AU2017297124B2 - Electrolysis cell and a method for repairing same - Google Patents

Electrolysis cell and a method for repairing same Download PDF

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AU2017297124B2
AU2017297124B2 AU2017297124A AU2017297124A AU2017297124B2 AU 2017297124 B2 AU2017297124 B2 AU 2017297124B2 AU 2017297124 A AU2017297124 A AU 2017297124A AU 2017297124 A AU2017297124 A AU 2017297124A AU 2017297124 B2 AU2017297124 B2 AU 2017297124B2
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steel
fss
pot shell
electrolysis cell
accordance
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AU2017297124A1 (en
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Eirik Hagen
Anders Lilleby
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Norsk Hydro ASA
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/08Cell construction, e.g. bottoms, walls, cathodes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/01Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/011Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of iron alloys or steels
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/28Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/08Cell construction, e.g. bottoms, walls, cathodes
    • C25C3/10External supporting frames or structures
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/005Ferrite

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Prevention Of Electric Corrosion (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

An electrolysis cell of Hall-Héroult type for producing aluminium having prebaked anodes of a carbonaceous material, and a cathode structure comprising a pot shell made out of a steel material and further having a bottom and sides supported by structural elements such as cradles and beams, wherein the cathode structure further comprises a protective and insulating lining inside the shell and a carbon based cathodic bottom with collector bars embedded therein, and where produced aluminium metal forms a layer onto said cathodic bottom, an electrolytic bath positioned above said aluminium metal where the anodes are in electrical contact with said electrolyte, wherein at least part of the steel pot shell and/or deck plates are made of a ferritic stainless steel (FSS) material. The method relates to a repair procedure for replacing parts of a commonly used carbon steel material with ferritic stainless steel material at least in parts of the steel pot shell and/or deck plates heavily exposed to corrosion and detonation. The replacement procedure can either result in a homogenous or composite material structure in affected areas.

Description

The present invention relates to a pot shell of an electrolysis cell and more particularly a pot shell material for an aluminium electrolysis cell of Hall-Heroult type. The invention also relates to a method for repairing such a pot shell.
Electrolysis cells for aluminium production based upon the Hall-H6roult principle commonly have prebaked anodes in its upper part and a cathode structure in its lower part. The cathode structure comprises mainly a steel pot shell formed as a pot with sides and a bottom and provided with vertical stiffeners and horizontal beams at its outside which are made out of steel too, the cathode structure further being provided with layers of protective and insulating lining materials inside its pot shell. In the mainly horizontal bottom part of the cathode structure there is commonly arranged electronic conducting carbon blocks. The cathode structure when in operation, contains a molten aluminium metal pad and above that molten bath material having temperatures that can be approximately 970° or even higher.
The main feature of the steel pot shell including its stiffeners and beams is to maintain the geometric and dimensional configuration of the cathode structure during its lifetime of operation. Due to continuous chemical swelling of the cathode material and lining as well the high temperatures involved and the effect this has on the properties of lining and steel components involved, several attempts have been carried out to make the steel pot shell structure and the configuration of stiffeners able to withstand this influence in a long lasting manner. Further, the inner part of the steel pot shell is exposed to high temperatures and corrosive gases. The most exposed areas has shown to be in the area from the top of the steel pot shell structure, i.e. the deck plate and at the inside of the steel pot shell behind the sidewall lining, down to the bath / metal interface or even down to the level where collector bars are embedded in the cathode carbon blocks.
An increased corrosion rate in this area has been observed following an increase in the electrical current in the cell.
The effect of this corrosion has a negative impact of the pot shell's ability to support the lining materials in an appropriate manner. Further, the corrosion product has a thermal conductivity that differs from the originally installed steel plate. This may result in an altered thermal behaviour of the cell in affected areas. Still further, it is acknowledged that this kind of corrosion may involve high reparation costs.
The mechanism for this particular increased corrosion rate is assumed to be connected with metal dusting corrosion.
Based upon these findings the inventors initiated a work that could lead to a reduced corrosion rate in the exposed part of the steel pot shell.
In theory, one solution could be to protect the mild steel quality that is applied today. In the upper side region this could be done by preventing corrosive gases passing through the solidified crust constituting the side ledge by making the sidelining more impermeable for such gases.
However, following the assumption that this corrosion effect could be related to the corrosion phenomenon metal dusting, the inventors started to do some corrosion experiments that led to a viable solution of the problem in that a more appropriate steel material for the pot shell was found.
Corrosive tests performed on this material, simulating the anticipated corrosion conditions led to the selection of a specific steel quality.
In full-scale operation this finding has proven to reduce the corrosion rate by a factor of 10. These and further advantages can be achieved in accordance to the invention as described in the accompanying patent claims.
In the following, the invention shall be further described by examples and figures where: Fig. 1 discloses a three dimensional view of a pot shell structure,
Fig. 2 discloses a theoretical imagination of the corrosion mechanism,
Fig. 3 discloses properties for various steel qualities, Fig. 4 discloses metal weight gain/increase related to exposure and temperature of different materials.
As can be seen from Fig. 1 , there is shown in a 3 D view a cut-out of a pot shell structure 10 where first of all only the steel plates are shown, and no vertical stiffeners and horizontal beams. Still further, only one part of one long side 11 , one part of one short side 12 and a part of the bottom 6 is shown.
The top of the long sidewall 11 comprises as a main constituent a deck plate 1 , and correspondingly the top of the short sidewall 12 comprises as a main constituent a short end deck plate 2.
Further, it can be seen that the upper parts of the long sidewall and the short sidewall comprise a part 3 and 4 respectively that is arranged beneath the deck plates 1 and 2. Between part 3 and the bottom there is arranged a lower part 7, showing openings 8, 8' for collector bars of the cathodic structure (not shown). Between part 4 and the bottom, there is a similar arrangement of a lower part 5, however without openings.
One or more of the components 1 - 4 can be made out of ferritic stainless steel (FSS), either as a homogenous material or composite covered onto the existing shell material by lining or cladding.
In case a homogenous material a suitable plate thickness will be between 15 and 25 mm, preferably 20 mm.
In case a composite material where the FSS material is covering the existing shell material by lining or cladding a suitable plate thickness will be 1 to 5 mm, preferably 3 mm. The components 5-7 can be made out of a steel quality for pot shell structures that is commonly used, for instance a carbon steel.
In present document the term carbon steel may also be used in reference to steel which is not stainless steel; in this use carbon steel may include alloy steels. In one embodiment the ferritic stainless steel (FSS) has the following alloying composition in wt %:
Cr = 10.5 - 18.0 c = 0.02 - 0.1
Ni = 0.0 - 0.5
Mn = 0.0 - 1.0
Mo = 0.0 - 1.25
Ti = 0.00 - 0.25
Nb = 0.00 - 0.35
rest unavoidable impurities and Fe.
This chemical composition is based upon the finding that the most important alloying elements are Cr and to some extent Ni to provide the achieved corrosion resistance for this specific application in an electrolysis cell.
In a second embodiment, the ferritic stainless steel (FSS) has the following alloying composition in wt %:
Cr = 10.5 - 18.0
C = 0.02 - 0.1
Ni = 0.1 - 0.5
Mn = 0.5 - 1.0
Mo = 0.5 - 1.25
Ti = 0.05 - 0.25
Nb = 0.05 - 0.35
rest unavoidable impurities and Fe.
Fig. 2 discloses a theoretical imagination of the corrosion mechanism and that metal dusting is the corrosion mechanism acting on the steel shell causing a severe damage much faster than observed before. The temperature cycling resulted by anode changes are assumed to affect both the steel susceptibility to metal dusting and the environmental conditions. Due to repeating anode changes in primary aluminium production the environment beneath the deck plate may cycle between reducing and oxidizing gas conditions and thus maintain conditions favoring metal dusting reactions.
Fig. 3 discloses physical properties for various steel qualities, among these carbon steels, ferritic stainless steels and austenitic stainless steels. It can be seen that the thermal expansion coefficient of ferritic stainless steel (Ferritic SS) and Carbon steels are very similar, as the thermal conductivity is a little bit less than the half. It can be seen that the austenitic steel is less suited for a low cost thermally loaded construction on the basis of the weight specific cost and coefficient of thermal expansion.
Fig. 4 discloses metal weight gain/increase related to exposure and temperature of different materials. Starting from left in the diagram:
S355JG3 - ordinary structural steel, carbon steel
16Mo3 - high temperature steel, boiler plate, carbon steel
P265H - high temperature steel, boiler plate, carbon steel
AISI316 - DIN 1.4404 - austenitic stainless steel
Nirosta 4003 - DIN 1.4003 - ferritic stainless steel
S235JR - low cost structural steel, carbon steel
As can be seen from the diagram, a shift from commonly used S235 (number six from left in the diagram) to DIN1.4003 (number five from left in the diagram) will dramatically reduce corrosion.
EN/DIN 1.4003 has a significantly lower corrosion rate when applied in the corrosive environment of the cells compared to other materials in use today, the factor is approximately 10 times lower.

Claims (13)

    Claims
  1. Electrolysis cell of Hall-Heroult type for producing aluminium having prebaked anodes of a carbonaceous material and a cathode structure comprising a pot shell made out of a steel material and further having a bottom and sides supported by structural elements such as cradles and beams, wherein the cathode structure further comprises a lining of protective and insulating materials inside the pot shell and further a carbon based cathodic bottom with collector bars embedded therein, and where produced aluminium metal forms a layer onto said cathodic bottom, and further having an electrolytic bath positioned above said aluminium metal where the anodes are in electrical contact with said electrolyte,
    characterised in that
    the pot shell above the cathode bar outlets comprises parts made of a ferritic stainless steel (FSS) material.
  2. Electrolysis cell in accordance with claim 1 ,
    characterised in that
    the deck plates (1 , 2) at the top of the steel shell comprises parts made of a ferritic stainless steel (FSS) material.
  3. Electrolysis cell in accordance with claim 1,
    characterised in that
    the sides of the pot shell below the collector bar outlets and the bottom of the pot shell comprises parts that are made of a ferritic stainless steel (FSS) material.
  4. Electrolysis cell in accordance with claim 1-3,
    characterised in that
    the pot shell is made of a ferritic stainless steel (FSS) material throughout its wall thickness and is a homogenous material.
  5. Electrolysis cell in accordance with claim 1-3,
    characterised in that
    the pot shell material is a composite material consisting of two layers, where the outer layer is made out a carbon steel (conventional material) and the inner layer is made of a ferritic stainless steel (FSS) material.
  6. 6. Electrolysis cell in accordance with any of claims 1 - 7,
    characterised in that
    the ferritic stainless steel (FSS) plate thickness is preferably between 1 and 25 mm.
  7. 7. Electrolysis cell in accordance with claim 4,
    characterised in that
    the ferritic stainless steel (FSS) plate thickness in the homogenous material is between 15 and 25 mm.
  8. 8. Electrolysis cell in accordance with claim 5,
    characterised in that
    the ferritic stainless steel (FSS) plate thickness in the composite material is between 1 and 5 mm.
  9. 9. Electrolysis cell in accordance with any of claims 1 - 8,
    characterised in that
    the ferritic FSS material is constituted in wt %
    Cr = 10.5-18.0
    C 0.02-0.1
    Ni = 0.0 - 0.5
    Mn =0.0-1.0
    Mo = 0.0-1.25
    Ti = 0.00 - 0.25
    Nb = 0.00 - 0.35
    rest unavoidable impurities and Fe.
  10. 10. Electrolysis cell in accordance with any of claims 1 -8,
    characterised in that
    the ferritic FSS material is constituted in wt %
    Cr = 10.5-18.0
    C = 0.02-0.1
    Ni = 0.1 - 0.5
    Mn =0.5-1.0
    Mo = 0.5-1.25
    Ti = 0.05 - 0.25
    Nb = 0.05 - 0.35 rest unavoidable impurities and Fe.
  11. 11. Method of repairing a cathode structure in an electrolysis cell of Hall-Heroult type for producing aluminium, comprising a pot shell made out of a steel material, the shell having a bottom and sides supported by structural elements such as cradles and beams, wherein the cathode structure further comprises a lining of protective and insulating materials inside the pot shell and a carbon based cathodic bottom with collector bars embedded therein, where the upper part of the steel pot shell and/or deck plates being weakened by corrosion at its inside,
    characterised in that
    -removal of any sidelining in areas affected;
    -followed by either cutting out of parts of the steel pot shell and/or deck plates affected by corrosion and replacing with fresh plate material,
    -or removing sufficient affected steel material and laying/cladding fresh plate material onto the existing steel shell and/or deck plates to make a composite material,
    -wherein the fresh plate material is a ferritic stainless steel (FSS) material.
  12. 12. Method in accordance with claim 11,
    characterised in that
    the ferritic FSS material is constituted in wt %
    Cr =10.5-18.0
    C = 0.02-0.1
    Ni =0.0-0.5
    Mn =0.0-1.0
    Mo = 0.0-1.25
    Ti = 0.00 - 0.25
    Nb = 0.00 - 0.35
    rest unavoidable impurities and Fe.
  13. 13. Method in accordance with claim 11 ,
    characterised in that
    the ferritic FSS material is constituted in wt %
    Cr =10.5-18.0
    C =0.02-0.1
    Ni =0.1 -0.5
    Mn =0.5-1.0
    Mo =0.5-1.25 Ti = 0.05 - 0.25
    Nb = 0.05 - 0.35
    rest unavoidable impurities and Fe.
AU2017297124A 2016-07-13 2017-06-01 Electrolysis cell and a method for repairing same Active AU2017297124B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NO20161170 2016-07-13
NO20161170A NO20161170A1 (en) 2016-07-13 2016-07-13 Electrolysis cell and a method for repairing same
PCT/NO2017/000018 WO2018012981A1 (en) 2016-07-13 2017-06-01 Electrolysis cell and a method for repairing same

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AU2017297124A1 AU2017297124A1 (en) 2019-01-03
AU2017297124B2 true AU2017297124B2 (en) 2022-07-14

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EP (1) EP3491174A4 (en)
AU (1) AU2017297124B2 (en)
CA (1) CA3030237C (en)
EA (1) EA035328B1 (en)
NO (1) NO20161170A1 (en)
NZ (1) NZ749316A (en)
WO (1) WO2018012981A1 (en)
ZA (1) ZA201900087B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3719577A (en) * 1971-03-18 1973-03-06 Aluminum Co Of America Magnetic field control in electrolysis cells using plates and/or bars
US3783121A (en) * 1972-03-24 1974-01-01 Aluminum Co Of America Magnetic field control in electrolysis cells
US4608135A (en) * 1985-04-22 1986-08-26 Aluminum Company Of America Hall cell
US7678244B2 (en) * 2002-10-14 2010-03-16 Aluminum Pechiney Electrolytic cell leak limiter

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB225494A (en) * 1923-11-30 1925-02-26 Aluminum Co Of America Improvements in or relating to methods of operating and lining electrolytic cells for electrolytic refining
GB596066A (en) * 1944-07-31 1947-12-29 Ind De L Aluminium Sa Improvements relating to cells for the electrolytic production or refining of aluminium
CH643602A5 (en) * 1979-10-17 1984-06-15 Alusuisse ELECTROLYSIS PAN.
NO158882C (en) * 1985-11-01 1988-11-09 Mosal Alu Elkem Spigerverk CATO BOX FOR ELECTROLYCLE CELLS AND PROCEDURES FOR THE MANUFACTURE OF CATALOG FOR ELECTROLYCLE CELLS.
DE10122326A1 (en) * 2001-05-08 2002-11-14 Norddeutsche Affinerie Process for repairing electrolysis cathodes
CN102230186B (en) * 2011-06-29 2012-12-12 东北大学设计研究院(有限公司) Cell shell device of aluminum electrolytic cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3719577A (en) * 1971-03-18 1973-03-06 Aluminum Co Of America Magnetic field control in electrolysis cells using plates and/or bars
US3783121A (en) * 1972-03-24 1974-01-01 Aluminum Co Of America Magnetic field control in electrolysis cells
US4608135A (en) * 1985-04-22 1986-08-26 Aluminum Company Of America Hall cell
US7678244B2 (en) * 2002-10-14 2010-03-16 Aluminum Pechiney Electrolytic cell leak limiter

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Slabbert, G.A. et al., "The effect of the matrix structure on the metal dusting rate in hydrocarbon environments", Journal of the Southern African Institute of Mining and Metallurgy (2013), 113(2), 81-90 *

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ZA201900087B (en) 2019-10-30
EP3491174A4 (en) 2020-08-19
EA035328B1 (en) 2020-05-28
AU2017297124A1 (en) 2019-01-03
EA201990280A1 (en) 2019-07-31
CA3030237C (en) 2023-08-08
NZ749316A (en) 2019-08-30
NO20161170A1 (en) 2018-01-15
CA3030237A1 (en) 2018-01-18
WO2018012981A1 (en) 2018-01-18
EP3491174A1 (en) 2019-06-05
BR112018076872A2 (en) 2019-04-02

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