WO2013030741A2 - Procédé de récupération de molybdène de qualité technique à partir de solutions acides diluées de lixiviation, hautement concentrées en arsenic provenant de résidus métallurgiques - Google Patents

Procédé de récupération de molybdène de qualité technique à partir de solutions acides diluées de lixiviation, hautement concentrées en arsenic provenant de résidus métallurgiques Download PDF

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Publication number
WO2013030741A2
WO2013030741A2 PCT/IB2012/054308 IB2012054308W WO2013030741A2 WO 2013030741 A2 WO2013030741 A2 WO 2013030741A2 IB 2012054308 W IB2012054308 W IB 2012054308W WO 2013030741 A2 WO2013030741 A2 WO 2013030741A2
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WO
WIPO (PCT)
Prior art keywords
solution
molybdenum
recovery
pls
technical grade
Prior art date
Application number
PCT/IB2012/054308
Other languages
English (en)
Spanish (es)
Other versions
WO2013030741A3 (fr
Inventor
Felipe Andrés LAGNO SÁNCHEZ
Ricardo Fernando SEPÚLVEDA LETELIER
Marcelo Gustavo ACUÑA GOYCOLEA
Original Assignee
Ecometales Limited
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 Ecometales Limited filed Critical Ecometales Limited
Priority to US14/240,567 priority Critical patent/US9279168B2/en
Priority to CN201280041055.6A priority patent/CN103906709B/zh
Priority to CA2844874A priority patent/CA2844874C/fr
Priority to MX2014002072A priority patent/MX349312B/es
Publication of WO2013030741A2 publication Critical patent/WO2013030741A2/fr
Publication of WO2013030741A3 publication Critical patent/WO2013030741A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/02—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/05—Processes using organic exchangers in the strongly basic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/07—Processes using organic exchangers in the weakly basic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/05—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds
    • B01J49/07—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds containing anionic exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
    • B01J49/57—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for anionic exchangers

Definitions

  • the present invention discloses a process for obtaining technical grade molybdenum trioxide from dilute acid leaching solutions (PLS) with a high concentration of arsenic, antimony or bismuth. Said solution is obtained through the leaching of metallurgical residues with high concentration of these impurities such as smelting powders.
  • PLS dilute acid leaching solutions
  • the present invention discloses a process for recovering molybdenum by ion exchange, through which molybdenum is separated from other metals also present in said solution by using ion exchange resins and controlled precipitation of As, Sb and Bi with magnesium or iron salts, followed by a precipitation of ammonium molybdate which is subsequently calcined to obtain technical grade molybdenum trioxide.
  • a mining process or method is the sum of methods by which, from a deposit, metals and / or metal compounds of commercial purity and quality are obtained, in a cost-effective manner and with an acceptable environmental impact.
  • one or more mineral values contained in an ore or concentrate are dissolved, generally using an aqueous solution of the leaching agent.
  • the term can also be extended to include the dissolution of secondary materials such as scrap, waste and scrap.
  • Leaching produces an aqueous solution rich in the extracted valuable metal ions (PLS) from which it must be possible to separate this metal and recover it with a high level of purity.
  • PLS valuable metal ions
  • a solid or gravel residue is produced which, ideally, has a sufficiently low content in the leached mineral values as to be discarded to a dump or tranque.
  • leaching may have a different objective than the one stated above. For example when a concentrate is leached to selectively remove certain impurities, and thus increase the quality of the concentrate (for example the removal of copper from molybdenite concentrates).
  • the leaching processes are not necessarily selective and, consequently, leaching solutions are produced that contain, in addition to the metal of interest, a varied range of impurities. This added to the fact that the concentration of the metal of interest may not be very high, makes it impossible to directly recover the metal of interest from the leaching solution, so that these solutions must be previously treated through purification and enrichment stages.
  • Purification eliminates impurities, selectively isolating valuable elements.
  • the enrichment of the solutions is also particularly beneficial for reducing the volumes of solution to be treated in the subsequent stages of metal recovery. This helps to reduce investment costs and increase recovery efficiency.
  • a process for recovering molybdenum in the form of molybdenum trioxide from dilute acidic solutions of leaching of metallurgical residues, with high arsenic, antimony or bismuth content is disclosed.
  • the object of the present invention is to recover molybdenum by ion exchange contained in leaching solutions diluted in molybdenum but which nevertheless contain a high concentration of arsenic, among others, in order to obtain a molybdenum product efficiently and economically profitably.
  • US 4,596,701 discloses a process for the purification of molybdenum trioxide, specifically discloses a method for the preparation of ammonium molybdate comprising contacting said concentrate with an aqueous solution of sulfuric acid, ammonium, sulfate and ammonium persulfate. to solubilize at least 2% of the molybdenum values of said concentrate.
  • the process of the present invention discloses the recovery of molybdenum by means of ion exchange, followed by an increase in the concentration of molybdenum in the regenerant, precipitation of impurities, precipitation of molybdenum, then drying and calcining to obtain the final product of molybdenum trioxide grade technician, as shown in Figure 1.
  • the present invention discloses a process for recovering about 70% or more specifically about 90% of the molybdenum present in the PLS as Mo0 3 technical grade.
  • the invention consists in the selective recovery of molybdenum, in the form of Mo0 3 , from the PLS solution generated from the leaching of smelting powders.
  • the present invention develops a molybdenum recovery process via ion exchange.
  • the process was validated on a pilot scale and the fundamental aspects of the process, validation stages and the methodology of industrial scaling as disclosed in the present invention, demonstrate a novel and inventive height process.
  • the ion exchange process consists of two stages that are repeated in ion exchange cycles: loading and regeneration of the resin; each followed by water wash stages.
  • the resin loading process consisted of capturing the molybdenum ion in the form of molybdate from the acid leaching solution, while the resin regeneration process consisted of the re-extraction or discharge of the molybdate ion by an alkaline regenerating solution.
  • the equations corresponding to the process are shown below:
  • R represents the ion exchange resin.
  • the resin used in this process is of the weak base anionic type or weak / strong base anionic type, presenting functional groups selected from secondary, tertiary amines, tertiary / quaternary amines and polyamines.
  • Molybdenum extraction with ion exchange resins is carried out by contacting the PLS solution containing Mo with an anionic resin. This contact can be carried out discontinuously, adding the resin to the solution and stirring, or continuously using columns.
  • the Mo loaded in the resin must be discharged by contacting the charged resin with an alkaline solution of ammonium hydroxide, where a Mo-laden solution contaminated in As, Sb or Bi is obtained which is partially co-extracted with the Mo
  • the removal of these impurities can be carried out by precipitation with a magnesium or iron salt where a solid product is obtained that must be treated for a subsequent disposal and obtain a regenerating solution loaded in Mo and virtually free of impurities (Fig. 2 ).
  • the chemical reactions using magnesium sulfate for arsenic, antimony and bismuth precipitations are:
  • the last stage to obtain molybdenum tritoxide is the calcination stage, where the ammonium molybdate precipitate is subjected to controlled heating from 20 to 700 ° C.
  • the temperature profile used ( Figure 3) that allows obtaining in the calcination stage of the present invention considers: one . - Heating from 20 to 260 ° C and maintenance for approximately 20 minutes to 2 hours, for hydration water removal.
  • step 4 Wash the post discharge resin with water, step similar to step 2. 5.- Add a magnesium or iron salt, such as magnesium sulfate, magnesium chloride or ferric sulfate, to the solution obtained in step 3, to obtain a pulp with a precipitate of arsenic and other impurities, which is separated into 2 lines: the obtained ammonia solution containing the Mo passes to the molybdenum precipitation stage and the solid obtained is taken to a stage of despondency and external arrangement to the process of the present invention. 6.
  • a magnesium or iron salt such as magnesium sulfate, magnesium chloride or ferric sulfate
  • step 5 Add H 2 S0 4 to the ammonia solution obtained in step 5 to precipitate molybdenum in the form of ammonium molybdate ((NhU ⁇ MosC ⁇ e) in an acidic environment between pH 1, 5 and 4, more preferably at pH 3.3 and in a temperature range between 50 2 C and 90 2 C more preferably at 70 2 C.
  • ammonium molybdate ((NhU ⁇ MosC ⁇ e)
  • step 7 Separate the precipitate from step 6, by filtration of the molybdate and the solution obtained is recycled to mix with the initial PLS solution.
  • the charged regenerating solution was fed to a 5 L impurity precipitation reactor, contacting it with 215.8 g magnesium sulfate (5% above the stoichiometric value).
  • the pulp was allowed to react for 120 min.
  • the solid was filtered and washed to be disposed.
  • the results obtained showed a high efficiency of impurity precipitation, obtaining a solution with only 41 mg / L of As and with concentrations of Sb and Bi under 10 mg / L. There was no co-precipitation of Mo.
  • the final molybdenum product exceeds conventional commercial concentration standards.
  • the purity obtained is compatible with the conventional market of technical grade molybdenum trioxide.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

La présente invention concerne un procédé de récupération de molybdène de qualité technique à partir de solutions acides diluées de lixiviation, hautement concentrées en arsenic, ledit procédé comprenant les étapes consistant à: (a) mettre en contact une solution acide de lixiviation préalablement filtrée provenant de la lixiviation des poussières de fonderie avec une résine anionique d'échange d'ions; (b) laver à l'eau la résine chargée; (c) extraire le molybdène de la résine d'échange d'ions avec une solution régénérante alcaline d'ammonium à une valeur de pH comprise entre 8 et 12, pour former du molybdate d'ammonium en solution; (d) laver à l'eau, la résine déchargée; (e) ajouter des sels de magnésium et/ou de fer à la solution ammoniacale récupérée pour obtenir un précipité qui est soumis à l'étape d'élimination de l'arsenic, et une solution qui contient le molybdate d'ammonium en solution; (f) ajouter de l'acide sulfurique à la solution ammoniacale exempte d'arsenic, pour précipiter le molybdène sous forme de molybdate d'ammonium dans un milieu acide à une valeur de pH comprise entre 1,5 et 4; (g) séparer le précipité formé par filtration du molybdate et remettre en circulation la solution obtenue dans la solution initiale de solution acide de lixiviation; (h) calciner le précipité séparé pour obtenir du trioxyde de molybdène et de l'ammoniac; et (i) récupérer l'ammoniac séparé en vue de son renvoi ultérieur dans le processus en tant que solution régénérante recirculée.
PCT/IB2012/054308 2011-08-26 2012-08-24 Procédé de récupération de molybdène de qualité technique à partir de solutions acides diluées de lixiviation, hautement concentrées en arsenic provenant de résidus métallurgiques WO2013030741A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US14/240,567 US9279168B2 (en) 2011-08-26 2012-08-24 Process for recovery of technical grade molybdenum from diluted leaching acid solutions (PLS), with highly concentrated arsenic, from metallurgical residues
CN201280041055.6A CN103906709B (zh) 2011-08-26 2012-08-24 从含有高浓度砷的冶金废渣稀酸浸溶液(pls)中回收工业级钼的方法
CA2844874A CA2844874C (fr) 2012-08-24 2012-08-24 Procede de recuperation de molybdene de qualite technique a partir de solutions acides diluees de lixiviation, hautement concentrees en arsenic provenant de residus metallurgiques
MX2014002072A MX349312B (es) 2011-08-26 2012-08-24 Proceso para la recuperacion de molibdeno grado tecnico a partir de soluciones acidas diluidas de lixiviacion (pls), altamente concentradas en arsenico, provenientes de residuos metalurgicos.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CL20952011 2011-08-26
CL2095-2011 2011-08-26

Publications (2)

Publication Number Publication Date
WO2013030741A2 true WO2013030741A2 (fr) 2013-03-07
WO2013030741A3 WO2013030741A3 (fr) 2013-04-25

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3681016A (en) * 1970-12-02 1972-08-01 Continental Ore Corp Recovery of rhenium and molybdenum values from solution
US4273745A (en) * 1979-10-03 1981-06-16 Amax Inc. Production of molybdenum oxide from ammonium molybdate solutions
US4596701A (en) * 1984-02-29 1986-06-24 Gte Products Corporation Process for purifying molybdenum trioxide
ES2004072A6 (es) * 1986-01-23 1988-12-01 France Mokta Comp Procedimiento para la separacion de molibdeno por via resina
US4891067A (en) * 1988-05-13 1990-01-02 Kennecott Utah Copper Corporation Processes for the treatment of smelter flue dust

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3681016A (en) * 1970-12-02 1972-08-01 Continental Ore Corp Recovery of rhenium and molybdenum values from solution
US4273745A (en) * 1979-10-03 1981-06-16 Amax Inc. Production of molybdenum oxide from ammonium molybdate solutions
US4596701A (en) * 1984-02-29 1986-06-24 Gte Products Corporation Process for purifying molybdenum trioxide
ES2004072A6 (es) * 1986-01-23 1988-12-01 France Mokta Comp Procedimiento para la separacion de molibdeno por via resina
US4891067A (en) * 1988-05-13 1990-01-02 Kennecott Utah Copper Corporation Processes for the treatment of smelter flue dust

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