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WO2010057329A1 - Procédé sono-électrochimique permettant de traiter des concentrés de sulfures métalliques - Google Patents

Procédé sono-électrochimique permettant de traiter des concentrés de sulfures métalliques Download PDF

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Publication number
WO2010057329A1
WO2010057329A1 PCT/CL2009/000022 CL2009000022W WO2010057329A1 WO 2010057329 A1 WO2010057329 A1 WO 2010057329A1 CL 2009000022 W CL2009000022 W CL 2009000022W WO 2010057329 A1 WO2010057329 A1 WO 2010057329A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper
cell
chamber
chalcopyrite
membrane
Prior art date
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.)
Ceased
Application number
PCT/CL2009/000022
Other languages
English (en)
Spanish (es)
Inventor
Ejnar Humberto Trollund Orellana
Luis Francisco Javier Gaete Garreton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rb Ingenieria Ltda
Original Assignee
Rb Ingenieria Ltda
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 Rb Ingenieria Ltda filed Critical Rb Ingenieria Ltda
Publication of WO2010057329A1 publication Critical patent/WO2010057329A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
    • 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
    • C22B3/02—Apparatus therefor
    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/045—Leaching using electrochemical processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • 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

  • Patent document US2006 / 0219571 discloses a method and apparatus for recovering precious metals by leaching using electro-generated chlorine, more precisely, the electrolixiviation apparatus is composed of two reaction chambers on both sides (one right and one left), where said chambers are divided by a central membrane; One of the reaction chambers is a leaching chamber that is equipped with an electrode for the electro generation of chlorine, to form stable chlorine, also having an agitator for the solution. The other reaction chamber is a reduction chamber equipped with electrodes used for the total or partial electrolytic recovery of the leached precious metal compounds.
  • the Apparatus may also include a separator / purifier for rapid recovery of certain precious metals, if necessary.
  • the invention disclosed in US2006 / 0219571 provides a simple method of leaching and an apparatus for carrying it out, which has a high efficiency in leaching and allows the recovery of precious metals leached.
  • Figure 3 corresponds to a diagram of a chalcopyrite particle of the prior art treated with reagents, where the ultrasonic waves break Ia sulfur layer, with which reagents can continuously attack the chalcopyrite.
  • Figure 8 corresponds to a block diagram, showing the input and output elements of the process with the material balance.
  • a first modality of a cell (6) of the present invention consisting of walls (7) and a floor (8), in which there are at least two chambers.
  • the first anodic chamber (9) has an anode (10) which is between the first membrane (11) and the second membrane (14), among which is the anolyte (17) and in the second
  • the cathode chamber (12) shows the cathode (13) which is between the second membrane (14) and the first membrane (11) of the subsequent anodic chamber, among which the catholyte (18).
  • the ultrasonic wave allows a greater diffusion rate of the reactants and products of the reaction to and from the surface of the solid and the sinus of the liquid, leaving the chalcopyrite particle accessible to the reagents. That is, maintaining the active sites in the particle where the reaction occurs.
  • the dissolution reaction of the chalcopyrite is "naturally" difficult due to the refractory and insoluble nature of the CuFeS 2 (S) species.
  • the reaction occurs in a combination of phases, it is a heterogeneous and microporic reaction, this is in addition to occurring in the pores of the particle, it also occurs in a solid-liquid interface, where important species diffusion processes are being generated between the phases .
  • the ultrasound favors the formation of chlorine gas by: Increasing mass transport, Chloride, from within the solution to the electrode / electrolyte interface; decrease of the thickness of the diffusional layer and of the anodic overpotential. Rapid release of chlorine gas bubbles formed on the electrode surface, facilitating the discharge of chlorine. Effect on electrolyte dissolution:
  • the copper deposition process is favored by ultrasound because the thickness of the diffusion layer in the electrode / electrolyte interface decreases; improves mass transport, Cu 2+ , in this interface which produces a decrease in the overload potential of said metal. (Lower energy consumption in the process).
  • the metal sulfide is dispersed to be treated in the electrolyte.
  • the electrolyte initially consists of a solution of sulfuric acid, hydrochloric acid and water.
  • chlorine is generated electrochemically at the anode, by oxidation of the chloride ions present in the electrolyte.
  • chlorine and its chlorinated derivatives oxidize metal sulphides generating the respective cationic species in solution; finally, metals, including copper, are recovered by a reduction in the cathode.
  • the process is capable of recovering metals and nonmetals, including iron and sulfur, by crystallization of species and separation of the generated solutions.
  • the process described is characterized by the simultaneous obtaining of: Chlorine and its compounds derived by the anodic oxidation of the chloride ion present in the electrolyte. Recovery by cathodic reduction of dissolved metal ions, by the action of chlorine in the chalcopyrite.
  • the anodic chamber (9) isolated from the cathodic (12), of an electrochemical cell is continuously fed with copper Chalcopyrite concentrate
  • the kinetics of the dissolution reaction is favored by the ultrasonic waves that are applied to the cell.
  • Equation (15) is obtained the reaction that governs the global process:
  • the catholyte solution contains mostly FeSO 4 (aq) whose solubility is highly favored by the temperature of the solution.
  • This previously cooled solution is taken to a crystallizer, strongly decreasing the solubility of the salt, precipitating the FeSO 4 x 7 H 2 O.
  • the suspension of the crystallized salt is taken to a thickener, which transforms this flow into a pulp that can be sent filtration equipment.
  • the supernatant liquid of the FeSO 4 thickener is sent to a second stage of crystallization to improve the efficiency of the process.
  • the pulp is deposited in a moving filter cloth (Alternatively it can be by Centrifugation) where the pulp is partially dried, generating a cake of approximately 50% humidity, in the filtration leaching water will be added to improve the purity of the product.
  • the cake is stored in outdoor storage fields so that additional drying is generated and subsequently fed into drying equipment where dry salt is finally obtained.
  • the filtered liquid contains an appreciable amount of FeSO 4 (fine crystals) and is recirculated to the crystallizer to take advantage of the product containing this liquid.
  • the process also contemplates the following steps: k) cooling the catholyte solution to precipitate the Iron Sulfate; I) bring the cooled solution to a device to crystallize the Iron Sulfate and separate the supernatant that is a solution of Sulfuric Acid as a product: m) subject the decanted crystals to a thickening stage generating a pulp; n) filter the pulp to remove excess solution producing a crystal cake; o) Drying the cake to produce dry iron sulfate.
  • the water and acid that is lost in any industrial process must be replaced.
  • the amount of water required, in general, is stoichiometric, according to the needs of each plant this may vary.
  • the chalcopyrite that is taken out of the cell and is not treated in the subsequent processes can be fed back.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention concerne un procédé permettant le traitement de concentrés de sulfures de cuivre, par exemple, la chalcopyrite, réalisé dans une cellule constituée de parois et d'un sol à l'intérieur de laquelle se trouvent au moins deux chambres; une première chambre anodique pourvue d'une anode et d'une première membrane, une seconde chambre cathodique pourvue d'une cathode et d'une seconde membrane. Le procédé susmentionné comprend les étapes suivantes: a) préparer l'électrolyte en dehors de ces chambres, au moyen d'une combinaison d'acides sulfurique, d'acide chlorhydrique et d'eau; b) charger la première chambre anodique et la seconde chambre cathodique avec l'électrolyte préparé à l'étape a); c) charger le concentré de sulfures de cuivre dans la chambre anodique; d) agiter l'anolyte mélangé à la chalcopyrite; e) connecter les électrodes de la cellule à la source d'énergie électrique pour générer du chlore dans l'anode; f1) générer dans la chambre anodique des ondes ultrasonores pour détruire la couche de soufre qui recouvre les particules de chalcopyrite, améliorant significativement la vitesse de lixiviation; f2) simultanément, dans la chambre cathodique, procéder à l'électrodéposition du cuivre métallique provenant du cuivre lixivié de la chambre anodique; g) ajuster le potentiel électrique de la cellule afin que se produise le dépôt du cuivre, ce qui évite certaines réactions non souhaitables de réduction d'autres espèces ioniques présentes dans la solution; h) régler la température autour de 50°C; i) alimenter en continu l'anolyte de la cellule en concentré de sulfures de cuivre et en eau, de manière à générer en continu les espèces HCI, H2SO4, FeSO4 y CuSO4, lesquelles sont dissoutes sous une forme ionique; y j) retirer en continu la solution de catholyte de la chambre cathodique.
PCT/CL2009/000022 2008-11-18 2009-11-17 Procédé sono-électrochimique permettant de traiter des concentrés de sulfures métalliques Ceased WO2010057329A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CL3423-2008 2008-11-18
CL2008003423A CL2008003423A1 (es) 2008-11-18 2008-11-18 Proceso para tratar concentrados sulfurados de cobre en celda de dos camaras, anodica y catodica, con primera y segunda membranas, respectivamente, donde el electrolito, combinacion de h2so4 y hci con agua, se cargan en ambas camaras y el concentrado se carga en la camara anodica, donde se generan ondas ultrasonicas; y celda.

Publications (1)

Publication Number Publication Date
WO2010057329A1 true WO2010057329A1 (fr) 2010-05-27

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Family Applications (1)

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PCT/CL2009/000022 Ceased WO2010057329A1 (fr) 2008-11-18 2009-11-17 Procédé sono-électrochimique permettant de traiter des concentrés de sulfures métalliques

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CL (1) CL2008003423A1 (fr)
WO (1) WO2010057329A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2434065C1 (ru) * 2010-08-31 2011-11-20 УЧРЕЖДЕНИЕ РОССИЙСКОЙ АКАДЕМИИ НАУК ИНСТИТУТ МЕТАЛЛУРГИИ УРАЛЬСКОГО ОТДЕЛЕНИЯ РАН (ИМЕТ УрО РАН) Способ переработки сульфидных медно-никелевых сплавов
WO2011150984A1 (fr) 2010-06-01 2011-12-08 Voldemars Belakovs Procédé de récupération de métaux nobles et d'autres sous-produits à partir d'un minerai
CN108707926A (zh) * 2018-06-19 2018-10-26 福建洋屿环保科技股份有限公司 一种废金刚石刀头电浸取回收铜工艺

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4062744A (en) * 1976-07-16 1977-12-13 The United States Of America As Represented By The Secretary Of The Interior Extraction of copper from sulfide ores

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4062744A (en) * 1976-07-16 1977-12-13 The United States Of America As Represented By The Secretary Of The Interior Extraction of copper from sulfide ores

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
ARRIAGADA P.A.: "Diseno, construccion and optimizacion of una celda of electro obtencion de cobre con cáthe whole particulado móvil basada in electrodiáfisis reactiva", TESIS DEPARTAMENTO INGENIERÍA OF MINAS., December 2006 (2006-12-01), Retrieved from the Internet <URL:http://www.cybertesis.cl/tesis/uchile/2006/arriagada_p/html/index-frames.html> *
CIFUENTES L. ET AL.: "Aspects of the devolpment of a copper electrowinning cell based on reactive electrodialysis", CHEMICAL ENGINEERING SCIENCE, vol. 59, 2004, pages 1087 - 1101 *
FAROOQ R. ET AL.: "Effect of ultrasound on the removal of copper from the modthe solutions for copper electrolysis process", WATER RESEARCH., vol. 36, 2002, pages 3165 - 3169 *
REISSE, J. ET AL.: "Sonoelectrochemistry in aqueous electrolyte: a new type of sonoelectroreactor", ELECTROCHIMICA ACTA., vol. 39, no. 1, 1994, pages 37 - 39 *
SCHNEIDER O. ET AL.: "Application of the electrochemical quartz crystal microbalance technique to copper sonoelectrochemistry. Part 1. Sulfate-based electrolytes", ELECTROCHIMICA ACTA., vol. 53, 2008, pages 5485 - 5495 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011150984A1 (fr) 2010-06-01 2011-12-08 Voldemars Belakovs Procédé de récupération de métaux nobles et d'autres sous-produits à partir d'un minerai
RU2434065C1 (ru) * 2010-08-31 2011-11-20 УЧРЕЖДЕНИЕ РОССИЙСКОЙ АКАДЕМИИ НАУК ИНСТИТУТ МЕТАЛЛУРГИИ УРАЛЬСКОГО ОТДЕЛЕНИЯ РАН (ИМЕТ УрО РАН) Способ переработки сульфидных медно-никелевых сплавов
CN108707926A (zh) * 2018-06-19 2018-10-26 福建洋屿环保科技股份有限公司 一种废金刚石刀头电浸取回收铜工艺

Also Published As

Publication number Publication date
CL2008003423A1 (es) 2010-10-29

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