EP2183409B1 - Procédé pour faire fonctionner des cellules électrolytiques au cuivre - Google Patents
Procédé pour faire fonctionner des cellules électrolytiques au cuivre Download PDFInfo
- Publication number
- EP2183409B1 EP2183409B1 EP08782805A EP08782805A EP2183409B1 EP 2183409 B1 EP2183409 B1 EP 2183409B1 EP 08782805 A EP08782805 A EP 08782805A EP 08782805 A EP08782805 A EP 08782805A EP 2183409 B1 EP2183409 B1 EP 2183409B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolyte
- copper
- cell
- feed
- electrode
- 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.)
- Active
Links
- 239000010949 copper Substances 0.000 title claims abstract description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 title abstract description 23
- 239000003792 electrolyte Substances 0.000 claims abstract description 74
- 210000004027 cell Anatomy 0.000 description 42
- 238000005192 partition Methods 0.000 description 10
- 239000010802 sludge Substances 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005243 fluidization Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Images
Classifications
-
- 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
Definitions
- the invention relates to a method for operating copper electrolysis cells, which comprise a plurality of vertically and mutually parallel anode and cathode plates, a longitudinal electrolyte inlet and an electrolyte effluent, and a novel copper electrolysis cell.
- m is the mass of copper produced in g
- M the molar mass of copper in g / mol
- i the current density in A / m 2
- A the electrode surface in m 2
- t the time in s
- z the valence of the reaction ions involved
- F the Faraday constant in As / mol.
- the currently technically feasible current densities are, for example, in a copper refining electrolysis at a maximum of 350 A / m 2 . This value results from the fact that in a technical electrolysis cell only about 30-40% of the theoretical limiting current density can be driven.
- This theoretical limiting current density i limit (equation 2) is a function of the copper ion concentration in the electrolyte (c °) and the diffusion layer thickness ⁇ N at the electrode. N, the number of ions involved in the process, F, the Faraday constant and D, the diffusion coefficient, are constant.
- i border n ⁇ F ⁇ D ⁇ c 0 ⁇ N
- the types of refining electrolysis cells used today are distinguished by the fact that the electrolyte is fed in on the front side and removed again on the opposite end side.
- the main flow therefore takes place between the cell wall and the electrodes or the cell bottom and the lower edges of the electrodes.
- This externally applied flow also called forced convection
- the flow between the electrodes is determined by the natural convection that results from the density difference of the electrolyte in front of the cathodes (lighter electrolyte due to depletion of copper ions) and before the anodes (heavier electrolyte due to the accumulation of copper ions).
- containers for electrolytic metal extraction are known in which, to achieve a parallel flow, the electrolyte inlet and outlet into or out of the electrode space is effected by perforated plates arranged parallel to the longitudinal walls.
- a parallel partition with openings for the passage of electrolyte into the electrode space is arranged only on one longitudinal wall.
- the passage openings are distributed over the entire electrode height and are aligned with the electrode interstices.
- a relatively simple means of achieving parallel flow in conventional electrolysis cells is the provision of tubular electrolyte supply and drainage devices which direct the electrolyte in opposite directions between the bath longitudinal walls and the electrode side edges in the two free spaces. Due to the larger cathode width, a jam of the electrolyte occurs in front of the cathode side edges, as a result of which the latter partially flows into the respective electrode gap.
- electrolytic bath in which the parallel flow is achieved by an inlet of the electrolyte from the bath floor.
- an electrolysis cell is described with longitudinal electrolyte inlet, in which on one or both longitudinal sides extending over the entire length of the bath extending to just below the cathode lower edge, down and closed at the sides, above the electrolyte level open electrolyte inlet box is attached to the the electrodes facing horizontal and parallel to the electrodes aligned through openings, which in the region of the lower cathode edges over a extend certain area of the cathode spaces.
- the cross-sectional area of all the passage openings is smaller than the open horizontal cross-sectional area at the top of the electrolyte inlet box in order to achieve a slight overpressure.
- the channel cell requires a large pump capacity to achieve the high flow rates.
- To separate the entrained anode sludge continuous electrolyte filtration is required.
- Leiteinbauten as a flow straightener and the arrangement of appropriately shaped partitions is associated with a very large material and manufacturing effort.
- the hanging of these baths with the electrodes requires great care, since the desired electrolyte circulation is guaranteed only if the required geometric conditions are precisely met.
- the present invention aims to avoid the above-mentioned disadvantages and problems of the prior art and has as its object to provide a method for operating (conventional) copper electrolysis cells and a copper electrolysis cell with which higher current densities and thus higher current yields than in State of the art are possible, the cathode quality, for example but not affected by fluidization of the anode sludge, disturbance of anode sludge deposition, or poor inhibitor distribution. Likewise, extensive changes to and complex installations in the cell should be avoided.
- This object is achieved in a first aspect in a method of the type mentioned above in that the electrolyte via the electrolyte inlet horizontally and parallel to the electrodes in each electrode gap at the level of the lower third of the electrodes at a speed of 0.3 to 1, 0 m / s is flowed, wherein the cathode plates are arranged stationary relative to the inflow direction.
- the electrolyte is flowed into the cell at a rate of 0.3 to 0.6 m / s.
- a further improvement of the method is possible if the electrolyte is not applied as usual and applied in the examples on the front side of the cell but longitudinally drained.
- the method according to the invention has the additional advantage that it can be carried out even with existing electrolysis cells without great effort with few changes to the existing facilities.
- a copper electrolytic cell comprising a plurality of vertically and parallelly disposed anode and cathode plates, a longitudinal electrolyte inlet, and an electrolyte drain, characterized in that the electrolyte inlet is located on a longitudinal wall thereof Cell which extends into the region of the electrode lower edge and comprises a closed feed box which can be attached to the end faces of the cell and can be connected to an electrolyte source and means for stationary arrangement of each cathode plate and in the lower third of the electrode height extending and respectively corresponding to the electrode gap Regions with at least one opening, in particular nozzle, for the directed supply of electrolyte is provided.
- the means for the fixed arrangement of the cathode plates are designed as means for vertical guidance.
- the means for vertical guidance are formed as circular discs or wheels, wherein the cathode plates are each centered between two adjacently arranged and spaced discs or wheels.
- the electrolyte drain is arranged on the front side.
- it can also advantageously be arranged longitudinally.
- the electrolyte feed box used in the cell according to the invention can also be used advantageously in already existing conventional electrolysis cells.
- Fig. 2 shows a schematic representation of a copper electrolysis cell according to the present invention, in which, for reasons of better visibility of the inventive electrolyte feed box in relation to the electrolytic cell itself has been highlighted graphically.
- the closed inlet box 1 extends along a side wall 3 of the bath 2 and is attached to the end walls 4 of the bath 2 fastened in the cell, wherein the Einh brieflyen 5 simultaneously serve the supply and discharge of the electrolyte in the actual feed box.
- the inlet box 1 with an electrolyte source for example via a flange 6, connectable.
- the inlet box 1 is arranged so deep in the cell that it extends into the region of the electrode lower edge.
- openings in particular nozzles 7, are arranged, wherein at least one opening is located in each region corresponding to the electrode gap and extending over the lower third of the electrode height ( Fig. 3 ).
- the electrolyte is flowed into the cell in the lower area of the electrode gap at a speed of 0.3 to 1.0 m / s in order to achieve the advantageous flow guidance mentioned above.
- the fixed arrangement is achieved by means for the vertical guidance of the cathode plates, which are formed as circular disks or wheels 8, wherein the cathode plates 9 are respectively centered between two adjacently arranged and spaced disks or wheels ( Fig. 4 ).
- the cathode plates which are formed as circular disks or wheels 8
- the cathode plates 9 are respectively centered between two adjacently arranged and spaced disks or wheels ( Fig. 4 ).
- a conventional industrial copper electrolysis cell was equipped with an electrolyte inlet according to the invention, comprising a feed box as described above.
- Table 1 gives the operating conditions and results of further experiments.
- Table 1 Experiment No. i Q v ⁇ 1 trip ⁇ 2 trip in A / m 2 in l / min in m / s in % in % 1 407 75 0.75 93.92 95.01 2 407 75 0.5 97.24 98,15 3 407 75 0.5 99.46 98.35 4 407 75 0.5 97.49 96.27 4a 407 75 0.5 92.1 93.77 5 498 150 1 98.99 93.47 6 498 75 0.5 99.55 99.28 7 498 100 0.67 99.53 99.13 8th 543 100 0.67 98.18 97.59
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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)
Abstract
Claims (9)
- Procédé de conduite de cellules d'électrolyse de cuivre qui comprennent plusieurs plaques d'anode et de cathode disposées à la verticale et parallèlement les unes aux autres, une amenée longitudinale d'électrolyte et une évacuation d'électrolyte,
caractérisé en ce que
l'électrolyte est injecté à l'horizontale et parallèlement aux électrodes dans chaque interstice entre électrodes, chaque fois à hauteur du tiers inférieur des électrodes et à une vitesse de 0,3 à 1,0 m/s, les plaques de cathode étant disposées fixement par rapport à la direction d'injection. - Procédé selon la revendication 1, caractérisé en ce que l'électrolyte est injecté dans la cellule à une vitesse de 0,3 à 0,6 m/s.
- Procédé selon les revendications 1 ou 2, caractérisé en ce que l'électrolyte peut s'écouler longitudinalement.
- Cellule d'électrolyse de cuivre comprenant plusieurs plaques d'anode et de cathode disposées à la verticale et parallèlement les unes aux autres, une amenée longitudinale d'électrolyte et une évacuation d'électrolyte,
caractérisée en ce que
l'amenée d'électrolyte comporte
un caisson d'amenée fermé qui s'étend sur une paroi longitudinale de la cellule jusqu'au niveau du bord inférieur des électrodes, qui peut être suspendu sur les côtés frontaux de la cellule et être relié à une source d'électrolyte et qui est doté de moyens qui permettent de disposer fixement chaque plaque d'électrode et
dans les zones qui s'étendent sur le tiers inférieur de la hauteur des électrodes et qui correspondent à chaque interstice entre électrodes, au moins une ouverture et en particulier un ajutage qui permet d'apporter l'électrolyte de manière orientée. - Cellule d'électrolyse de cuivre selon la revendication 4, caractérisée en ce que les moyens permettant de placer les plaques d'électrode en position fixe sont configurés comme moyens de guidage vertical.
- Cellule d'électrolyse de cuivre selon la revendication 5, caractérisée en ce que les moyens de guidage vertical sont configurés sous la forme de disques circulaires ou de roues, les plaques de cathode étant toutes centrées entre deux disques ou roues disposés l'un à côté de l'autre et à distance l'un de l'autre.
- Cellule d'électrolyse de cuivre selon l'une des revendications 4 à 6, caractérisée en ce que l'évacuation d'électrolyte est disposée en position frontale.
- Cellule d'électrolyse de cuivre selon l'une des revendications 4 à 6, caractérisée en ce que l'évacuation d'électrolyte est disposée en position longitudinale.
- Caisson d'amenée d'électrolyte pour cellule d'électrolyse de cuivre, le caisson d'amenée étant fermé et s'étendant sur une paroi longitudinale de la cellule jusqu'au niveau du bord inférieur des électrodes, caractérisé en ce que
il peut être suspendu sur les côtés frontaux, peut être relié à une source d'électrolyte et est doté de moyens permettant de placer chaque plaque de cathode en position fixe ainsi que de zones qui s'étendent sur le tiers inférieur de la hauteur des électrodes et qui correspondent chacune à un interstice entre électrodes, et
en ce qu'il présente une ouverture, en particulier une tuyère, qui permet d'amener l'électrolyte de manière orientée.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL08782805T PL2183409T3 (pl) | 2007-08-27 | 2008-08-07 | Sposób działania elektrolizerów do elektrolizy miedzi |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT0133707A AT505700B1 (de) | 2007-08-27 | 2007-08-27 | Verfahren zum betreiben von kupfer-elektrolysezellen |
PCT/AT2008/000277 WO2009026598A2 (fr) | 2007-08-27 | 2008-08-07 | Procédé pour faire fonctionner des piles électrolytiques au cuivre |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2183409A2 EP2183409A2 (fr) | 2010-05-12 |
EP2183409B1 true EP2183409B1 (fr) | 2011-04-20 |
Family
ID=40377687
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08782805A Active EP2183409B1 (fr) | 2007-08-27 | 2008-08-07 | Procédé pour faire fonctionner des cellules électrolytiques au cuivre |
Country Status (11)
Country | Link |
---|---|
US (1) | US8454818B2 (fr) |
EP (1) | EP2183409B1 (fr) |
JP (1) | JP5227404B2 (fr) |
CN (1) | CN101376990B (fr) |
AT (2) | AT505700B1 (fr) |
AU (1) | AU2008291662B2 (fr) |
CA (1) | CA2696635C (fr) |
DE (1) | DE502008003297D1 (fr) |
ES (1) | ES2365376T3 (fr) |
PL (1) | PL2183409T3 (fr) |
WO (1) | WO2009026598A2 (fr) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB201112606D0 (en) | 2011-07-22 | 2011-09-07 | Johnson Matthey Plc | Desulphurisation materials |
JP5632340B2 (ja) * | 2011-08-05 | 2014-11-26 | Jx日鉱日石金属株式会社 | 水酸化インジウム及び水酸化インジウムを含む化合物の電解製造装置及び製造方法 |
CN103255443B (zh) * | 2013-05-06 | 2015-11-25 | 阳谷祥光铜业有限公司 | 超高电流密度电解或电积槽 |
CN104018191B (zh) * | 2014-06-16 | 2017-01-11 | 南华大学 | 带流量控制管的电解槽 |
JP6410131B2 (ja) * | 2014-07-31 | 2018-10-24 | 佐々木半田工業株式会社 | 錫の高電流密度電解精製法 |
CN104831319A (zh) * | 2015-05-28 | 2015-08-12 | 杭州三耐环保科技股份有限公司 | 一种顶部进液双向平行流电解槽及其使用方法 |
CN105506670B (zh) * | 2015-12-18 | 2018-03-23 | 阳谷祥光铜业有限公司 | 一种铜电解或铜电积的装置与运行方法 |
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 |
JP7150769B2 (ja) * | 2020-01-30 | 2022-10-11 | Jx金属株式会社 | 電解装置及び電解方法 |
JP7150768B2 (ja) * | 2020-01-30 | 2022-10-11 | Jx金属株式会社 | 電解装置及び電解方法 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3558466A (en) * | 1968-03-04 | 1971-01-26 | Kennecott Copper Corp | Electrolytic cell |
JPS4919003Y1 (fr) * | 1970-01-22 | 1974-05-21 | ||
US3682809A (en) * | 1970-02-24 | 1972-08-08 | Kennecott Copper Corp | Electrolytic cell constructed for high circulation and uniform flow of electrolyte |
BE771215A (fr) * | 1970-06-24 | 1971-12-16 | Mansfeld Kom Wilhelm Veb | Bain d'electrolyse pour le raffinage electrolytique du cuivre |
JPS5237602Y2 (fr) * | 1972-05-29 | 1977-08-26 | ||
DD109031A1 (fr) * | 1973-11-22 | 1974-10-12 | ||
US3966567A (en) * | 1974-10-29 | 1976-06-29 | Continental Oil Company | Electrolysis process and apparatus |
DD125714A1 (fr) | 1976-04-21 | 1977-05-11 | ||
DE3469190D1 (en) * | 1983-11-08 | 1988-03-10 | Holzer Walter | Process and apparatus for separating, for example, copper from a liquid electrolyte introduced into a pluricellular electrolyser |
JPH0768629B2 (ja) * | 1987-07-06 | 1995-07-26 | 三菱マテリアル株式会社 | ユニット化された極板を用いた電解方法 |
JPH0389166U (fr) * | 1989-12-25 | 1991-09-11 | ||
US5066379A (en) * | 1990-06-14 | 1991-11-19 | Corrosion Technology, Inc. | Container for corrosive material |
US5492608A (en) * | 1994-03-14 | 1996-02-20 | The United States Of America As Represented By The Secretary Of The Interior | Electrolyte circulation manifold for copper electrowinning cells which use the ferrous/ferric anode reaction |
US5855756A (en) * | 1995-11-28 | 1999-01-05 | Bhp Copper Inc. | Methods and apparatus for enhancing electrorefining intensity and efficiency |
JP2002105684A (ja) * | 2000-09-29 | 2002-04-10 | Dowa Mining Co Ltd | 電解方法及びこれに使用する電解槽 |
-
2007
- 2007-08-27 AT AT0133707A patent/AT505700B1/de active
-
2008
- 2008-07-25 CN CN2008101334907A patent/CN101376990B/zh not_active Expired - Fee Related
- 2008-08-07 PL PL08782805T patent/PL2183409T3/pl unknown
- 2008-08-07 ES ES08782805T patent/ES2365376T3/es active Active
- 2008-08-07 AU AU2008291662A patent/AU2008291662B2/en active Active
- 2008-08-07 EP EP08782805A patent/EP2183409B1/fr active Active
- 2008-08-07 US US12/675,601 patent/US8454818B2/en active Active
- 2008-08-07 CA CA2696635A patent/CA2696635C/fr active Active
- 2008-08-07 DE DE502008003297T patent/DE502008003297D1/de active Active
- 2008-08-07 AT AT08782805T patent/ATE506467T1/de active
- 2008-08-07 JP JP2010522124A patent/JP5227404B2/ja active Active
- 2008-08-07 WO PCT/AT2008/000277 patent/WO2009026598A2/fr active Application Filing
Also Published As
Publication number | Publication date |
---|---|
DE502008003297D1 (de) | 2011-06-01 |
EP2183409A2 (fr) | 2010-05-12 |
CA2696635A1 (fr) | 2009-03-05 |
AU2008291662B2 (en) | 2011-10-06 |
AU2008291662A1 (en) | 2009-03-05 |
WO2009026598A2 (fr) | 2009-03-05 |
ATE506467T1 (de) | 2011-05-15 |
ES2365376T3 (es) | 2011-10-03 |
US20110056842A1 (en) | 2011-03-10 |
CA2696635C (fr) | 2014-10-07 |
JP5227404B2 (ja) | 2013-07-03 |
JP2010537051A (ja) | 2010-12-02 |
AT505700A1 (de) | 2009-03-15 |
PL2183409T3 (pl) | 2011-11-30 |
CN101376990A (zh) | 2009-03-04 |
WO2009026598A3 (fr) | 2009-08-13 |
US8454818B2 (en) | 2013-06-04 |
AT505700B1 (de) | 2009-12-15 |
CN101376990B (zh) | 2012-09-05 |
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