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WO2009106660A1 - Procédé de récupération de germanium dans une solution par la complexion et l'utilisation de résines échangeuses d' ions - Google Patents

Procédé de récupération de germanium dans une solution par la complexion et l'utilisation de résines échangeuses d' ions Download PDF

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Publication number
WO2009106660A1
WO2009106660A1 PCT/ES2009/000102 ES2009000102W WO2009106660A1 WO 2009106660 A1 WO2009106660 A1 WO 2009106660A1 ES 2009000102 W ES2009000102 W ES 2009000102W WO 2009106660 A1 WO2009106660 A1 WO 2009106660A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
resin
germanium
complex
carried out
Prior art date
Application number
PCT/ES2009/000102
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English (en)
Spanish (es)
Inventor
Constantino FERNÁNDEZ PEREIRA
Fátima ARROYO TORRALBO
Original Assignee
Universidad De Sevilla
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 Universidad De Sevilla filed Critical Universidad De Sevilla
Publication of WO2009106660A1 publication Critical patent/WO2009106660A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G17/00—Compounds of germanium
    • 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
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • 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

Definitions

  • the invention relates to a process for the recovery of germanium present in aqueous solutions, which is separated from other metals also present in said solution by the use of ion exchange resins.
  • the selective extraction is achieved by the formation of an organic germanium complex, which is adsorbed in a conventional anionic resin.
  • the germanium is desorbed from the resin by contacting it with an aqueous solution, which may have an acidic character. , basic or neutral.
  • an aqueous solution which may have an acidic character. , basic or neutral.
  • the possibility of selecting a desorption solution facilitates possible subsequent operations to obtain the highest purity germanium. After desorption, the resin can be regenerated for a new use.
  • germanium germanium
  • the estimated concentration of germanium (Ge) in the earth's crust is in the range 1-7 ppm, but its extraction is not simple, since it is quite dispersed and is only concentrated in some minerals such as germanite or renierite .
  • Germanium-rich coals have regained importance, due to the depletion of some germanium ores (Van Lier, RJ. M .; Dreisinger, DB (1995) Sep .Processes Proc. Symp. 203-24).
  • the Ge is generally recovered from the ashes, which may contain a concentration of Ge about ten times greater than that of the original coal, after a first stage of leaching it, obtaining an aqueous solution containing Ge in low concentrations next to other metals , such as Zn, Cu or Fe. Therefore, the separation and concentration of Ge from aqueous extracts of coal ashes is a great technological challenge.
  • aqueous solutions There are numerous methods described in the literature for the separation or recovery of the Ge present in aqueous solutions, among which the following can be mentioned:
  • the present invention relates to a process for the recovery of germanium from aqueous solutions and provides a simple and effective process for the concentration and selective separation of germanium from aqueous solutions containing other metals, such as zinc, antimony , arsenic, cobalt, vanadium, molybdenum or nickel.
  • the process of the invention comprises the following steps:
  • STAGE I formation of the Ge complex by adding to the aqueous solution some reagent that forms anionic complexes with this element, such as catechol, some dicarboxylic acids and other diphenols.
  • Catechol has been selected due to its selectivity towards Ge, and its low cost compared to other complexing agents.
  • This stage can be performed using different CATVGe molar proportions, although the minimum amount should be the stoichiometric proportion, which is 3.
  • STAGE II Extraction with ion exchange resins, which is done by contacting the fertile solution (F) that contains the Ge-CAT complex with a certain amount of resin. This contact can be made discontinuously, adding the resin to the solution and stirring, or continuously using columns.
  • the choice of the resin is carried out between the anionic resins, strongly basic and macroporous, which have pore sizes large enough to retain in them the germanium complex.
  • the amount of resin that needs to be added, expressed in the form of equivalents, must be at least 2 times the number of equivalents of Ge, although a greater excess can displace the equilibrium favorably to the extraction.
  • the contact time can be adjusted from a few minutes to longer times, depending on the type of contact and the required extraction performance. In the examples included in this patent, the contact has been maintained for 7h although it has been proven that shorter contact times also allow the extraction of the complex.
  • the contact can be continuous, using resin filled columns; or discontinuous, using containers with agitation. After the extraction, the resulting or refined aqueous solution (R) is practically free of germanium, while the rest of the metals remain in the refining, and the resin is loaded with the Ge-CAT complex.
  • STAGE III separation of the resin and the refining by filtration or by other methods.
  • STEP IV discharge of the Ge contained in the resin, for which the resin loaded with Ge is contacted with an eluent aqueous solution (E) containing the agent responsible for breaking the joint between the complex and the functional groups of The resin
  • E eluent aqueous solution
  • germanium can be concentrated, using a volume of solution E smaller than that of the original solution F, which allows a saving of reagents. It is not recommended that the ratio between F / E volumes be greater than 20, due to a decrease in discharge performance.
  • this contact can be carried out discontinuously or continuously. The contact time can also be adjusted from a few minutes to longer times. In the examples included in the present patent, the contact has been maintained for 7h although it has been proven that shorter contact times also allow the discharge of germanium.
  • STAGE V separation of the resin from the concentrated solution by filtration or by other methods, to obtain an aqueous phase concentrated in Ge and practically free of other elements, which will be called the concentrated solution (C).
  • the concentrated solution (C) can be reused again as an eluent solution in a new Ge discharge process, resulting in an increase in the final concentration of Ge with each reuse.
  • STEP VII regeneration of the resin by one or several cycles with different aqueous solutions before a new use, to reinstate the active groups, and condition it for its new use in the process.
  • HCI or NaCI can be used, if the resin is to be used in chloride form, or NaOH, if the resin is desired to have hydroxide form.
  • concentration of these solutions must be much higher than that of the eluent solutions (according to the manufacturer's specifications), and an excess greater than 100% of the theoretical capacity of the resin must be used.
  • Example 1 Extraction of Ge with a resin of type IRA-958 (Rohm-Haas).
  • the phases are separated: the resin, which is charged with the Ge complex, and the virtually free solution of that element (refined).
  • the refining is analyzed, and its Ge content turns out to be less than 5 mg / L, so the extraction yield is greater than 95%.
  • Example 2 Extraction of Ge with a resin of the type IRA-900 (Rohm-Haas) from a solution obtained by leaching an ash from a thermal power plant.
  • Solution L a liquid solution whose composition is shown in Table 1.
  • Solution L has been obtained by extracting a fly ash from a thermal power plant at room temperature for 24 hours, in a stirred reactor At atmospheric pressure
  • composition is shown in Table 2.
  • Said composition shows how the extracted germanium represents 92.6% of the initially present in the solution L, while the rest of the elements remain in the liquid solution, that is, they are hardly extracted by Ia resin, resulting in the selective operation for the Ge. As can be seen, they are only somewhat retained by the resin: Sb, V, Mo and Ni, much less As or Zn, but in all cases to a much lesser extent than germanium. It should also be noted that the initial amounts of elements such as V, Mo or Zn ( ⁇ 2.5 mg / L) in ash leachate (solution L) are much smaller than those of Ge (35.6 mg / L) .
  • Example 3 discharge of the adsorbed Ge onto an IRA-958 resin caused by a NaCI solution
  • the germanium-loaded resin is contacted with 150 ml of a 3M sodium chloride solution and both phases are kept stirred by flipping for 7 h at room temperature.
  • the phases are separated, and the sodium chloride solution now presents the composition indicated in Table 4.
  • the re-extracted germanium represents 89.2% of the resin content.
  • Example 4 Ge extraction with an IRA-958 resin and discharge produced by a NaCI solution
  • the phases are separated, and the refining is saved for analysis.
  • the extraction yields are shown in Table 5.
  • the extracted germanium represents 93.1% of that initially present in solution L, while the rest of the elements hardly change their concentration. Only partially adsorbed in the resin: Sb, Co, V, Mo, Ni or Zn, but in all cases to a much lesser extent than germanium, and in almost all cases, starting from much lower concentrations ( ⁇ 2.5 mg / L) than that of Ge in the original solution.
  • the germanium-loaded resin is contacted with 250 ml of a 3M sodium chloride solution and both phases are kept stirred by flipping for 7 h at room temperature. Then the phases are separated, and the sodium chloride solution is analyzed. The discharge yields are shown in Table 6. This table also shows the concentrations of these elements present in the concentrated solution (C).
  • Table 7 shows the global loading and unloading performance of each element in the operation explained in example 4.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé de récupération de germanium présent dans des solutions aqueuses, qui est séparé d'autres métaux également présents dans lesdites solutions par utilisation de résines à échangeuse d'ions. L'extraction sélective est obtenue par la formation d'un complexe organique de germanium qui est adsorbé dans une résine anionique classique. Finalement, le germanium est désorbé de la résine par contact de celle-ci avec une solution aqueuse, qui peut présenter un caractère acide, basique ou neutre. La possibilité de sélectionner une solution de désorption facilite les éventuelles opérations postérieures destinées à obtenir du germanium de pureté supérieure. Après la désorption, la résine peut se regénérer pour une nouvelle utilisation.
PCT/ES2009/000102 2008-02-28 2009-02-26 Procédé de récupération de germanium dans une solution par la complexion et l'utilisation de résines échangeuses d' ions WO2009106660A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ESP200800570 2008-02-28
ES200800570A ES2325292B1 (es) 2008-02-28 2008-02-28 Procedimiento para la recuperacion de germanio en disolucion mediante complejacion y utilizacion de resinas de intercambio ionico.

Publications (1)

Publication Number Publication Date
WO2009106660A1 true WO2009106660A1 (fr) 2009-09-03

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PCT/ES2009/000102 WO2009106660A1 (fr) 2008-02-28 2009-02-26 Procédé de récupération de germanium dans une solution par la complexion et l'utilisation de résines échangeuses d' ions

Country Status (2)

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ES (1) ES2325292B1 (fr)
WO (1) WO2009106660A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103866124A (zh) * 2014-04-16 2014-06-18 六盘水中联工贸实业有限公司 一种用TiO2·nH2O从含锗酸性溶液中提取锗的方法
CN106906364A (zh) * 2017-03-07 2017-06-30 云南临沧鑫圆锗业股份有限公司 从含锗含氟腐蚀液中回收锗的工艺方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB933563A (en) * 1960-02-12 1963-08-08 Forsch Ne Metalle Process for the recovery of germanium values
ES2257181A1 (es) * 2004-10-14 2006-07-16 Universidad De Alicante Procedimiento para la recuperacion de germanio en disolucion mediante carbon activo.
WO2007103277A2 (fr) * 2006-03-03 2007-09-13 Los Alamos National Security, Llc Séparation du germanium-68 et du gallium-68

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB933563A (en) * 1960-02-12 1963-08-08 Forsch Ne Metalle Process for the recovery of germanium values
ES2257181A1 (es) * 2004-10-14 2006-07-16 Universidad De Alicante Procedimiento para la recuperacion de germanio en disolucion mediante carbon activo.
WO2007103277A2 (fr) * 2006-03-03 2007-09-13 Los Alamos National Security, Llc Séparation du germanium-68 et du gallium-68

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103866124A (zh) * 2014-04-16 2014-06-18 六盘水中联工贸实业有限公司 一种用TiO2·nH2O从含锗酸性溶液中提取锗的方法
CN103866124B (zh) * 2014-04-16 2016-01-20 六盘水中联工贸实业有限公司 一种用TiO2·nH2O从含锗酸性溶液中提取锗的方法
CN106906364A (zh) * 2017-03-07 2017-06-30 云南临沧鑫圆锗业股份有限公司 从含锗含氟腐蚀液中回收锗的工艺方法

Also Published As

Publication number Publication date
ES2325292A1 (es) 2009-08-31
ES2325292B1 (es) 2010-06-24

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