WO2016016406A1 - Cellule d'extraction électrolytique de métal - Google Patents

Cellule d'extraction électrolytique de métal Download PDF

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Publication number
WO2016016406A1
WO2016016406A1 PCT/EP2015/067600 EP2015067600W WO2016016406A1 WO 2016016406 A1 WO2016016406 A1 WO 2016016406A1 EP 2015067600 W EP2015067600 W EP 2015067600W WO 2016016406 A1 WO2016016406 A1 WO 2016016406A1
Authority
WO
WIPO (PCT)
Prior art keywords
anodic
bar
cell according
anode
hanger bar
Prior art date
Application number
PCT/EP2015/067600
Other languages
English (en)
Inventor
Alessandro FIORUCCI
Luciano Iacopetti
Giuseppe Faita
Original Assignee
Industrie De Nora S.P.A.
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
Priority to CN201580040191.7A priority Critical patent/CN106574385B/zh
Priority to MX2017001467A priority patent/MX2017001467A/es
Application filed by Industrie De Nora S.P.A. filed Critical Industrie De Nora S.P.A.
Priority to KR1020177005659A priority patent/KR20170038880A/ko
Priority to PL15752958T priority patent/PL3175020T3/pl
Priority to ES15752958.7T priority patent/ES2687602T3/es
Priority to EP15752958.7A priority patent/EP3175020B1/fr
Priority to US15/500,288 priority patent/US20170211195A1/en
Priority to BR112017002063-7A priority patent/BR112017002063A2/pt
Priority to EA201790300A priority patent/EA032134B1/ru
Priority to JP2017526016A priority patent/JP6660387B2/ja
Priority to CA2953274A priority patent/CA2953274A1/fr
Priority to AP2017009682A priority patent/AP2017009682A0/en
Priority to AU2015295324A priority patent/AU2015295324B2/en
Publication of WO2016016406A1 publication Critical patent/WO2016016406A1/fr
Priority to PH12016502567A priority patent/PH12016502567A1/en
Priority to ZA2017/00176A priority patent/ZA201700176B/en

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
    • 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
    • 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
    • C25C7/02—Electrodes; Connections 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
    • C25C7/06—Operating or servicing

Definitions

  • Electrochemical plants for non-ferrous metal deposition such as for example plants for electrolytic extraction and refining of metals, also known respectively as electrowinning and electrorefining plants, typically make use of one or more electrolysers comprising a plurality of elementary cells, each containing an anode and a cathode.
  • the anodes and the cathodes are generally arranged in the electrolytic bath in alternate positions and mutually parallel.
  • Each electrode is mechanically and electrically connected to a hanger bar and is supplied with electricity through the contact of its respective hanger bar with a busbar.
  • the same bus-bar is shared between electrodes of same polarity, mutually connected in parallel.
  • the metal produced by the electrochemical reaction is deposited under the action of the passage of electrical current onto the cathode of each elementary cell.
  • the deposited product is harvested at periodic intervals, typically of some days, upon extraction of the cathodes from the relevant electrolyser.
  • the deposition of metal onto the cathode surface may take place in a non-uniform fashion giving rise to localised deposits, also known as dendrites or dendritic formations, growing towards the facing anode at increasing speed under the effect of the electrical current passage, until the onset of an electrical short circuit.
  • the metal produced by the electrochemical reaction is deposited under the action of the passage of electrical current onto the cathode of each elementary cell.
  • the deposited product is harvested at periodic intervals, typically of some days, upon extraction of the cathodes from the relevant electrolyser.
  • the deposition of metal onto the cathode surface may take place in a non-uniform fashion giving rise to localised deposits, also known as dendrites or dendritic
  • the invention relates to a an electrolyser for the electrowinning of metals made of a plurality of elementary cells, each cell comprising an anode and a cathode with an electrically conductive porous screen interposed therebetween, the anode being provided with a catalytic surface towards oxygen evolution reaction and the cathode being suitable for the deposition of metal from an electrolytic bath.
  • the cell further comprises an electrically conductive anodic hanger bar, electrically and mechanically connected to the anode, and an electrically conductive cathodic hanger bar, electrically and mechanically connected to the cathode.
  • Each elementary cell also comprises a device suitable for direct or indirect detection of the electric current flowing across the corresponding anodic hanger bar.
  • the electrolyser is also equipped with an anodic bus-bar, electrically connected to the anodic hanger bars of each cell and a cathodic bus-bar electrically connected to the cathodic hanger bars of each cell.
  • the electrolyser may also comprise a cathodic balancing bar placed parallel and in proximity to the anodic bus-bar.
  • the conductive porous screen, interposed between the anode and the cathode of the elementary cell is a structure that can present different degrees of compactness and is made in such a way as to allow the passage of the electrolytic solution without interrupting the ionic conduction between cathode and anode.
  • the dendrites that may be formed on one or more cathodes of the elementary cells come into contact with the facing porous screen before they can reach the anodic surface aft so that their growth is stopped, or in any case slowed down. It was observed that in case a dendritic formation comes into contact with the porous screen, part of the metal produced in the cell is deposited directly on the screen as a coating, provided the screen has some electrical conductivity.
  • the assembly consisting of cathode, dendrite and porous screen, by virtue of the existing electrical connection between these elements, additionally performs the function of new cathode of the elementary cell, furthermore being placed closer to the anode than the original one.
  • the lower ohmic drop in the electrolyte associated to the reduced gap between the new cathode and the anode causes an increase in the electric current flowing across the relevant anodic hanger bar. It was found that the extent of this current increase can be used as an indication of dendrite growth.
  • the direct or indirect detection of the electric current flowing in each anodic hanger bar can be effected on the bar itself, or on elements electrically connected thereto, by means of a detection device capable of measuring voltage or temperature variations.
  • the measurement of voltage variation is effected through the connection of the detection device to the relevant anodic bus-bar on one side and to the cathodic hanger bar on the other side by means of an electrically conductive and optionally flexible pressure contact.
  • This configuration can give the advantage of avoiding fixed electrical connections on the anodic hanger bar, facilitating subsequent maintenance operations of the cell.
  • the measurement of voltage variation is effected through the connection of the detection device to the corresponding anodic hanger bar in two points, located at a certain distance along the major axis thereof.
  • the measurement of the temperature variation can be effected by means of a thermosensitive device, for example a thermocouple. This measurement may be done, for example, with the thermosensitive device installed on each anodic hanger bar, preferably in correspondence of the terminal portion thereof, or alternatively on the anodic bus-bar in correspondence with each point of contact with the anodic hanger bars.
  • the thermosensitive device may be equipped with a chemically resistant lining, suitable to protect and/or to increase its thermal insulation from the surrounding environment.
  • the measurement of the temperature variation can be effected through the use of thermochromic paints which change their colour whenever the temperature exceeds a predetermined threshold.
  • thermochromic paints which change their colour whenever the temperature exceeds a predetermined threshold.
  • Such paints are applied either on the anodic hanger bar or on the anodic bus-bar in correspondence of the point of contact with the anodic hanger bar.
  • each detection device can be connected to its own microprocessor configured for the comparison between the measurement made by the device and a predetermined reference range; if the measure does not fall within the reference range, the microprocessor can activate one or more signalling systems acting sequentially or simultaneously.
  • the microprocessor and/or the signalling system can be turned off during the operation of cathode extraction, e.g. in view of product harvesting.
  • the microprocessor can be integrated with the signalling system and/or the detection device within a single unit.
  • the microprocessor is powered by the process electrical voltage, so as to avoid the use of batteries which would require a periodic replacement.
  • the microprocessor can be connected directly to the anodic bus-bar and to the cathodic balancing bar in case the electrolyser is equipped therewith. If the electrolyser does not include a cathodic balancing bar and one wishes to avoid fixed wirings which would interfere with the plant operations, the microprocessor directed to monitor a certain anodic hanger bar can be connected to the anodic bus-bar and to the hanger bar of the adjacent cathode via a preferably flexible pressure contact.
  • the microprocessor actuates at least one signalling system consisting of a light-emitting diode which can be coupled to an optical fibre, either directly or through an optical coupling device.
  • the optical fibre optionally lined with a polymeric material, allows transferring the light signal to the terminal portions of each anodic hanger bar or even better to the outside of the electrolyser, thereby facilitating its identification by the plant operating personnel and allowing to quickly spot the electrolyser and the relevant anode or anodes presenting direct or indirect current values outside the range of predetermined values.
  • the porous screen can be made of carbon fabrics of suitable thickness.
  • the porous screen can consist of a mesh or punched sheet made of a corrosion-resistant metal, for instance titanium, provided with a coating catalytically inert towards oxygen evolution reaction.
  • the corrosion-resistant metal for instance titanium
  • catalytically inert coating can be based on tin, tantalum, niobium or titanium, for example in the form of oxides.
  • the anodes are obtained from titanium meshes or expanded sheets coated with a catalytic material.
  • the catalyst-coated titanium mesh is inserted inside an envelope consisting of a permeable separator, for example a porous sheet of polymeric material or a cation-exchange membrane, fixed to a frame and surmounted by a demister.
  • the invention relates to an anodic element for elementary cells of electrolysers for metal electrowinning comprising an anode having a catalytic surface towards oxygen evolution reaction, a porous screen, an anodic hanger bar mechanically and electrically connected to the anode and a device suitable for direct or indirect detection of the electric current flowing across the anode hanger bar.
  • the device suitable for direct or indirect detection of the electric current can be made as
  • the alert signal can be acoustic, visual, electromagnetic or of any other nature, and can consist a combination of multiple signals.
  • the invention relates to a elementary cell of an electrolyser for metal electrowinning, comprising:
  • cathode suitable for the deposition of metal from an electrolytic bath arranged parallel to said anode
  • an electrically conductive anodic hanger bar integral with the anode
  • anodic hanger bar across the anodic hanger bar; - an anodic bus-bar, electrically conductive and electrically connected to the anodic hanger bar.
  • the invention relates to a process for obtaining copper from a solution containing cuprous and/or cupric ions comprising electrolysing the solution inside an electrolyser as hereinbefore described.
  • Figure 2 schematically shows a possible system for signalling the growth of dendritic formations in an elementary cell of an electrolyser for metal electrowinning representing another embodiment of the invention.
  • Figure 1 schematically shows an elementary cell of an electrolyser for metal
  • electrowinning comprising an anode (100) and a cathode (200) suitable for the deposition of metal from an electrolytic bath arranged parallel to the anode, a porous screen (300) interposed between anode and cathode, an anodic hanger bar (400) integral with the anode and electrically connected thereto, a cathodic hanger bar (450), a device (500) suitable for direct or indirect detection of the electric current flowing across anodic hanger bar (400), an electrically conductive anodic bus-bar (600) in electrical connection with anodic hanger bar (400).
  • Device (500) suitable for direct or indirect detection of the electric current can be connected to a microprocessor (700) configured for comparing the quantity detected by device (500) with a predetermined range of values.
  • Microprocessor (700) is connected to a signalling system (800) actuated in case the detection provides a value outside the reference range.
  • Figure 2 shows a device (500) suitable for direct or indirect detection of the electric current connected to a microprocessor (700) for comparing said detection with a predetermined range of values.
  • Microprocessor (700) is configured to actuate signalling system (800) in case the detection provides a value outside the reference range.
  • Signalling system (800) can consist of a light-emitting diode (801 ) which emits a light signal in case of actuation by microprocessor (800).
  • the signal of diode (801 ) is transported by an optical fibre (803), optionally coupled to diode (800) via an optical coupling system (802).
  • the extremity of the fibre from which light signal (803) is output is placed in an appropriate position, possibly easy to identify by staff (900) operating in the plant.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

La présente invention concerne un électrolyseur permettant l'extraction électrolytique de métaux non ferreux et comprenant une pluralité de cellules élémentaires intercalées, chaque cellule élémentaire étant équipée d'un dispositif conçu pour la détection d'anomalies dans la distribution de courant électrique à l'anode respective.
PCT/EP2015/067600 2014-08-01 2015-07-30 Cellule d'extraction électrolytique de métal WO2016016406A1 (fr)

Priority Applications (15)

Application Number Priority Date Filing Date Title
EA201790300A EA032134B1 (ru) 2014-08-01 2015-07-30 Ячейка для электрохимического извлечения металла
BR112017002063-7A BR112017002063A2 (pt) 2014-08-01 2015-07-30 célula elementar de um eletrolisador para extração eletrolítica de metais, eletrolisador, processo para obter cobre, e, elemento anódico
KR1020177005659A KR20170038880A (ko) 2014-08-01 2015-07-30 금속 전해 채취용 셀
MX2017001467A MX2017001467A (es) 2014-08-01 2015-07-30 Celda para extraccion electrolitica de metal.
ES15752958.7T ES2687602T3 (es) 2014-08-01 2015-07-30 Celda para extracción electrolítica de metal
EP15752958.7A EP3175020B1 (fr) 2014-08-01 2015-07-30 Cellule d'extraction électrolytique de métal
JP2017526016A JP6660387B2 (ja) 2014-08-01 2015-07-30 金属を電解採取するためのセル
CN201580040191.7A CN106574385B (zh) 2014-08-01 2015-07-30 用于金属电积的单元
PL15752958T PL3175020T3 (pl) 2014-08-01 2015-07-30 Komórka do elektrolitycznego otrzymywania metali
US15/500,288 US20170211195A1 (en) 2014-08-01 2015-07-30 Cell for metal electrowinning
CA2953274A CA2953274A1 (fr) 2014-08-01 2015-07-30 Cellule d'extraction electrolytique de metal
AP2017009682A AP2017009682A0 (en) 2014-08-01 2015-07-30 Cell for metal electrowinning
AU2015295324A AU2015295324B2 (en) 2014-08-01 2015-07-30 Cell for metal electrowinning
PH12016502567A PH12016502567A1 (en) 2014-08-01 2016-12-21 Cell for metal electrowinning
ZA2017/00176A ZA201700176B (en) 2014-08-01 2017-01-09 Cell for metal electrowinning

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI2014A001416 2014-08-01
ITMI20141416 2014-08-01

Publications (1)

Publication Number Publication Date
WO2016016406A1 true WO2016016406A1 (fr) 2016-02-04

Family

ID=51628381

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2015/067600 WO2016016406A1 (fr) 2014-08-01 2015-07-30 Cellule d'extraction électrolytique de métal

Country Status (20)

Country Link
US (1) US20170211195A1 (fr)
EP (1) EP3175020B1 (fr)
JP (1) JP6660387B2 (fr)
KR (1) KR20170038880A (fr)
CN (1) CN106574385B (fr)
AP (1) AP2017009682A0 (fr)
AR (1) AR101935A1 (fr)
AU (1) AU2015295324B2 (fr)
BR (1) BR112017002063A2 (fr)
CA (1) CA2953274A1 (fr)
CL (1) CL2017000259A1 (fr)
EA (1) EA032134B1 (fr)
ES (1) ES2687602T3 (fr)
MX (1) MX2017001467A (fr)
PE (1) PE20170233A1 (fr)
PH (1) PH12016502567A1 (fr)
PL (1) PL3175020T3 (fr)
TW (1) TWI687550B (fr)
WO (1) WO2016016406A1 (fr)
ZA (1) ZA201700176B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180245226A1 (en) * 2017-02-24 2018-08-30 Calera Corporation Monitoring condition of electrochemical cells
US10236526B2 (en) 2016-02-25 2019-03-19 Calera Corporation On-line monitoring of process/system

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102017567B1 (ko) * 2018-11-27 2019-09-03 주식회사 웨스코일렉트로드 전해 제련용 전극 조립체
CN109879376A (zh) * 2019-03-04 2019-06-14 苏州博创环保科技有限公司 一种封闭式电化学反应装置

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DE102005005819B3 (de) * 2005-02-08 2006-03-02 Jl Goslar Gmbh Bleianode, insbesondere für die Abscheidung von Zink aus Zinklauge, und Anordnung zur Gewinnung von Zink aus Zinklauge
WO2007071713A1 (fr) * 2005-12-20 2007-06-28 Industrie De Nora S.P.A. Cellule electrolytique pour depot de metal
US20100258435A1 (en) * 2007-07-31 2010-10-14 Ancor Tecmin S.A. System for monitoring, control, and management of a plant where hydrometallurgical electrowinning and electrorefining processes for non ferrous metals.
WO2011123896A1 (fr) * 2010-04-07 2011-10-13 Mipac Pty Ltd Dispositif de surveillance
WO2013060786A1 (fr) 2011-10-26 2013-05-02 Industrie De Nora S.P.A. Compartiment anodique pour cellules d'extraction électrolytique de métaux
WO2014032085A1 (fr) * 2012-08-28 2014-03-06 Hatch Associates Pty Limited Système de gestion et de détection de courant électrique amélioré pour installations électrolytiques
US20140209455A1 (en) * 2011-09-16 2014-07-31 Industrie De Nora S.P.A. Permanent system for continuous detection of current distribution in interconnected electrolytic cells
WO2014161929A1 (fr) * 2013-04-04 2014-10-09 Industrie De Nora S.P.A. Cellule électrolytique permettant une extraction par voie électrolytique de métaux

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US6139705A (en) * 1998-05-06 2000-10-31 Eltech Systems Corporation Lead electrode
ITMO20050345A1 (it) * 2005-12-23 2007-06-24 Minipan S R L Metodo per sottigliare la pasta sfoglia alimentare, apparecchiatura meccanica per la realizzazione del metodo e pasta sfoglia alimentare prodotta secondo questo metodo
US20110177407A1 (en) * 2008-09-24 2011-07-21 Sumitomo Electric Industries, Ltd. Electrochemical reactor, method for manufacturing the electrochemical reactor, gas decomposing element, ammonia decomposing element, and power generator
FI125211B (en) * 2013-03-01 2015-07-15 Outotec Oyj Method for measuring electric current flowing in an individual electrode in an electrolysis system and arrangement for the same
FI124587B (en) * 2013-06-05 2014-10-31 Outotec Finland Oy A device for protecting anodes and cathodes in an electrolytic cell system

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005005819B3 (de) * 2005-02-08 2006-03-02 Jl Goslar Gmbh Bleianode, insbesondere für die Abscheidung von Zink aus Zinklauge, und Anordnung zur Gewinnung von Zink aus Zinklauge
WO2007071713A1 (fr) * 2005-12-20 2007-06-28 Industrie De Nora S.P.A. Cellule electrolytique pour depot de metal
US20100258435A1 (en) * 2007-07-31 2010-10-14 Ancor Tecmin S.A. System for monitoring, control, and management of a plant where hydrometallurgical electrowinning and electrorefining processes for non ferrous metals.
WO2011123896A1 (fr) * 2010-04-07 2011-10-13 Mipac Pty Ltd Dispositif de surveillance
US20140209455A1 (en) * 2011-09-16 2014-07-31 Industrie De Nora S.P.A. Permanent system for continuous detection of current distribution in interconnected electrolytic cells
WO2013060786A1 (fr) 2011-10-26 2013-05-02 Industrie De Nora S.P.A. Compartiment anodique pour cellules d'extraction électrolytique de métaux
WO2014032085A1 (fr) * 2012-08-28 2014-03-06 Hatch Associates Pty Limited Système de gestion et de détection de courant électrique amélioré pour installations électrolytiques
WO2014161929A1 (fr) * 2013-04-04 2014-10-09 Industrie De Nora S.P.A. Cellule électrolytique permettant une extraction par voie électrolytique de métaux

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10236526B2 (en) 2016-02-25 2019-03-19 Calera Corporation On-line monitoring of process/system
US20180245226A1 (en) * 2017-02-24 2018-08-30 Calera Corporation Monitoring condition of electrochemical cells

Also Published As

Publication number Publication date
MX2017001467A (es) 2017-05-10
TW201606139A (zh) 2016-02-16
AU2015295324B2 (en) 2019-11-28
PE20170233A1 (es) 2017-04-19
EA201790300A1 (ru) 2017-06-30
EP3175020A1 (fr) 2017-06-07
CN106574385B (zh) 2020-06-05
PH12016502567B1 (en) 2017-04-17
TWI687550B (zh) 2020-03-11
JP2017524074A (ja) 2017-08-24
ES2687602T3 (es) 2018-10-26
JP6660387B2 (ja) 2020-03-11
CL2017000259A1 (es) 2017-07-21
PL3175020T3 (pl) 2018-12-31
AP2017009682A0 (en) 2017-01-31
US20170211195A1 (en) 2017-07-27
PH12016502567A1 (en) 2017-04-17
EP3175020B1 (fr) 2018-07-18
KR20170038880A (ko) 2017-04-07
BR112017002063A2 (pt) 2018-01-30
CA2953274A1 (fr) 2016-02-04
AU2015295324A1 (en) 2017-01-12
CN106574385A (zh) 2017-04-19
EA032134B1 (ru) 2019-04-30
ZA201700176B (en) 2018-08-29
AR101935A1 (es) 2017-01-25

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