EP2948577B1 - An electrode for aluminium production and a method of making same - Google Patents

An electrode for aluminium production and a method of making same Download PDF

Info

Publication number: EP2948577B1
Authority: EP; European Patent Office
Prior art keywords: electrode; barrier layer; diffusion barrier; accordance; conducting elements
Prior art date: 2013-01-22
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

EP14743388.2A

Other languages

German (de)

English (en)

French (fr)

Other versions

EP2948577A4 (en

EP2948577A1 (en

Inventor

Eirik Hagen

Bjarte ØYE

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.)

Norsk Hydro ASA

Original Assignee

Norsk Hydro ASA

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.)

2013-01-22

Filing date

2014-01-20

Publication date

2018-12-05

2014-01-20 Application filed by Norsk Hydro ASA filed Critical Norsk Hydro ASA

2015-12-02 Publication of EP2948577A1 publication Critical patent/EP2948577A1/en

2016-04-20 Publication of EP2948577A4 publication Critical patent/EP2948577A4/en

2018-12-05 Application granted granted Critical

2018-12-05 Publication of EP2948577B1 publication Critical patent/EP2948577B1/en

Status Active legal-status Critical Current

2034-01-20 Anticipated expiration legal-status Critical

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Classifications

- 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
- 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
- C25C3/12—Anodes
- 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
- C25C3/12—Anodes
- C25C3/125—Anodes based on carbon

Definitions

the present invention relates to an electrode for aluminium production and a method for making same.
Aluminium metal is presently produced by electrolysis of an aluminium containing compound dissolved in a molten electrolyte, and the electrowinning process is performed in smelting cells of conventional Hall-Heroult design. These electrolysis cells are equipped with horizontally aligned electrodes, where the electrically conductive anodes and cathodes of today's cells are made from carbon materials.
the electrolyte is based on a mixture of sodium fluoride and aluminium fluoride, with additions of alkaline and alkaline earth halides.
the electrowinning process takes place as the current passed through the electrolyte from the anode to the cathode causes the electrical discharge of aluminium ions at the cathode, producing aluminium metal.
pre-baked carbon anodes are fixed to steel studs that are part of an anode hanger.
the anode has pre-formed bores which allow the steel studs to be entered into them.
the fixation of the studs to the anode is commonly performed by pouring melted cast-iron in the annular space between each individual stud and the corresponding bore in the anode.
conductive particles can be applied for rodding as shown in the Applicant's own patent application WO09/099335 .
one well known and potent tool is to aim at the reduction of the cathodic and/or the anodic voltage drop. Indeed, reducing cathodic voltage drop reduces ohmic energy loss in the cathode, allowing operators to either increase potline amperage and/or reduce pot voltage that ultimately results in a reduction of the specific energy consumption per ton of produced aluminium.
WO04031452 which discloses collector bars of steel having a copper core
US5976333A and WO0163014 which both discloses various designs of a copper rod inserted in a steel tube embedded in a slot in a cathode block.
US6231745 describes copper and iron diffusion across their interface in a composite conductor.
US2006151333 describes a cathode collector separated by a contact zone and divided longitudinally into two sections of different electrical resistance, separated from one another by a mica sheet insulator.
Fe in the steel collector bar may diffuse into the Cu metal of an adjacent insert of copper.
This diffusion can result in an increase of ohmic resistivity of the composite collector bar, and followingly increase in the cathodic voltage drop over time.
the present invention relates to electrodes, anodes or cathodes, with composite conductors and a method for making same, where these detrimental effects can be reduced or avoided.
the invention relates to an electrode for production of aluminium metal by electrolysis of an aluminium containing compound dissolved in a molten electrolyte, where the electrowinning process is performed in smelting cells of conventional Hall-Heroult design.
the electrode comprises a calcinated carbon containing body having fixed thereto at least one composite metallic conductor comprising conducting elements of a Fe containing material and conducting elements of a Cu containing material.
the composite conductor comprises a diffusion barrier layer material at the interface between the two conducting materials. Several materials for the diffusion barrier layer have been achieved to as well as methods for application of the layer.
the invention relates to electrodes in general, but when referring to cathodes, there is one problem with collector bars in general, and that is that their operation temperature is well above 900°C, and other elements in contact with the collector bar may diffuse into the material and deteriorate the resistivity of the material. For normal steel collector bars, carbon (C) diffuses into the steel and the resistivity increases.
the increase in resistivity when Fe diffuses into Cu is measured, and shown in Fig. 2 .
the resistivity of Cu increase almost 100% when Cu becomes saturated with Fe. It is therefore desirable to have a barrier preventing the interdiffusion of Fe in Cu.
the required properties of a barrier preventing Fe to diffuse into Cu in a composite collector bar is:
a thin coating of TiB 2 powder was applied to a Cu - rod, and the effectiveness was measured in a diffusion experiment.
a Cu rod was dipped into TiB2 slurry and a 100 micron thick layer was applied.
the rod was put into a steel hollow and the assembly was heated to 950 °C for 14 days.
a barrier is not limited to the compounds mentioned here.
Other conductive metals, intermetallics or materials fulfilling the criteria, are potential barriers.
low solubility is also an important property.
the electrical conductivity of copper is very dependent of the impurity level, thus the solubility of a material defines the upper limit of the harm the material can do.
the barrier material should be able to block Fe, at the same time the barrier material itself must not enter the copper phase.
diffusion occurs more rapidly along grain boundaries and over free surfaces than through the interiors of crystals, i.e. impurities will diffuse faster into the metal along grain boundaries.
the solubility is low, the accumulation in the copper also should be expected to be low, and thus the potential reduction of the conductivity will be limited.
a good diffusion barrier also must have low solubility in copper, and possess sufficient electrical conductivity.
Atomic size factor rule The relative difference between the atomic diameters (radii) of the two species should be less than 15%. If the difference is >15%, the solubility is limited.
Crystal structure rule For appreciable solid solubility, the crystal structures of the two elements must be identical.
Valence rule A metal will dissolve a metal of higher valence to a greater extent then one of lower valence.
the solute and solvent atoms should typically have the same valence in order to achieve maximum solubility.
Electronegativity rule Electronegativity difference close to 0 gives maximum solubility. The more electropositive one element and the more electronegative the other, the greater is the likelihood that they will form an intermetallic compound instead of a substitutional solid solution. The solute and the solvent should lie relatively close in the electrochemical series.
a barrier metal in accordance to the present invention should fall outside the above rules in comparison with Cu and Fe, since it should not interfere with them.
interstitial solid solution When applying ceramics such as Refractory Hard Materials (RHM),as barrier material, interstitial solid solution can form if the smaller atom can be accommodated between the atoms in the metal lattice. According to Hagg's rule (see below) interstitial solid solution forms only if the atomic radius ratio of the two components r l /r m ⁇ 0.59.
RHM Refractory Hard Materials
RHM Refractory Hard Materials
W looks most promising, and possibly Mo and Ru.
W diffusion data from CRC handbook 58th Ed, 1977-1978, F-63-F-71 indicates that Fe diffuses four orders of magnitude slower into W than it does into Cu.
the composite conductor in the electrode comprises a diffusion barrier layer material at the interface between the two conducting materials. It has been demonstrated that;
the diffusion barrier layer can be made of a ceramic material or a RHM material.
Diffusion barrier layers of Nitrides or Borides such as TiN, TaN, ZrN, ZrB2, or TiB2 may also be applied.
Methods for applying these diffusion barrier layer materials can comprise to prepare it as a slurry and apply it to the conducting elements by dipping at least one of the two conducting elements in said slurry followed by drying, or it can be applied by powder coating.
a method for application of the diffusion barrier material may comprise that the barrier layer is applied by a Plasma coating technique.
Preferred barrier layers of a metallic material includes; Mo, W, Ta or Ru.
diffusion barrier layers can be prepared as a foil, by Chemical Vapor Deposition or Electroplating, and applied onto at least one of the two conducting elements before bringing these parts together.
the thickness of the barrier layer can preferably be in the range 1-1000 ⁇ m.

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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)
Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Cell Electrode Carriers And Collectors (AREA)

EP14743388.2A 2013-01-22 2014-01-20 An electrode for aluminium production and a method of making same Active EP2948577B1 (en)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
NO20130123A NO338410B1 (no)	2013-01-22	2013-01-22	En elektrode for aluminiumsfremstilling og en fremgangsmåte for tildannelse av samme
PCT/NO2014/000002 WO2014116117A1 (en)	2013-01-22	2014-01-20	An electrode for aluminium production and a method of making same

Publications (3)

Publication Number	Publication Date
EP2948577A1 EP2948577A1 (en)	2015-12-02
EP2948577A4 EP2948577A4 (en)	2016-04-20
EP2948577B1 true EP2948577B1 (en)	2018-12-05

Family

ID=51227824

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP14743388.2A Active EP2948577B1 (en)	2013-01-22	2014-01-20	An electrode for aluminium production and a method of making same

Country Status (10)

Country	Link
EP (1)	EP2948577B1 (ru)
CN (1)	CN104937144B (ru)
AU (1)	AU2014210417B2 (ru)
BR (1)	BR112015017071A2 (ru)
CA (1)	CA2896472C (ru)
EA (1)	EA028191B1 (ru)
NO (1)	NO338410B1 (ru)
NZ (1)	NZ709857A (ru)
SA (1)	SA515360744B1 (ru)
WO (1)	WO2014116117A1 (ru)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US5704993A (en) *	1995-10-10	1998-01-06	The Regents Of The Univerisity Of California, Office Of Technology Transfer	High conductivity composite metal
US6231745B1 (en) *	1999-10-13	2001-05-15	Alcoa Inc.	Cathode collector bar
US6528185B2 (en) *	2001-02-28	2003-03-04	Hong Kong Polytechnic University	Cobalt-tungsten-phosphorus alloy diffusion barrier coatings, methods for their preparation, and their use in plated articles
DE10227034A1 (de) *	2002-06-17	2003-12-24	Km Europa Metal Ag	Kupfer-Gießform
WO2004035870A1 (en) *	2002-10-18	2004-04-29	Moltech Invent S.A.	Anode current feeding connection stem
DE10261745B3 (de) *	2002-12-30	2004-07-22	Sgl Carbon Ag	Kathodensystem zur elektrolytischen Aluminiumgewinnung
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

2013
- 2013-01-22 NO NO20130123A patent/NO338410B1/no not_active IP Right Cessation
2014
- 2014-01-20 AU AU2014210417A patent/AU2014210417B2/en not_active Ceased
- 2014-01-20 BR BR112015017071A patent/BR112015017071A2/pt active Search and Examination
- 2014-01-20 CN CN201480005438.7A patent/CN104937144B/zh not_active Expired - Fee Related
- 2014-01-20 EP EP14743388.2A patent/EP2948577B1/en active Active
- 2014-01-20 EA EA201500763A patent/EA028191B1/ru not_active IP Right Cessation
- 2014-01-20 CA CA2896472A patent/CA2896472C/en not_active Expired - Fee Related
- 2014-01-20 NZ NZ709857A patent/NZ709857A/en not_active IP Right Cessation
- 2014-01-20 WO PCT/NO2014/000002 patent/WO2014116117A1/en active Application Filing
2015
- 2015-07-09 SA SA515360744A patent/SA515360744B1/ar unknown

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number	Publication date
AU2014210417B2 (en)	2017-06-29
EP2948577A4 (en)	2016-04-20
BR112015017071A2 (pt)	2017-07-11
WO2014116117A1 (en)	2014-07-31
EA028191B1 (ru)	2017-10-31
NZ709857A (en)	2019-07-26
AU2014210417A1 (en)	2015-07-16
CN104937144A (zh)	2015-09-23
CN104937144B (zh)	2019-09-03
SA515360744B1 (ar)	2018-12-10
CA2896472C (en)	2020-04-14
NO20130123A1 (no)	2014-07-23
CA2896472A1 (en)	2014-07-31
EA201500763A1 (ru)	2015-11-30
EP2948577A1 (en)	2015-12-02
NO338410B1 (no)	2016-08-15

Publication	Publication Date	Title
US3028324A (en)	1962-04-03	Producing or refining aluminum
US6719890B2 (en)	2004-04-13	Cathode for a hall-heroult type electrolytic cell for producing aluminum
AU2017203090B2 (en)	2019-04-18	Systems and methods of protecting electrolysis cells
KR20110060926A (ko)	2011-06-08	알루미늄 환원 셀용의 고전류 밀도에서 작동하는 산소 발생 금속 애노드
US6521115B2 (en)	2003-02-18	Nickel-iron alloy-based anodes for aluminium electrowinning cells
AU2014248631B2 (en)	2016-07-21	Systems and methods of protecting electrolysis cell sidewalls
WO2003071005A2 (en)	2003-08-28	Carbon containing cu-ni-fe anodes for electrolysis of alumina
US6248227B1 (en)	2001-06-19	Slow consumable non-carbon metal-based anodes for aluminium production cells
AU755103B2 (en)	2002-12-05	Nickel-iron alloy-based anodes for aluminium electrowinning cells
US20100258434A1 (en)	2010-10-14	Composite Collector Bar
US20160194772A1 (en)	2016-07-07	Iron-based anode for obtaining aluminum by the electrolysis of melts
EP2948577B1 (en)	2018-12-05	An electrode for aluminium production and a method of making same
Haarberg	2020	Electrodeposition of aluminium containing alloys from molten fluoride electrolytes containing metal oxides
CA2567127A1 (en)	2005-12-15	High stability flow-through non-carbon anodes for aluminium electrowinning
RU2734512C1 (ru)	2020-10-19	Термохимически стойкий анод для электролиза алюминия
WO2014003571A1 (en)	2014-01-03	Electrode and a method for making same
RU2200213C2 (ru)	2003-03-10	Токоподвод к самообжигающемуся аноду алюминиевого электролизера
WO2023276440A1 (ja)	2023-01-05	チタン含有電析物の製造方法及び金属チタン電析物
RU2471892C1 (ru)	2013-01-10	Способ производства металлов электролизом расплавленных солей
CN114182303A (zh)	2022-03-15	电解槽、特别是用于生产铝的电解槽

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