EP0132647B1 - Revêtement de cuve d'électrolyse pour la production de l'aluminium - Google Patents

Revêtement de cuve d'électrolyse pour la production de l'aluminium Download PDF

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Publication number
EP0132647B1
EP0132647B1 EP84107810A EP84107810A EP0132647B1 EP 0132647 B1 EP0132647 B1 EP 0132647B1 EP 84107810 A EP84107810 A EP 84107810A EP 84107810 A EP84107810 A EP 84107810A EP 0132647 B1 EP0132647 B1 EP 0132647B1
Authority
EP
European Patent Office
Prior art keywords
lining
graphite blocks
graphite
blocks
thermal conductivity
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.)
Expired
Application number
EP84107810A
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German (de)
English (en)
Other versions
EP0132647A2 (fr
EP0132647A3 (en
Inventor
Karl Wilhelm Friedrich Dr. Etzel
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.)
Sigri GmbH
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Sigri GmbH
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Filing date
Publication date
Application filed by Sigri GmbH filed Critical Sigri GmbH
Publication of EP0132647A2 publication Critical patent/EP0132647A2/fr
Publication of EP0132647A3 publication Critical patent/EP0132647A3/de
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Publication of EP0132647B1 publication Critical patent/EP0132647B1/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
    • C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
    • 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
    • C25C3/085—Cell construction, e.g. bottoms, walls, cathodes characterised by its non electrically conducting heat insulating parts

Definitions

  • the invention relates to a tub for the melt flow electrolytic production of aluminum, which consists of a steel tub lined with graphite blocks, a heat-insulating layer between the tub and the lining, and cathodic power supply lines let into the lining.
  • Cells for the production of aluminum by electrolysis of aluminum oxide, which is dissolved in a fluoride melt, consist of a trough-shaped cathodic part which receives the molten electrolyte and the cathodically separated molten aluminum.
  • Metallic materials have only limited resistance to the electrolyte and the electrolysis products at the electrolyte temperature of 940 to 980 ° C and must therefore be protected against the attack of electrolyte and electrolysis products.
  • the cathodic part of the electrolytic cell therefore usually consists of a trough or a trough made of steel, which is lined with a temperature and corrosion-resistant material.
  • the lining also connects the actual molten aluminum cathode with the cathodic power supply, so that the material must also be a good electrical conductor. Therefore, almost exclusively carbon and graphite blocks are used for the lining of the tub, which are connected to one another by carbon-containing tamping and cementing compounds and form a layer impermeable to molten metal and electrolyte.
  • the functionality of the lining is essentially determined by its chemical and thermal resistance and its electrical resistance.
  • Joulesche heat is developed in the lining, which is partly necessary for setting the electrolysis temperature. Because of the temperature difference between the electrolyte and the tub, greater energy losses due to heat conduction can only be avoided if the thermal resistance of the lining is very high.
  • a heat-insulating layer of ceramic insulating materials is usually arranged between the lining made of carbon or graphite blocks and the tub.
  • carbon-bonded graphite blocks are also used, without the geometry and type of heat insulation being adapted to the changed material properties.
  • blocks consisting essentially of petroleum coke and heated to a high temperature, preferably at least 2000 ° C., have a particularly favorable resistance to the electrolyte (DE-OS 2 112 287).
  • the properties of these blocks are approximately: bulk density - 1.57 g / cm 3 , porosity - 27%, spec. electrical resistance - 14 ⁇ m.
  • the heat-insulating layer usually consists of refractory stones or powders with a thickness between 50 and 250 mm (US Pat. No. 3,434,957) and it is also known to assemble the heat-insulating layer from several individual layers (US Pat. No. 3,723,286). Finally, it is known to change the temperature gradients between the bottom and the side part of the lining by means of special insulating elements between these parts (US Pat. No. 4,118,304). These measures are not tailored to the material quality of the lining and their effects are limited accordingly.
  • the invention is therefore based on the object of extending the life of electrolysis cells for producing aluminum and reducing the energy requirement by coordinating the heat-insulating layer and a lining of graphite stones.
  • the accessible porosity of the graphite blocks is at most 18% and according to another embodiment, the thermal conductivity is 100 to 120 W / m - K and the spec. electrical resistance 6 to 10 ⁇ m.
  • graphite blocks which have been impregnated with a carbonizable impregnating agent and impregnated for pyrolysis of the impregnating agent and have been heated to about 700 to 1,000 ° C. for pyrolysis of the impregnating agent.
  • Coal tar pitch and petroleum pitch are particularly suitable as impregnating agents.
  • the heat-insulating layer advantageously consists of chamotte, the compressive strength of which is more than 10 MPa.
  • graphite is understood to mean carbon bodies which have been subjected to a graphitization treatment and have been heated to a temperature above about 2500 ° C.
  • the result of this treatment depends essentially on the starting products, e.g. B. type of coke used, and the manufacturing parameters, e.g. B. the molding process, so that the products referred to as graphite are only able to a small extent to meet the requirements in a cell for the melt flow electrolytic production of aluminum. It has been found that the useful for this purpose part 'of the material group graphite can be sorted out with the help of its material properties.
  • the mixture is formed into blocks and the blocks in a first stage for carbonizing the binder to about 1,000 ° C. and heated to 2600 to 3000 ° C in a second stage.
  • the use of raw materials with upstream structural elements and the use of higher temperatures result in graphite blocks with a comparatively high thermal conductivity and a low specific electrical resistance.
  • the thermal conductivity of the blocks is 80 to 120 W / m-K and the specific electrical resistance is 6 to 13 ⁇ m.
  • the comparatively low resistance brings about a substantial reduction in the voltage drop in the lining, in which less Joule heat is generated accordingly.
  • the open pore volume of the graphite blocks accessible to the melt must also be reduced.
  • the accessible pore volume should be at most 22% and, according to a preferred embodiment of the invention, at most 18%.
  • the graphite blocks forming the lining of the trough are expediently glued to one another without any joints, the term “seamless joints being understood to have a width of at most 1 mm.
  • the plastic compounds described in EP 0 027 534 are particularly suitable as joint cement.
  • the usual joints with a width of 20 mm and more are weak points in the lining, which are easily destroyed by thermal stress or by diffusing melt.
  • the steel trough is designated 1.
  • the heat-insulating layer consists of the sub-layers 2 and 3, the thermal conductivity of which is 0.1 to 0.2 W / m - K and 0.8 to 1.2 W / m - K.
  • the ratio of the thermal resistance of the layers is about 0.05.
  • Current bars or rails 5 are embedded in the graphite blocks 4 resting on the layer 3.
  • the thermal conductivity of the graphite blocks is 80 to 120 W / m - K, the specific electrical resistance 6 to 13 ⁇ m and the accessible pore volume is at most 22%.
  • the thickness ratio of the graphite layer 4 to the sum of the layers 2 and 3 is 1.5 to 1.6.
  • the graphite blocks 4 completely line the tub floor, the tub side surfaces are shielded by the block 6, which consists of graphite or carbon.
  • the actual cathode is the aluminum layer 7.
  • the anodes 9 with the anodic power supply 10 are immersed in the molten electrolyte 8 and are protected against the attack of atmospheric oxygen by the crust 11, which mainly consists of alumina.
  • the voltage drop measured when commissioning a cell to extract aluminum is essentially a function of the lining.
  • the voltage drop of a lining made of carbon blocks is about 400 mV
  • a lining made of carbon-bonded graphite blocks is about 300 mV
  • a lining made of graphite blocks according to the invention is only about 200 mV.
  • the temperature of the tub for these linings and a heat-insulating layer, formed from two sub-layers A and B with the thermal conductivity 1.0 and 0.1 W / m - K, is approximately 150 to 50 ° C (Table 1).
  • the low energy losses of the lining according to the invention can of course only be realized if the parameters measured when the electrolysis cell is started up do not change or change only slightly during the operation of the cell.
  • 2 shows the increase in the voltage drop as a function of the operating time; A is a liner made of carbon blocks, B is a liner made of carbon-bonded graphite and C is one made of graphite blocks.
  • the increase in the voltage drop with the operating time is essentially caused by the increasing decomposition and destruction of the lining.
  • the original advantage of linings according to the invention not only remains when the electrolysis cell is in operation, but also increases as the operating time progresses.

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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)

Claims (5)

1. Cuve pour la fabrication par électrolyse ignée de l'aluminium, cuve constituée d'une cuve en acier revêtue de blocs de graphite, d'une couche d'isolation calorifuge entre la cuve et le revêtement et des amenées de courant cathodique insérées dans le revêtement, cuve caractérisée en ce que :
a) le revêtement est constitué de blocs de graphite avec une conductibilité thermique de 80 à 120 W/m - K, une résistance électrique spécifique de 6 à 13 µΩm et un volume accessible de pores de 22 % au maximum,
b) la couche d'isolation comprend au moins deux couches partielles avec une conductibilité thermique de 0,1 à 0,2 et de 0,8 à 1,2 W/m - K,
c) le rapport des épaisseurs du revêtement et de la couche d'isolation est de 1,5 à 3,0.
2. Cuve selon la revendication 1, caractérisée en ce que les blocs de graphite ont une porosité accessible de 18 % au maximum.
3. Cuve selon les revendications 1 et 2, caractérisée en ce que les blocs de graphite ont une conductibilité thermique de 100 à 120 W/m - K et une résistance électrique spécifique de 6 à 10 µΩm.
4. Cuve selon les revendications 1 à 3, caractérisée en ce que les blocs de graphite contiennent un coke formé par carbonisation d'un moyen d'imprégnation du groupe des brais de houille ou des brais de pétrole.
5. Cuve selon les revendications 1 à 4, caractérisée en ce que la couche d'isolation est constituée de schamotte avec une résistance à la pression d'au moins 10 MPa.
EP84107810A 1983-07-28 1984-07-05 Revêtement de cuve d'électrolyse pour la production de l'aluminium Expired EP0132647B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3327230 1983-07-28
DE19833327230 DE3327230A1 (de) 1983-07-28 1983-07-28 Auskleidung fuer elektrolysewanne zur herstellung von aluminium

Publications (3)

Publication Number Publication Date
EP0132647A2 EP0132647A2 (fr) 1985-02-13
EP0132647A3 EP0132647A3 (en) 1985-03-13
EP0132647B1 true EP0132647B1 (fr) 1987-03-04

Family

ID=6205144

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84107810A Expired EP0132647B1 (fr) 1983-07-28 1984-07-05 Revêtement de cuve d'électrolyse pour la production de l'aluminium

Country Status (7)

Country Link
US (1) US4589967A (fr)
EP (1) EP0132647B1 (fr)
JP (1) JPS6052589A (fr)
AU (1) AU565836B2 (fr)
CA (1) CA1248495A (fr)
DE (1) DE3327230A1 (fr)
NO (1) NO161008C (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8522138D0 (en) * 1985-09-06 1985-10-09 Alcan Int Ltd Linings for aluminium reduction cells
NO157462C (no) * 1985-10-24 1988-03-23 Hydro Aluminium As Laminert karbonkatode for celler til smelte-elektrolytisk fremstilling av aluminium.
DE4201490A1 (de) * 1992-01-21 1993-07-22 Otto Feuerfest Gmbh Feuerfestes material fuer elektrolyseoefen, verfahren zur herstellung und verwendung des feuerfesten materials
FR2789093B1 (fr) 1999-02-02 2001-03-09 Carbone Savoie Cathode graphite pour l'electrolyse de l'aluminium
FR2789091B1 (fr) 1999-02-02 2001-03-09 Carbone Savoie Cathode graphite pour l'electrolyse de l'aluminium
WO2003002043A2 (fr) * 2001-06-29 2003-01-09 Coloplast A/S Sac de recueil de fluides anatomiques
US7126928B2 (en) * 2003-08-05 2006-10-24 Qualcomm Incorporated Grant, acknowledgement, and rate control active sets
FR2900665B1 (fr) 2006-05-03 2008-06-27 Carbone Savoie Soc Par Actions Cuve d'electrolyse d'obtention d'aluminium
US20090236233A1 (en) * 2008-03-24 2009-09-24 Alcoa Inc. Aluminum electrolysis cell electrolyte containment systems and apparatus and methods relating to the same
UA111247C2 (uk) * 2011-11-11 2016-04-11 Сгл Карбон Се Спосіб вимірювання профілів поверхонь в працюючих алюмінієвих електролізерах
JP6457397B2 (ja) * 2012-12-13 2019-01-23 エスジーエル・シーエフエル・シーイー・ゲーエムベーハーＳＧＬ ＣＦＬ ＣＥ ＧｍｂＨ アルミニウムを還元するための電解槽の壁用側壁レンガ

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1146259B (de) * 1960-10-28 1963-03-28 Aluminium Ind Ag Verfahren zum Auskleiden der Waende der Kathodenwanne einer Aluminium-elektrolysezelle und nach diesem Verfahren hergestellte Kathodenwanne
US3434957A (en) * 1966-02-18 1969-03-25 Arthur F Johnson Aluminum reduction cell with aluminum and refractory layered bottom construction
US3616045A (en) * 1969-02-17 1971-10-26 Tatabanyai Aluminiumkoho Process for increasing the strength and electrical conductivity of graphite or carbon articles and/or for bonding such articles to each other to ceramic articles or to metals
JPS4941006B1 (fr) * 1970-03-16 1974-11-06
US4046650A (en) * 1970-03-16 1977-09-06 Sumitomo Aluminum Smelting Co., Ltd. Carbon block for cathodes of aluminum
DE2105247C3 (de) * 1971-02-04 1980-06-12 Schweizerische Aluminium Ag, Zuerich (Schweiz) Ofen für die Schmelzflußelektrolyse von Aluminium
US3723286A (en) * 1971-11-08 1973-03-27 Kaiser Aluminium Chem Corp Aluminum reduction cell
JPS5332811A (en) * 1976-09-07 1978-03-28 Mitsubishi Keikinzoku Kogyo Reduction of heat radiation in the aluminium electrolytic cell
DE2942469C2 (de) * 1979-10-20 1983-09-15 Sigri Elektrographit Gmbh, 8901 Meitingen Kohlenstoffhaltige Kontaktmasse
CH653711A5 (de) * 1981-04-22 1986-01-15 Alusuisse Elektrolysewanne.
GB2103657A (en) * 1981-07-18 1983-02-23 British Aluminium Co Ltd Electrolytic cell for the production of aluminium
US4411758A (en) * 1981-09-02 1983-10-25 Kaiser Aluminum & Chemical Corporation Electrolytic reduction cell

Also Published As

Publication number Publication date
JPS6052589A (ja) 1985-03-25
NO842315L (no) 1985-01-29
NO161008B (no) 1989-03-13
EP0132647A2 (fr) 1985-02-13
AU3086284A (en) 1985-01-31
NO161008C (no) 1989-06-21
DE3327230C2 (fr) 1990-08-23
DE3327230A1 (de) 1985-02-07
US4589967A (en) 1986-05-20
CA1248495A (fr) 1989-01-10
EP0132647A3 (en) 1985-03-13
AU565836B2 (en) 1987-10-01

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