US20150034491A1 - Anode and method of operating an electrolysis cell - Google Patents

Anode and method of operating an electrolysis cell Download PDF

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Publication number
US20150034491A1
US20150034491A1 US14/382,709 US201314382709A US2015034491A1 US 20150034491 A1 US20150034491 A1 US 20150034491A1 US 201314382709 A US201314382709 A US 201314382709A US 2015034491 A1 US2015034491 A1 US 2015034491A1
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Prior art keywords
anode
cell
electrolyte
attached
conductive element
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Abandoned
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US14/382,709
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English (en)
Inventor
Ville Nieminen
Michael H. Barker
Henri Virtanen
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Outotec Finland Oy
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Outotec Finland Oy
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Assigned to OUTOTEC (FINLAND) OY reassignment OUTOTEC (FINLAND) OY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NIEMINEN, VILLE, BARKER, MICHAEL H., VIRTANEN, HENRI
Publication of US20150034491A1 publication Critical patent/US20150034491A1/en
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    • 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
    • C25C7/04—Diaphragms; Spacing elements
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C25D17/12—Shape or form
    • 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
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

Definitions

  • the invention relates to a new kind of anode to be used in electrowinning.
  • the invention also relates to a method of operating an electrolysis cell to be used in the electrowinning of metals.
  • Electrowinning is a process where a metal dissolved in an electrolyte is reduced on a cathode by means of an electrical current.
  • a current is passed through the anode through the electrolyte solution containing the metal value so that the metal value is extracted as it is deposited in an electroplating process onto the cathode.
  • an electrical current is applied to the sulfate based electrolysis system, metal is precipitated on the surface of the cathode and water decomposes on the anode where acid and oxygen are formed.
  • Electrowinning takes place in an electrolytic cell that contains a number of anodes and a number of cathodes arranged in an alternating manner.
  • electrowinning requires a large number of cathodes and anodes in a single electrolytic cell.
  • Anode used in electrowinning has been lead based anode, which could have a negative effect on the quality of copper deposited.
  • lead based anodes One significant disadvantage of using such lead based anodes is that during electrowinning operations small amounts of lead are released from the surface of the anode, which causes the undesirable particulates to be suspended in the electrolyte.
  • the lead sludge must be cleaned periodically from the cell bottom e.g. every 45 to 90 days, and during this time the electrowinning cell is not producing metal.
  • MMO coated anodes consist of conductive mixed metal oxide coatings on valve metal substrates, usually titanium or nickel.
  • Dimensionally Stable Anode or DSA® is a well-known type of MMO-coated anode.
  • the electrode includes a hanger bar and an electrode body including at least one conductor rod and a substrate, a connection coupling the hanger bar and the at least one conductor rod, and a seal isolating the connection.
  • An electrode comprises a hanger bar including at least one recessed hole, and an electrode body comprising at least one conductor rod press fit into said at least one recessed hole and a substrate coupled to said conductor rod.
  • Past research and development efforts have focused on ways to increase production capacity per plant area for copper electrowinning, which directly impacts on the cost-effectiveness of the electrowinning process.
  • To increase the production of the electrolysis plant and cell it is desirable to increase the current density during electrolysis, and achieve a higher deposition rate of copper on the cathodes.
  • the current density on the cathode side is limited by the quality of the copper deposited, as due to the increased overvoltage on the cathodes more impurities are deposited with increasing current density.
  • Publication WO 2005/080640 presents a process for electrochemically winning or refining copper, where the idea of the invention is to increase the copper loading per cathode. To increase the economic efficiency of such processes and plants, it is proposed in accordance with the publication to immerse at least one cathode into the electrolyte over a length of at least 1.2 meters during operation of the electrolysis.
  • An object of the invention is to provide an anode for electrowinning process, especially when the anode is to be used with “jumbo” cathodes having a great length (of 1.2 m or longer) and for avoiding problems stabilizing the position of the anode inside the electrolytic cell.
  • the invention presents an anode for an electrowinning process in an electrolytic cell having cell walls and a bottom cell for holding an electrolyte and electrolyte feeding means.
  • the anode comprises of a hanger bar for supporting the anode, a conducting rod for distributing the current to the anode, an anode body having at least partly conductive structure, which anode body allows the penetration of the electrolyte and is at least partly covered by electrocatalytic coating, when in connection with the anode there is arranged a non-conductive element, which is restricted to the conductive structure of the anode body at least from its one side and which non-conductive element is arranged at a distance A from the electrolyte surface level, when the non-conductive element provides a means for attaching the anode to the cell.
  • the length A is arranged to be between 0.3-2 meters, which depends on the size of the electrodes and process parameters.
  • the non-conductive element of the anode is formed by excluding part of the anode body from electrocatalytic coating, for example at least 2 percent of the anode surface is excluded from electrocatalytic coating.
  • the non-conductive element is made of at least one non-conductive object attached to the anode body.
  • the anode is being attached into the electrolytic cell by anchoring elements located in the cell bottom, in the cell wall, in the electrolyte feeding means or attached to the cathode next to the anode.
  • the conductive structure of the anode body consists of a mesh structure, including preferably at least one of the following; Ti, Ni, Pb, Ta, Zr or Nb and the electrocatalytic coating consists of a Pt-group metal oxide or a mixture of metal oxides.
  • the height B between the upper part of the non-conductive element and anode bottom surface is arranged to be between 0.05-0.3 m.
  • the invention also describes a method of operating an electrolysis cell to be used in the electrowinning of metal, when metal is electrodeposited on the cathode surface from an electrolyte solution in an electrolytic cell having cell walls and a cell bottom, which cell contains electrolyte where anodes and cathodes are immersed in alternating fashion, in which the anode is supported by a hanger bar on the conducting rod, which distributes the current to the anode, when the anode body has at least a partly conductive structure allowing the penetration of the electrolyte and an electrocatalytic coating, when the anode is attached inside the electrolytic cell by a non-conductive element arranged in connection with the anode, which non-conductive element is restricted to the conductive structure of the anode body at least from its one side and which non-conductive element is arranged at a distance A from the electrolyte surface level.
  • the anode is attached into the electrolytic cell bottom by anchoring elements.
  • the anode is attached into the electrolytic cell wall, into the electrolyte feeding means or the cathode next to the anode by anchoring elements.
  • the electrolyte is fed at least from two manifolds in the cell, when the other one is at the bottom of the cell.
  • the anode could be used in the electrowinning of the metal copper, Cu.
  • the anode can easily be attached in the cell, anode warping is avoided, good mixing effect of electrolyte inside the cell is reached by using the anode according to the invention. Also copper growth on the cathode surface will be more even.
  • good electrolyte mixing is obtained and metal ion concentration gradients can be avoided.
  • Better anode attaching and anchoring in the cell can be achieved by coating only part of the surface of the anode with the electrocatalytic coating.
  • FIG. 1 schematically shows an anode according to the invention, where the non-conductive part of the anode is part of the anode body.
  • FIG. 2 shows another embodiment of the anode, where the non-conductive element is attached to the anode.
  • FIG. 3 a schematically shows an anode according to the invention, where the anchoring elements are located on the electrolytic cell bottom.
  • FIG. 3 b schematically shows an anode according to the invention, where the anchoring elements are located on the electrolytic cell walls.
  • FIG. 3 c schematically shows an anode according to the invention, where the anchoring elements are located on the electrolyte feeding means.
  • FIG. 3 d schematically shows an anode according to the invention, where the non-conductive element is attached to the anode and attached to the anchoring elements.
  • FIGS. 1 and 2 shows an anode 1 for electrowinning of metals, such as copper in an electrolytic cell 2 having cell walls 3 and cell bottom 4 for holding an electrolyte 5 .
  • the anode comprises of a hanger bar 7 for supporting the anode on the conducting rod 8 , which distributes the current to the anode, an anode body 9 having at least partly conductive structure allowing the penetration of the electrolyte and an electrocatalytic coating.
  • a non-conductive element 10 , 12 , 14 in connection with the anode 1 at a distance A from the electrolyte surface level 11 , when the distance A is arranged to be at an interval 0.3-2 meter. This depends on the size of the anode used.
  • the non-conductive element 10 , 12 , 14 provides means for attaching the anode 1 inside the electrolytic cell 4 , which is important when using long anodes with long cathodes. When using long cathodes, it is important that the anode is fixed and rigid in its place and possible warping of the anode is prevented.
  • the non-conductive element consists of any suitable material that is not electrically conductive and could be selected based on the process needs. It is possible that the non-conductive element could consist of several pieces or is made from one piece.
  • FIGS. 3 a , 3 b , 3 c and 3 d describe different ways for attaching the anode inside the electrolytic cell 4 .
  • the non-conductive element 10 , 12 , 14 of the anode provides means for attaching the anode 1 for example in the cell bottom 3 , to the walls 2 or to the electrolyte feeding means 6 by anchoring elements 13 , which are attached to the non-conductive elements. It is also possible to attach the anode next to the cathode inside the electrolytic cell (not shown in figures).
  • the anode When the anode is attached to the cathode by using non-conductive element, it means that it acts as a spacer, which is known to be used to align the electrodes and separate them at a fixed distance from each other in order the electrolytic process to function.
  • FIG. 3 b One way for attaching the anode is presented in FIG. 3 b , when the anchoring elements 13 are located in both sides of the anode, which anchoring elements are attached to the non-conductive element 14 and from its other side to the electrolytic cell walls 2 .
  • By attaching the anchoring elements 13 to the electrolyte feeding means 6 as presented in FIG. 3 c , it saves space inside the electrolytic cell.
  • the anode When using a long anode, it is important that the anode is rigid and straight and positioned from even distance from the adjacent cathodes.
  • the anode can be anchored inside electrolytic cell 4 by supportive anchoring elements 13 , which could be of any shape (e.g. V-neck) and suitable for attaching them to the non-conductive elements 10 , 12 , 14 .
  • the electrolytic cell may be used for electrowinning of several metal values.
  • An electrowinning cell as described herein may be configured for the extraction of a variety of metal values.
  • FIG. 3 d schematically shows an anode, where the non-conductive element 12 is attached to the anode and attached to the anchoring elements 13 .
  • the non-conductive element is attached to the cathode next to the anode, when the non-conductive element functions as a cathode guide, i.e. during cathode harvests it guides the cathode into the correct position and prevents any contact between the cathode and the anode body.
  • the distance between electrolyte surface level 11 and the non-conductive element is arranged to be in interval 0.3-2 meter when the height B between the upper part 16 of the non-conductive element 10 , 12 , 14 and anode bottom surface 15 is arranged to be between 0.05-0.3 m. Then the immersion of the anode is enough to be used with long cathodes.
  • One way is to form the non-conductive element 10 , 12 , 14 of the anode 1 is by excluding the anode body 9 from electrocatalytic coating when at least 2 percent of the anode 1 surface is excluded from electrocatalytic coating.
  • the conductive structure of the anode body consists for example of a mesh structure allowing the penetration of the electrolyte, when the anode mesh consists of preferably one of the following metals; Ti, Ni, Pb, Ta, Zr or Nb.
  • Catalytic coating preferably consists of Pt-group metal oxide.

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  • 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)
US14/382,709 2012-03-09 2013-03-06 Anode and method of operating an electrolysis cell Abandoned US20150034491A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI20120075A FI125808B (en) 2012-03-09 2012-03-09 Anode and method for operating an electrolytic cell
FI20120075 2012-03-09
PCT/FI2013/050242 WO2013132157A1 (en) 2012-03-09 2013-03-06 Anode and method of operating an electrolysis cell

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US (1) US20150034491A1 (es)
JP (1) JP5898346B2 (es)
CN (1) CN104204307B (es)
CA (1) CA2865989C (es)
CL (1) CL2014002375A1 (es)
ES (1) ES2524193B1 (es)
FI (1) FI125808B (es)
MX (1) MX355084B (es)
PE (1) PE20142392A1 (es)
WO (1) WO2013132157A1 (es)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI125515B (en) * 2013-03-01 2015-11-13 Outotec Oyj A method of measuring and arranging an electric current flowing at a single electrode of an electrolysis system
CN105063728A (zh) * 2015-08-18 2015-11-18 江苏金曼科技有限责任公司 一种防腐蚀铂钛网
GB201603224D0 (en) 2016-02-24 2016-04-06 Barker Michael H And Grant Duncan A Equipment for a metal electrowinning or liberator process and way of operating the process

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3979275A (en) * 1974-02-25 1976-09-07 Kennecott Copper Corporation Apparatus for series electrowinning and electrorefining of metal
US4207153A (en) * 1979-02-16 1980-06-10 Kennecott Copper Corporation Electrorefining cell with bipolar electrode and electrorefining method
US4282082A (en) * 1980-01-29 1981-08-04 Envirotech Corporation Slurry electrowinning apparatus
US4319970A (en) * 1979-03-29 1982-03-16 Huttenwerke Kayser Aktiengesellschaft Method and apparatus for electrolytic separation of metals, particularly copper
US5282934A (en) * 1992-02-14 1994-02-01 Academy Corporation Metal recovery by batch electroplating with directed circulation
US20060021880A1 (en) * 2004-06-22 2006-02-02 Sandoval Scot P Method and apparatus for electrowinning copper using the ferrous/ferric anode reaction and a flow-through anode
US20090288856A1 (en) * 2008-05-24 2009-11-26 Phelps Dodge Corporation Multi-coated electrode and method of making
US20100006543A1 (en) * 2007-01-15 2010-01-14 Tokyo Electron Limited Plasma processing apparatus, plasma processing method and storage medium
WO2012051446A2 (en) * 2010-10-14 2012-04-19 Freeport-Mcmoran Corporation Improved electrowinning process

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CA971505A (en) * 1970-09-04 1975-07-22 International Nickel Company Of Canada Electrowinning metal utilizing higher current densities on upper surfaces
US5783050A (en) * 1995-05-04 1998-07-21 Eltech Systems Corporation Electrode for electrochemical cell
US7378011B2 (en) * 2003-07-28 2008-05-27 Phelps Dodge Corporation Method and apparatus for electrowinning copper using the ferrous/ferric anode reaction
JP4389846B2 (ja) * 2005-06-22 2009-12-24 三菱マテリアル株式会社 縁部絶縁部材
JP2009161810A (ja) * 2008-01-07 2009-07-23 Sumitomo Metal Mining Co Ltd 脱銅板の積載設備
US20100065433A1 (en) * 2008-09-12 2010-03-18 Victor Vidaurre Heiremans System and apparatus for enhancing convection in electrolytes to achieve improved electrodeposition of copper and other non ferrous metals in industrial electrolytic cells
US8697702B2 (en) * 2008-12-01 2014-04-15 Novartis Ag Method of optimizing the treatment of Philadelphia-positive leukemia with imatinib mesylate

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3979275A (en) * 1974-02-25 1976-09-07 Kennecott Copper Corporation Apparatus for series electrowinning and electrorefining of metal
US4207153A (en) * 1979-02-16 1980-06-10 Kennecott Copper Corporation Electrorefining cell with bipolar electrode and electrorefining method
US4319970A (en) * 1979-03-29 1982-03-16 Huttenwerke Kayser Aktiengesellschaft Method and apparatus for electrolytic separation of metals, particularly copper
US4282082A (en) * 1980-01-29 1981-08-04 Envirotech Corporation Slurry electrowinning apparatus
US5282934A (en) * 1992-02-14 1994-02-01 Academy Corporation Metal recovery by batch electroplating with directed circulation
US20060021880A1 (en) * 2004-06-22 2006-02-02 Sandoval Scot P Method and apparatus for electrowinning copper using the ferrous/ferric anode reaction and a flow-through anode
US20100006543A1 (en) * 2007-01-15 2010-01-14 Tokyo Electron Limited Plasma processing apparatus, plasma processing method and storage medium
US20090288856A1 (en) * 2008-05-24 2009-11-26 Phelps Dodge Corporation Multi-coated electrode and method of making
WO2012051446A2 (en) * 2010-10-14 2012-04-19 Freeport-Mcmoran Corporation Improved electrowinning process

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Publication number Publication date
MX355084B (es) 2018-04-04
FI125808B (en) 2016-02-29
MX2014010731A (es) 2015-04-10
CL2014002375A1 (es) 2015-01-16
ES2524193A2 (es) 2014-12-04
ES2524193B1 (es) 2015-09-02
CA2865989C (en) 2016-12-13
ES2524193R1 (es) 2014-12-29
JP5898346B2 (ja) 2016-04-06
CA2865989A1 (en) 2013-09-12
FI20120075A (fi) 2013-09-10
PE20142392A1 (es) 2015-02-02
JP2015509558A (ja) 2015-03-30
CN104204307A (zh) 2014-12-10
CN104204307B (zh) 2017-06-09
WO2013132157A1 (en) 2013-09-12

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