Electrolysis: processes – compositions used therein – and methods – Electrolytic synthesis – Utilizing fused bath
Reexamination Certificate
2000-07-15
2002-04-30
Bell, Bruce F. (Department: 1741)
Electrolysis: processes, compositions used therein, and methods
Electrolytic synthesis
Utilizing fused bath
C205S385000, C204S243100, C204S247300, C204S290030, C204S290040, C204S290060, C204S290080, C204S290090, C204S290100, C204S290120, C204S290130, C204S290140
Reexamination Certificate
active
06379526
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to non-carbon metal-based anodes for use in cells for the electrowinning of aluminium by the electrolysis of alumina dissolved in a molten fluoride-containing electrolyte, and to methods for their fabrication and reconditioning, as well as to electrowinning cells containing such anodes and their use to produce aluminium.
BACKGROUND ART
The technology for the production of aluminium by the electrolysis of alumina, dissolved in molten cryolite containing salts, at temperatures around 950° C. is more than one hundred years old.
This process, conceived almost simultaneously by Hall and Héroult, has not evolved as many other electrochemical processes.
The anodes are still made of carbonaceous material and must be replaced every few weeks. The operating temperature is still not less than 950° C. in order to have a sufficiently high solubility and rate of dissolution of alumina and high electrical conductivity of the bath.
The anodes have a very short life because during electrolysis the oxygen which should evolve on the anode surface combines with the carbon to form polluting CO
2
and small amounts of CO and fluoride-containing dangerous gases. The actual consumption of the anode is as much as 450 Kg/Ton of aluminium produced which is more than ⅓ higher than the theoretical amount of 333 Kg/Ton
The frequent substitution of the anodes in the cells is still a clumsy and unpleasant operation. This cannot be avoided or greatly improved due to the size and weight of the anode and the high temperature of operation.
Several improvements were made in order to increase the lifetime of the anodes of aluminium electrowinning cells, usually by improving their resistance to chemical attacks by the cell environment and air to those parts of the anodes which remain outside the bath. However, most attempts to increase the chemical resistance of anodes were coupled with a degradation of their electrical conductivity.
U.S. Pat. No.4,614,569 (Duruz/Derivaz/Debely/Adorian) describes non-carbon anodes for aluminium electrowinning coated with a protective coating of cerium oxyfluoride, formed in-situ in the cell or pre-applied, this coating being maintained by the addition of cerium compounds to the molten cryolite electrolyte. This made it possible to have a protection of the surface only from the electrolyte attack and to a certain extent from the gaseous oxygen but not from the nascent monoatomic oxygen.
EP Patent application 0 306 100 (Nyguen/Lazouni/Doan) describes anodes composed of a chromium, nickel, cobalt and/or iron based substrate covered with an oxygen barrier layer and a ceramic coating of nickel, copper and/or manganese oxide which may be further covered with an in-situ formed protective cerium oxyfluoride layer.
Likewise, U.S. Pat. Nos. 5,069,771, 4,960,494 and 4,956,068 (all Nyguen/Lazouni/Doan) disclose aluminium production anodes with an oxidized copper-nickel surface on an alloy substrate with a protective barrier layer. However, full protection of the alloy substrate was difficult to achieve.
A significant improvement was described in U.S. Pat. No. 5,510,008, and in International Application WO96/12833 (Sekhar/Liu/Duruz) involved a anode having a micropyretically produced body from a combination of nickel, aluminium, iron and copper and oxidising the surface before use or in-situ during electrolysis. By said micropyretic methods materials have been obtained whose surfaces when oxidised are active for the anodic reaction and whose metallic interior has low electrical resistivity to carry a current from high electrical resistant surface to the busbars. However it would be useful, if it were possible, to simplify the manufacturing process of these materials obtained from powders and increase their life to make their use economic.
Metal or metal based anodes are highly desirable in aluminium electrowinning cells instead of carbon-based anodes. Many attempts were made to use metal-based anodes for aluminium production, however they were never adopted by the aluminium industry because of their poor performance.
OBJECTS OF THE INVENTION
An object of the invention is to substantially reduce the consumption of the active anode surface of an aluminium electrowinning anode which is attacked by the nascent oxygen by enhancing the reaction of nascent oxygen to biatomic molecular gaseous oxygen.
Another object of the invention is to provide a coating for an aluminium electrowinning anode which has a high electrochemical activity and also a long life and which can be replaced as soon as such activity decreases or when the coating is worn out.
A major object of the invention is to provide an aluminium electrowinning anode which has no carbon so as to eliminate carbon-generated pollution and reduce the cost of operation.
SUMMARY OF THE INVENTION
The invention provides a non-carbon metal-based anode of a cell for the electrowinning of aluminium, in particular by the electrolysis of alumina dissolved in a molten fluoride-containing electrolyte. The anode comprises an electrically conductive metal substrate resistant to high temperature, the surface of which becomes passive and substantially inert to the electrolyte, and an electrochemically active coating adherent to the surface of the metal substrate making and keeping the surface of the anode conductive and electrochemically active for the oxidation of oxygen ions present at the electrolyte interface.
Whereas conventional coatings are usually used to protect a conductive substrate of a cell component from chemical and/or mechanical attacks destroying the substrate, this particular treatment is applied in the form of a coating onto a passivatable substrate to maintain the anode surface conductive and electrochemically active and protect it from electrolyte attack wherever the coating covers the surface even though the coating may be imperfect or incomplete.
This allows the coated surfaces of the anode to remain electrochemically active during electrolysis, while the remaining parts of the surface of the metal substrate become inert to the electrolyte. This passivation property offers a self-healing effect, i.e. when the surface of the anode is imperfectly covered, damaged or partly worn out, parts of the metal substrate which come into contact with the electrolyte are automatically passivated during electrolysis and become inert to the electrolyte and not corroded.
Metal substrates providing for this self-healing effect in molten fluoride-based electrolyte may be made of one or more metals selected from nickel, cobalt, chromium, molybdenum, tantalum and the Lanthanide series of the Periodic Table, and their alloys or intermetallics, such as nickel-plated copper.
The coatings usually comprise:
a) at least one electrically conductive and electrochemically active constituent,
b) an electrocatalyst, and
c) a bonding material substantially resistant to cryolite and oxygen for bonding these constituents together and onto the passivatable metal substrate.
These constituents are usually co-applied though it is possible to provide sequential application of the different constituents.
The presence of one or more electrocatalysts is desirable, although not essential for the invention. Likewise the presence of bonding material is not always necessary.
Coatings can be obtained by applying their active constituents and their precursors by various methods which can be different for each constituent and can be repeated in several layers. For example, a coating can be obtained by directly applying a powder onto the passivatable metal substrate or constituents of the coating may be applied from a slurry or suspension containing colloidal or polymeric material. The colloidal material can be a binder solely or can be part of the active material. The colloidal material may include at least one colloid selected from colloidal alumina, ceria, lithia, magnesia, silica, thoria, yttria, zirconia, tin oxide, zinc oxide and colloid containing the active material.
When a slurry or a suspension containing colloidal material is
de Nora Vittorio
Duruz Jean-Jacques
Deshmukh Jayadeep R.
Moltech Invent SA
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