EP0099804A2 - Verfahren zur Abscheidung von Metallen aus hypersauren Medien durch ionische Flotation - Google Patents

Verfahren zur Abscheidung von Metallen aus hypersauren Medien durch ionische Flotation Download PDF

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Publication number
EP0099804A2
EP0099804A2 EP83401389A EP83401389A EP0099804A2 EP 0099804 A2 EP0099804 A2 EP 0099804A2 EP 83401389 A EP83401389 A EP 83401389A EP 83401389 A EP83401389 A EP 83401389A EP 0099804 A2 EP0099804 A2 EP 0099804A2
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EP
European Patent Office
Prior art keywords
flotation
hyperacid
medium
surfactant
anionic surfactant
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Legal status (The legal status 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 status listed.)
Granted
Application number
EP83401389A
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English (en)
French (fr)
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EP0099804A3 (en
EP0099804B1 (de
Inventor
Pierre Blazy
El-Aid Jdid
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Association dite INSTITUT MONDIAL DU PHOSPHATE
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Association dite INSTITUT MONDIAL DU PHOSPHATE
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Priority to AT83401389T priority Critical patent/ATE33564T1/de
Publication of EP0099804A2 publication Critical patent/EP0099804A2/de
Publication of EP0099804A3 publication Critical patent/EP0099804A3/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/02—Froth-flotation processes

Definitions

  • the present invention relates to a process which aims at 1 asparation of different metals from the hyperacid media in which they are contained and at their possible recovery for their valorization, such a process using the principle of ionic flotation and s' applying more particularly to concentrated acid media and in particular to industrial phosphoric acid for the wet process.
  • K. SHAKIR J. of Appl. Chem. Biotech. 21-1973 emphasized the importance of choosing the pH of the collector and the medium, as well as the concentrations of uranyl, collector and sulfate ions for recovery uranium by ionic flotation, and described optimal uranium recoveries using cationic collectors in solution in ethanol and a starting pH greater than 2, for the flotation of uranium from dilute aqueous sulfuric solutions .
  • C. JACOBELLI-TURI, S. TERENZI and M. PALMERA I & EC PROCESS DESIGN AND DEVELOPMENT, Vol. 6, n ° 2, April 1967, p.
  • n ° 2 (1971) 7 described the elimination of 90% of the cadmium contained in the waste waters coming from mining operations, in particular from iron mines, by flotation by means of an alkyl-xanthate and in particular of an ethylbutyl- or amyl-xanthate present at 10, 1.5 and 1 equivalent per cadmium ion respectively for a cadmium ion concentration of 1 mg / liter in the solution, thus causing precipitation of cadmium xanthate, even in the case where these waters also contain Fe 2+ ions and Zn ions.
  • a surfactant consisting of a strongly basic quaternary ammonium salt, namely hexadecyltrimethylammonium iodide which plays the role of a soluble ion exchanger.
  • the ionic flotation agents described in the cited literature are not suitable for solving the problems posed by the separation of rare metals (such as Uranium, Z irconium, Yttrium for example) or of polluting metals (such as Cadmium by example) contained in wet phosphoric acid made from phosphate ores containing more or less appreciable amounts of such metals; in addition, they are generally only effective in a dilute aqueous medium and only on condition of adjusting the pH of the medium to adapt it to their operating conditions.
  • rare metals such as Uranium, Z irconium, Yttrium for example
  • polluting metals such as Cadmium by example
  • the present invention therefore aims to provide a process for the separation of different metals contained in hyperacid media, by ionic flotation, which is particularly applicable to the recovery of metals from concentrated acidic media, which is carried out at pH of the acidic medium, without requiring adjustment, and which makes it possible to achieve almost quantitative recovery yields.
  • the subject of the present invention is a process for the almost quantitative separation of metals present at very low concentrations in a acidic environment, by flotation using a surfactant which acts as a collector, which process is characterized in that a concentrated acid containing a metal to be recovered present at low level is added to a solution concentration, a solution of an anionic surfactant in quantity such that the ratio is equal to or greater than 3.5 and is preferably between 3.5 and 6, to cause the formation of a coprecipitate, or of a metal-ion anion surfactant complex, by causing, by all appropriate means, the formation in the concentrated acid solution of a fine dispersion of air bubbles on which the coprecipitate is adsorbed which is raised to the surface of the solution by the upward movement of said air bubbles, surface where it is collected in foams and recovered.
  • the surfactant used is preferably an anionic collector having at least one polar part and at least one hydrocarbon chain of length greater than C 6 , and stable in hyperacid media, taken in particular from sulfhydryls and organophosphorus compounds.
  • the anionic surfactant of sulhydryl type used is diethyldithiophosphate or another dialkyldithiophosphate in which the alkyl groups are lower alkyls.
  • the anionic surfactant used has both hydrophobic properties and chelating properties and comprises at least one hydrocarbon chain which gives it a hydrophobic character and at least a portion polar which gives it a chelating character, such a surfactant presents both hydrophobic and chelating properties being a suitable dialkyldiphosphonic compound.
  • the ionic flotation reaction is carried out at the pH of the hyperacid medium from which the metal sought is recovered, without requiring a specific adjustment of the pH of the medium.
  • anionic active in the medium are obtained by all appropriate means such as agitation, porous bottom, pressurization-followed by degassing, in particular.
  • the precipitation of the metal by the appropriate anionic surfactant takes place at a temperature between room temperature and 80 ° C.
  • the uranium in the VI state present in phosphoric acid is previously reduced to state IV by means of an appropriate reducing agent, such as iron powder in particular, before being brought into contact with the anionic surfactant with which it is called to form a co-precipitate.
  • an appropriate reducing agent such as iron powder in particular
  • the process which is the subject of the present invention applies with advantage to the separation of different metals from concentrated acid solutions, and in particular to the separation of rare metals such as uranium, zirconium, Yttrium, among others, to the separation of transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn) and to the separation of other metals such as Cd, As, Sn, Sb, Th, rare earths, etc ...
  • the present invention relates more particularly to the methods of separation of different metals contained at low concentrations in hyperacid media, by ionic flotation, in accordance with the above provisions, as well as the means for the implementation of these methods and the production lines. concentrated acids in which said metal separation processes are included.
  • the attached graph represents the curve of the variation in recovery as a function of ⁇ , in industrial phosphoric acid.
  • Phosphoric acid solutions are prepared at concentrations of 1, 2, 3.7 and 5.5 M.
  • the concentration of each solution in Cd 2+ is 5.10 4 M.
  • a suitable surface-active flotation agent such as diethyldithiophosphate, in the phosphoric acid solution, at a concentration of 4 times that of cadmium, or 2.10 -3 M. for 20 minutes. It is observed during packaging that the "diethyldithiophosphate-cadmium" coprecipitate appears more quickly in media concentrated in acid.
  • The% of Cadmium eliminated increases when the phosphoric acid concentration increases, due to the fact that cadmium is less and less solvated in concentrated phosphoric acid media (N. BENLAKHDIM Doctoral thesis of the 3rd Cycle, Laboratory of Analytical Chemistry and Electro - chemistry, University of Nancy I, July 1981).
  • the procedure is the same as in Example 5 but the concentration of the diethyldithiophosphate used as an anionic flotation agent is varied, for an H 3 P0 4 concentration of 5.5 M.
  • the ratio W is defined such that:
  • Phosphoric acid solutions are prepared at concentrations of 2.0, 3.7 and 5.5M.
  • concentration of As III in each solution is 5.10 -4 M.
  • a suitable flotation surfactant such as diethylphosphate, in the phosphoric acid solution, so that the ratio

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  • Manufacture And Refinement Of Metals (AREA)
  • Gas Separation By Absorption (AREA)
  • Physical Water Treatments (AREA)
EP83401389A 1982-07-16 1983-07-06 Verfahren zur Abscheidung von Metallen aus hypersauren Medien durch ionische Flotation Expired EP0099804B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83401389T ATE33564T1 (de) 1982-07-16 1983-07-06 Verfahren zur abscheidung von metallen aus hypersauren medien durch ionische flotation.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8212450 1982-07-16
FR8212450A FR2530161A1 (fr) 1982-07-16 1982-07-16 Perfectionnements apportes aux procedes de separation de metaux contenus dans des milieux hyperacides, par flottation ionique

Publications (3)

Publication Number Publication Date
EP0099804A2 true EP0099804A2 (de) 1984-02-01
EP0099804A3 EP0099804A3 (en) 1984-03-28
EP0099804B1 EP0099804B1 (de) 1988-04-20

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EP83401389A Expired EP0099804B1 (de) 1982-07-16 1983-07-06 Verfahren zur Abscheidung von Metallen aus hypersauren Medien durch ionische Flotation

Country Status (4)

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EP (1) EP0099804B1 (de)
AT (1) ATE33564T1 (de)
DE (1) DE3376299D1 (de)
FR (1) FR2530161A1 (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986003142A1 (fr) * 1984-11-30 1986-06-05 Institut National De Recherche Chimique Appliquee Perfectionnement apporte a la separation et a la recuperation de solides a partir de liquides les contenant et faisant appel au procede de flottation ionique, et moyen pour la mise en oeuvre de ce perfectionnement
GB2203602A (en) * 1987-03-26 1988-10-19 British Petroleum Co Plc Pipe containing conductor with connector at each end
KR100886178B1 (ko) * 2006-12-05 2009-02-27 한국전자통신연구원 이득 특성과 대역폭 특성이 향상된 제한 증폭기
US20170352917A1 (en) * 2015-02-27 2017-12-07 Fujifilm Corporation Solid electrolyte composition, electrode sheet for battery and method for manufacturing the same, and all solid state secondary battery and method for manufacturing the same
CN109482356A (zh) * 2018-12-05 2019-03-19 核工业北京化工冶金研究院 一种铌钛铀矿浮选的组合捕收剂及方法
WO2024191280A1 (fr) 2023-03-16 2024-09-19 Universite Mohammed VI Polytechnique Procédé de traitement de l'acide phosphorique par flottation ionique
CN121528604A (zh) * 2026-01-19 2026-02-13 南华大学 一种Ce2S3@Fe复合材料及其制备方法和应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120192064B (zh) * 2025-05-26 2025-08-01 浙江大学 一种高纯石英砂提纯中的浮选废水处理方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2750254A (en) * 1949-11-16 1956-06-12 Robert A Blake Process of recovering uranium from its ores
GB911792A (en) * 1958-06-04 1962-11-28 Felix Sebba A process for removing or concentrating ions from aqueous solutions
US3570772A (en) * 1969-08-22 1971-03-16 American Cyanamid Co Di(4-5 carbon branched primary alkyl) dithiophosphate promoters for the flotation of copper middlings
FI59538C (fi) * 1977-05-04 1981-09-10 Berol Kemi Ab Saett att anrika sulfidisk nickelmalm
US4289609A (en) * 1978-05-02 1981-09-15 Uranium Recovery Corporation Process for removing solid organic materials and other impurities from wet-process phosphoric acid
US4278640A (en) * 1979-03-19 1981-07-14 International Minerals & Chemical Corporation Method for solvent extraction of metallic mineral values from acidic solutions
US4263148A (en) * 1979-04-09 1981-04-21 Earth Sciences, Inc. Process for removing humic matter from phosphoric acid solutions

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986003142A1 (fr) * 1984-11-30 1986-06-05 Institut National De Recherche Chimique Appliquee Perfectionnement apporte a la separation et a la recuperation de solides a partir de liquides les contenant et faisant appel au procede de flottation ionique, et moyen pour la mise en oeuvre de ce perfectionnement
FR2574002A1 (fr) * 1984-11-30 1986-06-06 Inst Nat Rech Chimique Perfectionnement apporte a la separation et a la recuperation de solides a partir de liquides les contenant et faisant appel au procede de flottation ionique, et moyen pour la mise en oeuvre de ce perfectionnement
US4844873A (en) * 1984-11-30 1989-07-04 Institut National De Recherche Chimique Applique Separation and recovery of solids from liquids containing them using the ionic flotation process
GB2203602A (en) * 1987-03-26 1988-10-19 British Petroleum Co Plc Pipe containing conductor with connector at each end
GB2203602B (en) * 1987-03-26 1990-11-14 British Petroleum Co Plc Electrical cable assembly
KR100886178B1 (ko) * 2006-12-05 2009-02-27 한국전자통신연구원 이득 특성과 대역폭 특성이 향상된 제한 증폭기
US20170352917A1 (en) * 2015-02-27 2017-12-07 Fujifilm Corporation Solid electrolyte composition, electrode sheet for battery and method for manufacturing the same, and all solid state secondary battery and method for manufacturing the same
CN109482356A (zh) * 2018-12-05 2019-03-19 核工业北京化工冶金研究院 一种铌钛铀矿浮选的组合捕收剂及方法
WO2024191280A1 (fr) 2023-03-16 2024-09-19 Universite Mohammed VI Polytechnique Procédé de traitement de l'acide phosphorique par flottation ionique
FR3146604A1 (fr) 2023-03-16 2024-09-20 Universite Mohammed VI Polytechnique Procédé de traitement de l’acide phosphorique par flottation ionique
CN121528604A (zh) * 2026-01-19 2026-02-13 南华大学 一种Ce2S3@Fe复合材料及其制备方法和应用
CN121528604B (zh) * 2026-01-19 2026-03-27 南华大学 一种Ce2S3@Fe复合材料及其制备方法和应用

Also Published As

Publication number Publication date
DE3376299D1 (en) 1988-05-26
FR2530161A1 (fr) 1984-01-20
EP0099804A3 (en) 1984-03-28
EP0099804B1 (de) 1988-04-20
ATE33564T1 (de) 1988-05-15
FR2530161B1 (de) 1985-01-25

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