Spent Si N Bonded Sic Sidelining Materials in Aluminium Electrolysis Cells
Spent Si N Bonded Sic Sidelining Materials in Aluminium Electrolysis Cells
Abstract
Fabrication
Introduction
Si3N4 bonded SiC materials have during the last decades become
the state of the art sidelining material in aluminium electrolysis
cells due to its excellent oxidation resistance compared with
traditional carbon lining, poor electrical conductivity, and high
thermal conductivity. By using Si3N4 bonded SiC materials, the
total thickness of the sidelining and the sideledge can be reduced
and larger anodes can be used [1-4]. In modern cell designs, the
thickness of sidelining blocks can be down to 5 cm thickness.
During the operation, Si3N4 bonded SiC materials will suffer the
chemical degradation [5-8,11,13]. The development towards high
amperage cells with thinner sidelining and the demand for long
pot lifetime call for a better understanding of the chemical
stability of Si3N4 bonded SiC materials.
Si3N4 binding phase is rarely phase pure and consists of - and Si3N4 phase formed by different mechanisms [9]. The ratio
between the two phases will vary according to the fabrication
condition. -Si3N4 phase is typically dominant in the whole block.
The content of -Si3N4 phase is higher in the interior of the block
than close to the surface [13].
Experimental
Spent Sidelining Materials and Sampling
Three different spent sidelining blocks have been analyzed, which
are supplied by two producers and taken from autopsies with
different ages in operation: 270 days (Sicatec 75, LIRR, China),
604 days (Sicatec 75, LIRR, China) and 1569 days (Refrax 20,
Saint Gobain). The cross section of the spent sideling block is
shown in Figure 1.
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Results
Mineralogical and Chemical Analysis of Spent Sidelining
The phase composition of the blocks at the age of 270 and 604
days are similar. The main degradation products detected are
Si2ON2 in the gas zone and Na2SiO3 in the electrolyte zone, see
Figure 3. The basic conditions at the electrolyte zone induced by
Na related reactions were confirmed by a pH paper test. The
content of - Si3N4 phase is more pronounced in the gas zone than
in the electrolyte zone and in the pristine materials.
Figure 4. XRD profiles for samples from electrolyte and gas zone
of spent block at the age of 1569 days (Refrax). - represents Si3N4; - represents -Si3N4. Un-labeled peaks are for SiC.
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Si contents for all blocks are in the range of 0.2-0.7wt% and have
no significant change with age. The amount of the degradation
phases and -Si3N4, -Si3N4 present in the spent blocks at
different ages is summarized in Table 1. The data were obtained
by quantitative Rietveld refinement.
Table 1. Rietveld refinement of the X-ray diffraction patterns.
Unit of phase amount is wt%.
1: close to the frozen bath. 4 or 5: close to the steel shell.
For the younger cell (270 days), the content of reaction product
phases in the electrolyte zone is much higher than in the gas zone.
For the older cell (1569 days), the oxidation in the gas zone is
more severe and Si2ON2 is found down to the electrolyte zone.
Na2SiO3 is restricted to the electrolyte zone, which means that
although Na(g) diffusing from the carbon cathode into the
sidelining in the horizontal direction, it does not penetrate much
further upwards in the vertical direction. We propose that excess
oxygen containing species diffusing downwards from the top of
the sideling condenses the Na(g) and retards further diffusion and
reaction of Na(g). Finally, it should be noted that the amount of
the degradation phase Na2SiO3 in the older cell is not higher than
that in the younger cell.
-Si3N4 phase is dominant in the binder phase of the pristine
block. The /-Si3N4 ratio is less than one. In the gas zone after
degradation by pot gas, the ratio increases due to the reduction of
the -Si3N4 phase content and increase in -Si3N4 phase. The ratio
is even revised and larger than 1 in the block at the age of 270 and
1569 days, which implies that -Si3N4 dominates in the gas zone.
This indicates -Si3N4 is more reactive and suggests the
possibility of to -Si3N4 transformation [13]. The phenomenon
is more pronounced in the cell at the age of 1569 days: /-Si3N4
ratio could reach 16.4 and -Si3N4 phase is as low as 0.5 wt%.
/-Si3N4 ratio seems to have a relationship with the amount of
Si2ON2 as shown in Figure 5. With increasing Si2ON2 amount, the
/-Si3N4 ratio increases accordingly. It implies that -Si3N4 is
preferably oxidized to form Si2ON2 and that the to -Si3N4
transformation may be related to the formation of Si2ON2. In any
case, /-Si3N4 ratio correlates well with the degree of the
oxidation by pot gas.
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Figure 7. Oxygen content vs. distance to the bath for the spent
sidelining blocks at the age of 270, 604 and 1569 days.
Microstructure
Thermal Conductivity
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Simulation
Discussion
Reaction Schemes and Diffusion Route
During normal operation, the sidelining block is almost always
covered by a frozen electrolyte layer (ledge) or crust and the
sidelining is not exposed to the aluminium pad and the electrolyte
directly [20]. However, the lining materials still deteriorate
gradually over time due to Na(g) diffusion and the accompanied
reactions leading to deterioration. An overall proposed path for
the diffusion of the gaseous species into the sidelining is shown in
Figure 13.
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(1.3)
Acknowledgement
References
[1]
[2]
[3]
Saint-Gobain Ceramics,
http://www.refractories.saintgobain.com/data
/element/node/application.
[4]
[5]
[6]
(1.4)
(1.6)
(1.7)
[7]
[8]
[9]
[10]
[11]
[12]
Simonsen AS.
http://www.simonsen.eu/PRODUCTS/sicatec-75.pdf.
[13]
[14]
Conclusion
Autopsies of the spent blocks at different ages show generally the
same trends. The fine grained Si3N4 binder phase is the
chemically degraded part of the sidelining materials. Degradation
in the upper part (gas zone) prefers -Si3N4 resulting in the
formation of Si2ON2 by oxidizing gases (air or CO/CO2). The /Si3N4 ratio is to some degree related to the amount of Si2ON2
phase and correlates well with the degree of the oxidation by pot
gas. Chiolite can be observed in gas zone due to the condensation
reaction of NaAlF4 in case of less protection of side ledge.
Density, porosity and thermal conductivity have no significant
change in this region. In the infiltrated lower part of the sidelining
oxidation was influenced by the presence of Na(g) and the product
was Na2SiO3. The reaction products densify the block
considerably. Thermal conductivity in this part decreases due to
the formation of Na2SiO3 phase with significantly lower thermal
conductivity. Na(g) diffusivity is proposed to be governed by the
oxidation reactions. Na(g) will be retarded in the infiltration area
instead of penetrating throughout the block due to the reactions
with oxidizing species from the top of the block. Finally, the
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