EP1733075B1 - Element cathodique pour l'equipement d'une cellule d'electrolyse destinee a la production d'aluminium - Google Patents

Element cathodique pour l'equipement d'une cellule d'electrolyse destinee a la production d'aluminium Download PDF

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Publication number
EP1733075B1
EP1733075B1 EP05744310.3A EP05744310A EP1733075B1 EP 1733075 B1 EP1733075 B1 EP 1733075B1 EP 05744310 A EP05744310 A EP 05744310A EP 1733075 B1 EP1733075 B1 EP 1733075B1
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EP
European Patent Office
Prior art keywords
bar
insert
cathode element
block
cathode
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
Application number
EP05744310.3A
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German (de)
English (en)
French (fr)
Other versions
EP1733075A2 (fr
Inventor
Delphine Bonnafous
Jean-Luc Basquin
Claude Vanvoren
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.)
Rio Tinto France SAS
Original Assignee
Aluminium Pechiney SA
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 Aluminium Pechiney SA filed Critical Aluminium Pechiney SA
Priority to SI200532251T priority Critical patent/SI1733075T1/sl
Priority to PL05744310T priority patent/PL1733075T3/pl
Publication of EP1733075A2 publication Critical patent/EP1733075A2/fr
Application granted granted Critical
Publication of EP1733075B1 publication Critical patent/EP1733075B1/fr
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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
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/16—Electric current supply devices, e.g. bus bars
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/08—Cell construction, e.g. bottoms, walls, cathodes

Definitions

  • the present invention relates to the production of aluminum by igneous electrolysis. It relates more particularly to the cathode elements used in the electrolysis cells intended for the production of aluminum.
  • the cost of energy is an important item in the operating costs of the electrolysis plants. Therefore, reducing the specific consumption of electrolysis cells becomes a major issue for these plants.
  • the specific consumption of a cell corresponds to the energy consumed by the cell to produce one ton of aluminum. It is expressed in kWh / t and, with constant Faraday efficiency, it is directly proportional to the electrical voltage across the electrolysis cell.
  • the voltage of an electrolysis cell can be subdivided into several voltage drops: the anode voltage drop, the voltage drop in the bath, the electrochemical voltage, the cathodic voltage drop and the line losses.
  • the present invention relates to the reduction of the cathodic voltage drop in order to reduce the specific consumption of the electrolysis cells.
  • the cathodic voltage drop depends on the electrical resistance of the cathode element, which comprises a cathode block of carbon material and one or more metal connection bars.
  • the materials constituting the cathode blocks have evolved over time to become less and less resistive at the passage of the current. This allowed to increase the intensities through the cells, while maintaining a constant cathodic voltage drop.
  • the cathodic blocks were in anthracite (amorphous carbon). This material provided a fairly strong electrical resistance.
  • these blocks were gradually replaced, from the 1980s, by so-called “semi-graphitic” blocks (containing graphite quantities ranging from 30% to 50%) then by so-called “graphitic” blocks containing 100% of graphite grains but whose binder joining these grains remains amorphous.
  • the graphite grains of these blocks since they are not very resistive, the blocks offer a lower resistance to current flow and consequently, at constant intensity, the drop in cathodic voltage drops.
  • cathode blocks have led to the emergence of new problems such as, for example, the erosion of cathodes.
  • new problems such as, for example, the erosion of cathodes.
  • the more graphite blocks contain graphite the more susceptible they are to erosion problems at the top of the block.
  • the current density is not distributed homogeneously over the entire width of the tank and there is, on the surface of the cathode, a peak current density located at each end of the block. This current density peak causes localized erosion of the cathode, erosion all the more marked that the block is rich in graphite.
  • the insert is flush - with a given tolerance - the surface of the end of said outer portion.
  • the or each insert is made of copper or copper-based alloy.
  • an insert according to the invention makes it possible simultaneously to obtain a very large reduction in the overall cathodic voltage drop (for example 0.2 V for a bar with a copper insert against 0.3 V for a bar totally in steel) and a very strong reduction in the current density at the top of the block (at least of the order of 20%).
  • the applicant has had the idea of combining a zone of non-sealing near the head of the cathode block and at least one insert in each outer portion of the connecting bar which preferably extends over substantially the entire length of the section. It has been found that, unexpectedly, the combined effect of these characteristics makes it possible to very significantly reduce the peak of density of the current existing at the head of the block, that is to say near the ends of the block, while significantly reducing the cathodic voltage drop. In particular, she noted that the non-sealing zone makes it possible to substantially reduce the impact of the slope foot on the peak of current density.
  • the invention is particularly interesting when said carbon material contains graphite.
  • a method of manufacturing a connecting bar which can be used in a cathode element according to the invention, advantageously comprises the formation of a longitudinal cavity - typically a blind hole - in a steel bar from one end thereof, the manufacture of an insert of more conductive material than the steel constituting the bar, of length and section corresponding to those of the cavity, and then the introduction of the insert into the cavity.
  • the invention also relates to an electrolysis cell comprising at least one cathode element according to the invention.
  • an electrolysis cell 1 comprises a tank 10 and at least one anode 4.
  • the tank 10 comprises a box 2 whose bottom and the side walls are covered with elements of refractory material 3 and 3 '.
  • Cathodic blocks 5 rest on the bottom refractory elements 3.
  • Connection bars 6, generally made of steel, are sealed in the lower part of the cathode blocks 5.
  • the seal between the connection bar (s) 6 and the cathode block 5 is typically produced by means of cast iron or conductive paste 7.
  • the cathode blocks 5 have a substantially parallelepipedal shape, of length Lo, one of the side faces 21 has one or more longitudinal grooves 15 for housing the connecting bars 6.
  • the grooves 15 open at the head of the block and generally extend from one end to the other of the block.
  • the so-called "off-block" portion 22 of the bar 6 which emerges from the cathode block 5 has a length E.
  • the cathode blocks 5 and the connecting bars 6 form cathode elements 20 which are generally assembled out of the tank and added thereto during the formation of its lining.
  • An electrolytic cell 10 typically comprises more than a dozen cathode elements 20 arranged side by side.
  • a cathode element 20 may comprise one or more connecting bars, which pass through the block from one side, or one or more pairs of half-bars, typically aligned, which extend only over a portion of the block.
  • connection bars 6 The purpose of the connection bars 6 is to collect the current that has passed through each cathode block 5 and to return it to the network of conductors outside the tank. As illustrated in figure 1 , the connecting bars 6 pass through the tank 10 and are typically connected to a connecting conductor 13, generally made of aluminum, by a flexible aluminum connector 14 connected to the (x) section (s) 19 of the bars which come out of the tank 10.
  • the tank 10 contains a sheet of liquid aluminum 8 and an electrolyte bath 9, above the cathode blocks 5, and the anodes 4 dive into the bath 9.
  • a solidified bath slope 12 is generally formed on the side coatings 3 '.
  • a portion 12 ' of this embankment 12, called “foot of slope”, can encroach on the upper lateral surface 28 of the cathode block 5.
  • the foot of the embankment electrically isolates the cathode and increases the peak of current density at the top of the block.
  • the figure 2 represents an electrolysis cell 1 for aluminum production, in which the same elements are designated by the same references as previously.
  • each end of connecting bar 6 is equipped with a metal insert 16, preferably copper or copper alloy, which extends over a length Lc, typically from substantially the or each outer end of the bar 6 .
  • the insert 16 is located, at least partly, in the or each outer segment 19 of the connecting rod 6 which is intended to be located outside of vessel 10.
  • the or each insert 16 is preferably housed in a cavity forming a blind hole inside the bar 6. This variant avoids the exposure of the insert to the possible infiltrations bath or liquid metal.
  • the cavity may optionally be a groove on a lateral face of the bar, as illustrated in FIG. figure 7 .
  • the insert preferably covers at least 90% of the length of the or each outer portion 19 of the connecting bar 6 in which it is housed in order to optimize the voltage drop reduction obtained using the 'invention.
  • the end surface 24, which is intended to be outside the tank 10, is generally substantially vertical when the cathode element 20 is installed in a tank.
  • the or each insert 16 is substantially flush, that is to say with a given tolerance, the surface 24 of the end of the outer portion 19 of the bar 6.
  • Said determined tolerance is preferably less than or equal to ⁇ 1 cm.
  • each insert 16 is recessed, by a determined distance, with respect to the surface 24 of the end of the outer section 19 of the bar 6. Said determined distance is preferably less than or equal to 4 cm.
  • the cavity formed by the removal of the insert may advantageously contain a refractory material to prevent heat loss by radiation and / or convection.
  • the length Lc of the insert 16 is typically between 10 and 300%, preferably between 20 and 300%, and more preferably between 110 and 270%, of the length E of the so-called "off-block" part 22 of the bar 6 which emerges from the cathode block 5 and in which the insert is housed.
  • At least one zone 17 situated between the bar 6 and the cathode block 5 does not contain any sealing material.
  • This so-called “non-sealing” zone is advantageously filled, in whole or in part, with an electrically insulating material, such as a refractory material, typically in the form of fibers or fabrics; this material is interposed between the bar 6 and the cathode block 5, in the non-sealing zone 17, as illustrated in FIG. figure 5 .
  • the or each non-sealing zone 17 is located near the end 25 of the cathode block 5, called “pack header", which emerges from the bar and covers a given surface S.
  • the or each zone non-sealing 17 is flush with the surface 27 of the block head 25 from which the bar 6 emerges .
  • the cathode element comprises two parallel connecting bars which pass through the cathode block from one side to the other. Each bar then comprises two out-of-block portions 22 and two outer portions 19.
  • the cathode element comprises four connecting bars (also called "half-bars") which each open at one end of the block. Each bar then comprises a single out-of-block portion 22 and a single outer portion 19.
  • a conductive sealing material 7 is interposed between the block 5 and each bar 6, except in the zones at the ends of the block 5 where there are non-sealing zones 17, which can be filled with refractory materials.
  • the total area A of the determined surface (s) S of the non-sealing zone (s) 17 of each connecting bar 6 is typically between 0.5 and 25%, preferably between 2 and 20%, more preferably between 3 and 15%, of the area Ao the surface So of the bar 6 which is likely to be sealed, called "sealable surface".
  • the sealable surface So corresponds to the surfaces of the portion 23 of the bar 6 which are opposite the internal surfaces of the groove 15 in the block 5.
  • each half-connecting bar 6 has a non-sealing zone 17 at one end only 25, the total area A is equal to the area of the determined surface S of this non-sealing zone.
  • the Applicant has found that when the discontinuity of the bar near the center of the block is relatively short, which is generally the case, it hardly changed the current distribution and the voltage drop, so that the area A could be determined as if the bars were continuous from one end to the other.
  • the determined surface S is typically of simple shape in order to facilitate the formation of the non-sealing zone 17.
  • the area of the determined surface S is typically equal to Ls ⁇ ( 2H + W).
  • the length Ls of each non-sealing zone 17 is preferably between 0.5 and 25%, preferably between 2 and 20%, more preferably between 3 and 15%, of the half-length Lo. / 2 of the block.
  • the section of the insert 16 also influences the reduction of the cathodic voltage drop.
  • the cross section of each insert is between 1 and 50%, and preferably between 5 and 30%, of the cross section of the bar 6. In fact, beyond 30% of total insert section, the additional amount of driver provides a significant additional cost for a small increase in performance.
  • the insert 16 typically takes the form of a bar.
  • the shape of the cross section of the insert 16 is free, this shape being able to be rectangular (as illustrated in FIG. figure 5 ), circular (as illustrated in figure 6 or 7 ), ovoid or polygonal ... It is, however, advantageously circular to facilitate the manufacture of the connecting bar, including the realization of the cavity for housing the insert.
  • the Applicant has carried out numerical calculations intended to evaluate the distribution of the cathodic current at the surface 28 of the cathode block obtained with configurations according to the prior art and according to the invention.
  • the figure 8 presents the results of a calculation corresponding to connection bar dimensions and a current intensity typical of existing electrolysis cells.
  • the curves correspond to the current density J at the upper surface 28 of the block, expressed in kA / m 2 , as a function of the distance D from the end of the block.
  • the cell has 20 cathode elements arranged side by side and each having two connection bars, as illustrated in FIG. figure 3 .
  • the total intensity is 314 kA.
  • the connecting bars have a length L equal to 4.3 m, a height H equal to 160 mm and a width W equal to 110 mm.
  • the length E of the connecting bars leaving the cathode blocks is 0.50 m.
  • Curve A relating to the prior art, corresponds to a connection bar made entirely of steel.
  • the cathodic voltage drop is 283 mV (between the center of the liquid metal sheet and the anode frame of the downstream tank).
  • Curve B corresponds to a steel bar having the same dimensions as in case A, but having a cylindrical copper insert with a length equal to 1.53 m, the diameter of which is equal to 4.13 cm.
  • the insert is placed along the longitudinal axis of symmetry of the bar and extends approximately from the center of the bar (i.e. approximately from the central plane P of the vessel) to about half the thickness of the side coating 3 ' of the cell.
  • the cathode voltage drop is 229 mV.
  • the The reduction in cathodic drop is about 19% and the reduction in current density peak is about 18%.
  • Curve C corresponds to a steel bar having the same dimensions as in case A, but comprising a cylindrical copper insert with a length Lc equal to 1.30 m, the diameter of which is equal to 4.5 cm (corresponding to a volume of copper identical to that of case B).
  • the insert is placed along the longitudinal axis of symmetry of the bar and extends, as in the figure 2 from the outer end of the bar to the inside of the cell.
  • the non-sealing zone is 0.18 m long and covers the three normally sealed sides of the bar.
  • the cathodic voltage drop is 190 mV. With respect to case A, the reduction of the cathode drop is about 32% and the reduction of the current density peak is about 37%.
  • the distribution of cathodic current is much more homogeneous than in cases A and B.

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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)
EP05744310.3A 2004-04-02 2005-03-30 Element cathodique pour l'equipement d'une cellule d'electrolyse destinee a la production d'aluminium Active EP1733075B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
SI200532251T SI1733075T1 (sl) 2004-04-02 2005-03-30 Katodni element za opremo elektrolitske celice, namenjene za proizvodnjo aluminija
PL05744310T PL1733075T3 (pl) 2004-04-02 2005-03-30 Element katodowy do wyposażenia elektrolizera przeznaczonego do produkcji aluminium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0403497A FR2868435B1 (fr) 2004-04-02 2004-04-02 Element cathodique pour l'equipement d'une cellule d'electrolyse destinee a la production d'aluminium
PCT/FR2005/000757 WO2005098093A2 (fr) 2004-04-02 2005-03-30 Element cathodique pour l'equipement d'une cellule d'electrolyse destinee a la production d'aluminium

Publications (2)

Publication Number Publication Date
EP1733075A2 EP1733075A2 (fr) 2006-12-20
EP1733075B1 true EP1733075B1 (fr) 2019-03-13

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EP05744310.3A Active EP1733075B1 (fr) 2004-04-02 2005-03-30 Element cathodique pour l'equipement d'une cellule d'electrolyse destinee a la production d'aluminium

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Country Link
US (1) US7618519B2 (tr)
EP (1) EP1733075B1 (tr)
CN (1) CN1938454B (tr)
AR (1) AR051433A1 (tr)
AU (1) AU2005232010B2 (tr)
BR (1) BRPI0509509B1 (tr)
CA (1) CA2559372C (tr)
EG (1) EG24808A (tr)
FR (1) FR2868435B1 (tr)
NO (1) NO343609B1 (tr)
PL (1) PL1733075T3 (tr)
RU (1) RU2364663C2 (tr)
SI (1) SI1733075T1 (tr)
TR (1) TR201906708T4 (tr)
WO (1) WO2005098093A2 (tr)
ZA (1) ZA200608183B (tr)

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EP1927679B1 (en) 2006-11-22 2017-01-11 Rio Tinto Alcan International Limited Electrolysis cell for the production of aluminium comprising means to reduce the voltage drop
TW200925328A (en) 2007-10-29 2009-06-16 Bhp Billiton Aluminium Technologies Ltd Composite collector bar
WO2011148347A1 (en) 2010-05-28 2011-12-01 Kan-Nak S.A. Hall-heroult cell cathode design
CN102758216B (zh) * 2011-04-29 2015-04-15 沈阳铝镁设计研究院有限公司 一种均化铝电解槽铝液中电流分布的方法
FR2976593B1 (fr) * 2011-06-16 2014-09-05 Rio Tinto Alcan Int Ltd Cuve d'electrolyse destinee a etre utilisee pour produire de l'aluminium
CN102234820B (zh) * 2011-08-04 2013-03-20 中国铝业股份有限公司 一种减少铝电解槽铝液水平电流的方法
BR112014005689A2 (pt) 2011-09-12 2017-03-28 Alcoa Inc célula de eletrólise de alumínio com dispositivo e método de compressão
CN103014765B (zh) * 2011-09-24 2016-07-06 沈阳铝镁设计研究院有限公司 减小铝液中水平电流的阴极结构
EA029173B1 (ru) 2012-08-09 2018-02-28 Мид Маунтин Матириалз, Инк. Уплотнительный узел для катодных токоотводящих стержней
WO2014043066A1 (en) * 2012-09-11 2014-03-20 Alcoa Inc. Current collector bar apparatus, system, and method of using the same
CN103233245B (zh) * 2013-05-23 2015-04-29 黄河鑫业有限公司 一种监测和准确判断在线电解槽阴极内衬破损的方法
EP3221496B1 (en) 2014-11-18 2023-08-16 Novalum SA Cathode current collector for a hall-heroult cell
GB2542150A (en) * 2015-09-09 2017-03-15 Dubai Aluminium Pjsc Cathode assembly for electrolytic cell suitable for the Hall-Héroult process
GB2548830A (en) * 2016-03-29 2017-10-04 Dubai Aluminium Pjsc Cathode block with copper-aluminium insert for electrolytic cell suitable for the Hall-Héroult process
RU2657682C2 (ru) * 2016-07-19 2018-06-14 Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" Катодный токоподводящий стержень алюминиевого электролизера
CN109863258B (zh) * 2016-07-26 2022-05-31 东海Cobex有限责任公司 用于霍尔-埃鲁电池的阴极集流器/连接器
CA3031708C (en) * 2016-07-26 2022-08-23 Cobex Gmbh Cathode assembly for the production of aluminum
SI3510183T1 (sl) * 2016-09-09 2024-05-31 Glencore Technology Pty Limited Izboljšave obešalnih drogov
GB2554702A (en) * 2016-10-05 2018-04-11 Dubai Aluminium Pjsc Cathode assembly for electrolytic cell suitable for the Hall-Héroult process
CN109666953A (zh) * 2017-10-16 2019-04-23 沈阳铝镁设计研究院有限公司 一种复合、高导电阴极钢棒
CN110605677B (zh) * 2019-09-16 2024-02-06 中冶天工集团有限公司 一种可拆卸式阴极炭块组装固定装置及使用方法
CN115103931A (zh) * 2019-12-24 2022-09-23 阿迪特亚比拉科技私人有限公司 用于提高铝还原池在冶炼工艺中的性能的装置
NO20201415A1 (en) * 2020-12-21 2022-06-22 Storvik As Method for producing a cathode steel bar with copper insert, and method for removing a copper insert from a used cathode bar
JP2024517923A (ja) * 2021-05-10 2024-04-23 ノヴァルム エス．アー． アルミニウム製造セルにおけるカソード集電棒
DE102022129669A1 (de) 2022-11-09 2024-05-16 Novalum Sa Kathodenstromkollektor und -verbinderanordnung für eine Aluminium-Elektrolysezelle
DE102022129667A1 (de) 2022-11-09 2024-05-16 Novalum Sa Kathodenstromkollektoranordnung für eine Aluminium-Elektrolysezelle
DE102022129668A1 (de) 2022-11-09 2024-05-16 Novalum Sa Kathodenstromkollektor und -verbinderanordnung für eine Aluminium-Elektrolysezelle

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DE812211C (de) * 1947-09-05 1951-08-27 Alais & Froges & Camarque Cie Verfahren zur Herstellung des unteren Teiles des Tiegels von Zellen zur schmelzfluessigen Elektrolyse und nach diesem Verfahren her-gestellte Zelle fuer die Schmelzflusselektrolyse
DE2631673A1 (de) * 1975-07-17 1977-01-20 Savoie Electrodes Refract Kathodenelement fuer elektrolysezellen, insbesondere zur aluminiumelektrolyse
US5976333A (en) * 1998-01-06 1999-11-02 Pate; Ray H. Collector bar

Also Published As

Publication number Publication date
CA2559372A1 (fr) 2005-10-20
PL1733075T3 (pl) 2019-08-30
FR2868435B1 (fr) 2006-05-26
TR201906708T4 (tr) 2019-05-21
BRPI0509509A (pt) 2007-09-11
NO343609B1 (no) 2019-04-15
CN1938454B (zh) 2011-12-28
US20050218006A1 (en) 2005-10-06
BRPI0509509B1 (pt) 2015-10-27
AR051433A1 (es) 2007-01-17
FR2868435A1 (fr) 2005-10-07
AU2005232010B2 (en) 2009-11-19
EP1733075A2 (fr) 2006-12-20
RU2006138619A (ru) 2008-05-10
WO2005098093A3 (fr) 2006-07-20
CA2559372C (fr) 2012-09-04
US7618519B2 (en) 2009-11-17
EG24808A (en) 2010-09-19
SI1733075T1 (sl) 2019-06-28
AU2005232010A1 (en) 2005-10-20
ZA200608183B (en) 2008-07-30
NO20064798L (no) 2006-12-21
CN1938454A (zh) 2007-03-28
RU2364663C2 (ru) 2009-08-20
WO2005098093A2 (fr) 2005-10-20

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