Classifications

• • 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 either sulfuric acid or nitric acid at a concentration greater than 1.6 M, or hydrochloric acid or hydrobromic acid f. a concentration of between 1.3 M and 2.2 M.
• 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 benzene, toluene, xylene and Solvesso type cuts (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 benzene, toluene, xylene and Solvesso type cuts (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.
• 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 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 ⁇ -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. Among these, use will be made in particular of those of general formula
• the preferred p 8-alkenyl hydroxy-quinolines have the general formula in which R 1 , R 2 , R 3 , R 41 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. 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.
• this temperature although less favorable than a higher temperature, is however sufficient to ensure satisfactory extraction yields; moreover, the step of regenerating the solvent and recovering the gallium is carried out in such a way that the organic phase is treated in order to recover the gallium by an acid solution at a temperature lower than that of the extraction step 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 in the following manner: in a first extraction device, the solution of sodiun aluminate depleted in alumina as a result of its "decomposition" is sent 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 it 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 it 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.
• the alkyl radical R contains, 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 oxygen in the air also leads to a certain degradation during prolonged use; this latter degradation affecting in 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 gallium contained in basic aqueous solutions, characterized in that, under an inert atmosphere, the aqueous solution is brought into contact with an organic phase containing mainly an organic solvent and at least one hydroxyquinoline. substituted.
• 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 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 ⁇ -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 p 8-alkenyl hydroxy-quinolines have the general formula in which R 1 , 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 a process for recovering gallium contained in basic aqueous solutions by liquid / liquid extraction, characterized 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 strong acid, and / or the separation of the remaining organic phase from the aqueous phase, and / or the recovery of gallium from the aqueous phase 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 2.227.897, 2.307.047, 2.307. 882 and 2.365.641.
• a Bayer detergent with composition Al 2 O 3 : 82 g / l, Na 2 0: 185 g / 1, Ga: 240 mg / 1 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 title of hydroxyquinoline in the organic phase is analyzed by gas chromatography. The results obtained are recorded in the following table which expresses the percentage loss of hydroxyquinoline.

Landscapes

• 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)

Applications Claiming Priority (3)

Publications (2)

Family

ID=26220127

Family Applications (1)

Country Status (10)

Cited By (8)

Families Citing this family (3)

Citations (3)

• 1977
  • 1977-07-13 FR FR7721607A patent/FR2397464A2/fr active Granted
• 1978
  • 1978-06-27 EP EP78400035A patent/EP0000457B1/de not_active Expired
  • 1978-07-10 JP JP8389378A patent/JPS5440212A/ja active Granted
  • 1978-07-11 FI FI782222A patent/FI68087C/fi not_active IP Right Cessation
  • 1978-07-11 GR GR56752A patent/GR66020B/el unknown
  • 1978-07-12 CA CA000307275A patent/CA1117767A/fr not_active Expired
  • 1978-07-12 AU AU37963/78A patent/AU517726B2/en not_active Expired
  • 1978-07-12 IT IT50271/78A patent/IT1105093B/it active
  • 1978-07-13 ES ES471694A patent/ES471694A1/es not_active Expired
  • 1978-12-07 KR KR7803585A patent/KR810001297B1/ko active
• 1979
  • 1979-03-28 ES ES479023A patent/ES479023A1/es not_active Expired
  • 1979-03-28 ES ES479022A patent/ES479022A1/es not_active Expired

Patent Citations (3)

Also Published As

Similar Documents

Legal Events