012
 in which R ,, R 2 , R 3 , R 4 , R s represent a hydrogen or an optionally substituted hydrocarbon group.

Les hydroxyquinoléines peuvent être mises en oeuvre seules ou en mélange.The hydroxyquinolines can be used alone or as a mixture.

La proportion en hydroxyquinoléine substituée dans la phase organique n'est pas critique et peut varier dans de larges limites. Toutefois, une proportion comprise entre 1 et 50% en volume rapportée à la phase organique convient généralement, une proportion comprise entre 6 et 12% étant économiquement favorable.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.

Il peut être avantageux d'ajouter dans la phase organique d'extraction un agent modifieur choisi parmi le groupe comprenant les corps à fonction alcool et les esters phosphoriques.It may be advantageous to add to the organic extraction phase a modifying agent chosen from the group comprising bodies with alcohol function and phosphoric esters.

La présente invention concerne également un procédé de récupération du gallium contenu dans des solutions aqueuses basiques par extraction liquide/liquide caractérisé en ce que l'on met en contact, sous atmosphère inerte, la solution aqueuse avec une phase organique contenant principalement un solvant organique et au moins une hydroxyquinoléine substituée, on opère la séparation de la phase organique de la phase aqueuse, qu'au moins une fois, d'une part, on met en contact la phase organique avec une solution d'acide fort, et, d'autre part, on sépare la phase organique restante de la phase aqueuse et qu'ensuite on récupère le gallium de la phase aqueuse.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.

La présente invention concerne également la récupération du gallium contenu dans des solutions aqueuses basiques par extraction liquide/liquide par mise en contact de la solution aqueuse avec une phase organique contenant principalement un solvant organique et une hydroxyquinoléine substituée caractérisé en ce que la séparation de la phase organique de la phase aqueuse, et/ou la mise en contact de la phase organique avec une solution d'acide fort, et/ou la séparation de la phase organique restante de la phase aqueuse, et/ou la récupération du gallium de la phase aqueuse sont effectuées sous atmosphère inerte.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.

L'acide mis en oeuvre est choisi parmi le groupe comprenant l'acide chlorhydrique, l'acide sulfurique, l'acide nitrique, l'acide bromhydrique; sa concentration dans la ou les étapes de régénération du solvant chargé en gallium est celle qui a été relevée ci-dessus pour les différentes variantes de mise en oeuvre du procédé selon les demandes de brevet français numéros 2.277.897, 2.307.047, 2.307.882 et 2.365.641.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.

L'exemple donné ci-après montre que le fait de travailler sous atmosphère inerte lors de la phase d'extraction du gallium de la lessive Bayer permit de réduire considérablement la perte en hydroxyquinoléine, ce qui améliore notablement l'économie du procédé.The example given below shows that working under an inert atmosphere during the gallium extraction phase of Bayer detergent makes it possible to considerably reduce the loss of hydroxyquinoline, which significantly improves the economy of the process.

Exemple: l'hydroxyquinoléine de formule:

Figure imgb0013
a été soumise à un test d'utilisation lors de la phase d'extraction du gallium.Example: hydroxyquinoline of formula:
Figure imgb0013
 was subjected to a usage test during the gallium extraction phase.

Une lessive Bayer de composition AI203:82 g/I, Na2O: 185 g/I, Ga: 240 mg/I est agitée avec une phase organique constituée de l'hydroxyquinoléine en solution à 10% dans un mélange 90-10 kérosène-décanol, l'opération étant effectuée à 50°C à l'air libre ou en atmosphère d'azote. En fonction du temps d'agitation, on analyse par chromatographie en phase gazeuse le titre en hydroxyquinoléine dans la phase organique. Les résultats obtenus sont consignés dans le tableau suivant qui exprime le pourcentage de perte en hydroxyquinoléine.

Figure imgb0014
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. As a function of the stirring time, 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.
Figure imgb0014

Claims (9)

1. Process for the liquid/liquid extraction of 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 having the formula
Figure imgb0023
in which R1, R2, R3, R4, R5 and R6, which are identical or different, are chosen from amongst the group comprising hydrogen and alkyl, alkenyl, cycloaliphatic and aromatic radicals, it being impossible for R1, R2, R3, R4, R5 and R6 to represent H simultaneously, characterised in that the reaction is carried out under an inert atmosphere.
2. Process according to Claim 1, characterised in that the inert atmosphere consists of nitrogen or argon.
3. Process according to Claim 1, characterised in that the organic solvent is chosen from amongst the group comprising aliphatic and aromatic hydrocarbons which may or may not be substituted by halogen.
4. Process according to Claim 1, characterised in that the hydroxyquinoline is chosen from amongst the group comprising the a-alkenyl-8-hydroxyquinolines of the general formula
Figure imgb0024
in which R1, R2 and R3 represent a hydrogen or a hydrocarbon group, the β-alkenyl-8-hydroxy- quinolines of the formula
Figure imgb0025
in which R1, R2, R3, R4 and R5 represent a hydrogen or a hydrocarbon group, and the alkyl-8-hydroxy- quinolines of the formula
Figure imgb0026
in which n is between 5 and 20.
5. Process according to Claim 1, characterised in that the proportion of substituted hydroxyquinoline in the organic phase is between 1 and 50% by volume, relative to the organic phase.
6. Process according to Claim 1, characterised in that a modifier, chosen from amongst the group comprising substances with an alcohol group and phosphoric acid esters, is added to the organic phase.
7. Process for the recovery of gallium contained in basic aqueous solutions, by liquid/liquid extraction according to Claim 1, characterised in that the aqueous solution is brought into contact, under an inert atmosphere, with an organic phase mainly containing an organic solvent and at least one substituted hydroxyquinoline, and the organic phase is separated from the aqueous phase, in that, at least once, on the one hand the organic phase is brought into contact with a solution of strong acid, and on the other hand the remaining organic phase is separated from the aqueous phase, and in that the gallium is then recovered from the aqueous phase.
8. Process according to Claim 7, characterised in that the separation of the organic phase from the aqueous phase, and/or the bringing of the organic phase into contact with a solution of strong acid, and/or the separation of the remaining organic phase from the aqueous phase, and/or the recovery of the gallium from the aqueous phase, are carried out under an inert atmosphere.
9. Process according to Claim 7 or 8, characterised in that the acid is chosen from amongst the group comprising hydrochloric acid, sulphuric acid, nitric acid and hydrobromic acid.
EP78400035A 1977-07-13 1978-06-27 Process for the recovery of gallium from very basic solutions by liquid/liquid extraction. Expired EP0000457B1 (en)

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FR7721607A FR2397464A2 (en) 1977-07-13 1977-07-13 PROCESS FOR RECOVERING GALLIUM FROM VERY BASIC SOLUTIONS BY LIQUID / LIQUID EXTRACTION
FR7721607 1977-07-13
KR7803585A KR810001297B1 (en) 1977-07-13 1978-12-07 Method for extraction of gallium values

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FR2460276A1 (en) * 1979-07-03 1981-01-23 Rhone Poulenc Ind PROCESS FOR TREATING RARE EARTH OXIDES AND GALLIUM MIXTURES
FR2532296B1 (en) * 1982-08-26 1985-06-07 Rhone Poulenc Spec Chim PROCESS FOR THE EXTRACTION OF GALLIUM USING SUBSTITUTED HYDROXYQUINOLEINS AND ORGANOPHOSPHORUS COMPOUNDS
SE8206377A0 (en) * 1982-11-10 1984-05-11 Madan Khorshed New chelating biskinoline compounds
SE8206378L (en) * 1982-11-10 1984-05-11 Sverker Hogberg NEW CHELATING CINOLIC SOCIETY COMPOUNDS
CH655710A5 (en) * 1983-11-17 1986-05-15 Sulzer Ag METHOD FOR LIQUID-LIQUID EXTRACTION OF GALLIUM FROM SODIUM ALUMINATE SOLUTION WITH THE AID OF AN ORGANIC EXTRACTION AGENT.
CH656643A5 (en) * 1983-11-29 1986-07-15 Sulzer Ag METHOD FOR THE LIQUID-LIQUID EXTRACTION OF GALLIUM FROM BASIC, AQUEOUS SOLUTIONS BY MEANS OF AN ORGANIC EXTRACTION AGENT.
DE3508041A1 (en) * 1985-03-07 1986-09-11 Preussag Ag Metall, 3380 Goslar METHOD FOR LIQUID-LIQUID EXTRACTION OF GALLIUM, GERMANIUM OR INDIUM FROM AQUEOUS SOLUTIONS
NO158028C (en) * 1985-12-16 1988-06-29 Elkem As GALLIUM EXTRACTION.
JPH01117370U (en) * 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 (en) * 1990-12-19 1993-03-19 Rhone Poulenc Chimie PROCESS FOR THE EXTRACTION OF GALLIUM WITH SUBSTITUTED HYDROXYQUINOLEIN.

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