Anode characterisation and gas diffusion behaviour in aluminium smelting

Epma Putri, Geoffrey Brooks, Graeme Snook, and Ingo Eick

Citation: AIP Conference Proceedings 1805, 040001 (2017); doi: 10.1063/1.4974422

View online: http://dx.doi.org/10.1063/1.4974422
View Table of Contents: http://aip.scitation.org/toc/apc/1805/1
Published by the American Institute of Physics

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 Anode Characterisation and Gas Diffusion Behaviour in
Aluminium Smelting
Epma Putri1,*, Geoffrey Brooks1, Graeme Snook2, Ingo Eick3
1
Faculty of Science, Engineering and Technology, Swinburne University, Hawthorn, Victoria 3122, Australia
2
CSIRO, Mineral Resources, Clayton, Victoria 3169, Australia
3
Hydro Aluminium Deutschland GmbH, 41468 Neuss, Germany
*
Corresponding author: eputri@swin.edu.au

Abstract. Over the past century, significant research on different aspects of the Hall-Héroult process has been conducted
to increase energy efficiency. Bubble generation at the anode reaction and its contribution to the overall voltage drop in
aluminium production holds significant potential for energy saving, yet the details of the gas transport mechanism for
bubble nucleation behaviour are not completely understood. The multi-step electrochemical reaction releases
predominantly CO2 gas along with CO gas, which is a reduction product formed by reaction of CO 2 with the anode
carbon. Complicating the reaction is the multiple paths by which the gas can diffuse (either through the porous anode or
the electrolyte bath). There has been no detailed investigation of the correlation between gas diffusion as a function of
anode and bath properties. In the present study, the porosity measurement techniques in the anode will be used to
understand the relation of gas diffusion and anode properties. A porosimetric study was conducted for two different
anode samples using mercury intrusion porosimetry (MIP) and hydrostatic method. The MIP method provides important
anode properties information such as density, percent porosity, pore size distribution, permeability, and tortuosity factor
which affect gas diffusion and anode performance. The Knudsen number obtained from MIP data shows both Knudsen
diffusion and molecular diffusion need to be considered when predicting the effective diffusion.

Keywords: porosity, gas diffusion, anode properties

INTRODUCTION
In recent years, there has been an increasing amount of literature on anode bubble behaviour as industry seeks to
reduce the negative effect on the bubble formation. The bubbles constrain the current passage that passes through
the electrolysis cell and increases the electrolyte resistance thus, in turn results in higher energy consumption for the
smelting process 1. The bubble layer is shown in the schematically in Fig. 1. The bubbles are formed as the result of
continuous CO2 and CO gas evolution under carbon anode during electrolysis. The bubble nucleation reaction takes
place in the interface between active electrolysis sites and the porous anode with approximately 15 to 25% being
interconnected pores 2. The overall cell reaction is:

2 Al2O3 + 3 C = 4 Al + 3 CO2 (1)

The voltage drop caused by bubble formation itself contributes ~0.25 V of the total cell voltage 4.19 V 3. Despite
the important role of the bubble layer, the details of bubble nucleation behaviour and the gas transport mechanism
for this process are not completely understood. Einarsrud et al 4 proposed there are two possibilities of the gas path,
namely transport through pores in the anode or through the bath. However, there are limited measurement data for
gas diffusion in both media and the correlation between anode and bath properties such as composition, porosity,
and permeability of anode material are not fully understood. A porosimetric study on the anode is required to

Proceedings of the 1st International Process Metallurgy Conference (IPMC 2016)

AIP Conf. Proc. 1805, 040001-1–040001-9; doi: 10.1063/1.4974422
Published by AIP Publishing. 978-0-7354-1473-0/$30.00

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understand gas transport mechanism of bubble nucleation in Hall-Héroult cell and its correlation with other anode
properties.

FIGURE 1. Schematic diagram of Hall-Héroult cell 5

Anode Porosity
Typical prebaked anodes for aluminium production consist of 65% petroleum coke, 20% anode butts, and 15%
coal tar pitch. The costs of these raw materials amount to approximately 50% of the total anode production costs
[10]. Anode properties and performance are related to three fundamental components: carbon microstructure,
impurities, and porosity accompanied by their interactions 6. The presence of pores in the carbon anode due to the
raw materials, chemical reaction and the manufacturing process are inevitable. This study will review the porosity
measurement techniques for carbon anode and its contribution to understanding the outcome for anode performance.
Fischer and Perruchoud 7 differentiated the pore size influence on the internal anode reaction. The authors
suggested that the small pore sizes generate most of the internal pore volume and are well connected to the exterior
surface of the particles by the feeder pores (transitional and macro pores). Thereafter, the reactant gas (e.g., air or
CO2) can rapidly diffuse and react with the active surfaces.
Significant progress in anode porosimetry study has been achieved through the investigations by Sadler and
Algie 8. They performed mercury porosimetry to investigate internal oxidation from the anode butt. In their study,
the pore entrance radius (PER) measurement reported in the range of 0.002 to 100 ߤm with most of the measured
porosity located in the range of pore radius around 1 to 5 Ɋm. The results indicate the anode porosity profile
influences the sub-surface reaction between carbon dioxide and carbon anode via pore growth and enlargement of
fine porosity (< 0.01Ɋm). Engvoll 9 observed similar porosity identification with same technique in the range 0.0037
to 80 μm. Alternatively, Suriyapraphadilok 10 performed similar measurements with helium pycnometer which gave
higher factors of pore volume than the results reported from previous research due to the higher accuracy when
compared with mercury porosimetry.
Rorvik and Øye 11 conducted anode porosity investigations using microscopy and image analysis. The samples
were impregnated with fluorescent epoxy which will reveal the structure of the pore under the ultraviolet light of the
microscope. Then, the sample was analyzed using a high-end microscope and a computer equipped with a motorized
stage controller. The systematic movement allows the generation of a series of adjacent images. The image analysis
shows that the majority of pores in the anode exhibit porosity with a radius between 10 to 50 Ɋm. The disadvantage

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of the use of the fluorescent epoxy is its restricted penetration to the closed pores. However, loss of closed pores is
not a major error because the qualitative observation shows that the pores are heavily connected.
In more recent years, the investigation of material porosity using X-ray tomography has been developed.
Sommerseth 12 evaluated anode surfaces with respect to consumption, density, pore distribution and real active area
before and after electrolysis. Through CT scanning, anode surface and pores in the anode structure could be
investigated. The bubble coke has lower consumption rate and poorer wetting characterization towards the
electrolyte than the bulk material. Therefore, it wa concluded a possible reason of coke bubble consumption is
because of high porosity grains and electronic resistivity rather than CO 2 gas being blocked by the electrolyte
penetration.

Gas Diffusion in Porous Solid

Diffusion can be defined as the net transport of matter in a system by random molecule motion. The movement
acts to remove chemical potential differences and will eventually produce an equilibrium state of concentration 13. In
porous media, diffusion can be categorized as mechanisms namely pure molecular diffusion, pure Knudsen
diffusion, mixed diffusion and random porous material, as shown schematically in Fig. 2. These mechanisms can be
predicted by the ratio between the mean free path and pore size of the porous media. The Knudsen number (K n) is
calculated using Eq. (2).

FIGURE 2. Distinct mechanism by which molecular species get transported (a) pure molecular diffusion; (b) pure Knudsen
diffusion; (c) mixed diffusion; d) random porous material

O
Kn (2)
dp

where dp is diameter of pores which is evaluated based on the average pore size or chord length distribution and ߣ is
the gas mean free path, which is calculated by Eq. (3).

k BT
O (3)
2 PSd g2

where kB is the Boltzmann constant (1.3807 x 10-23 J/K), T is the temperature of gas (K), P is the gas pressure, and d g
is the effective diameter of gas molecule that can be estimated using appropriate covalent and Van der Waals radii.

040001-3
 Molecular diffusion is observed in solids with large pores or high system pressure and dominates if the Knudsen
number is smaller than 0.1. Because the pore size is greater than the free path of the diffusing gas, the molecule-
molecule collision is more significant when compared to the molecule-wall collision. Furthermore, consideration of
the Knudsen diffusion becomes more necessary for Knudsen numbers greater than 10. When the free path of the
diffusing gas is much larger than the pore size, the molecules collide with the wall more often than between
themselves 14. Hence, molecule-wall collisions become more significant. The diffusion mechanism prediction in
anodes can be obtained by measuring the porosity and the average pore size using MIP.

Mercury Intrusion Porosimetry (MIP)

Mercury porosimetry is an established technique for measuring the porosity characteristics of solids by liquid
mercury penetration into the carbon sample with applied pressure 15. Mercury is used almost exclusively as the
liquid of choice for intrusion porosimetry because it is non-wetting to most solid materials. MIP method has many
advantages including: 1) fast determination speed, usually every 1-2 hours for a sample; 2) high measuring pressure,
so it is suitable for cores with high, medium or low permeability, and complete capillary pressure curve can be
obtained for further analysis; 3) irregularly shaped rock samples can be tested; 4) measuring range for pore diameter
is relatively wide 3 to 360 nm.
However, this method has several limitations. It does not measure the actual pore size, instead it determines the
largest entrance to the pore. The exertion from high pressures can also be subject to errors in the porosity
interpretation due to further compaction or collapse of loosely packed material. Moreover, this technique has size
range limitations. The smallest pore size depends on the maximum pressure while the largest measurable pore size is
dependent on the height of the sample which determines a minimum head pressure. For example, in the instrument
with 400 MPa maximum pressures, the smallest pore size that can be detected is 3.5 nm and the maximum pore size
is 1 mm diameter in a 1 cm high sample 15.

MATERIAL AND EXPERIMENTAL METHOD

In order to obtain a pore properties comparison from different carbon materials, samples from two different
anode production batch (L-26, L-44) from Hydro aluminium AS and also graphite to compare the homogeneity of
the carbon sample and its behaviour. The investigated anode carbon (L-26, L-44) was received physical and
chemical characterization given in Table 1. The analysis was performed in the laboratory at Hydro Aluminium,
Norway.

TABLE 1. Physical and chemical properties of the investigated carbon anode.

Impurities (ppm)
Anode Density (g/cm³)
S V Si Fe Ca Ni Na K
L-26 1.63 1.97 206 136 424 82 136 178 10
L-44 1.635 1.9 201 112 420 91 147 340 9

Three samples each material were tested by the hydrostatic method according to ISO 5017:2013 for bulk density
and apparent porosity determination. The hydrostatic method is based on Archimedes principle and used because it
is a simple and non-destructive test. The same samples were tested use mercury intrusion porosimetry method to
obtained further pore characterization. During a MIP test, each sample underwent two analyses: low-pressure and
high-pressure analyses. Entrance radius of pores is proportional to the applied pressure and the volume of intruded
mercury is recorded.The highest pressure produced by Micromeritics AutoPore IV 9510 as seen in Figure 3 is 60
000 psia, and the pore throat diameter corresponding to this pressure according to Washburn equation is about 6 nm.
The largest pore throat diameter recorded by MIP is about 300 μm under low-pressure analysis.

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 FIGURE 3. Micromeritics AutoPore IV 9510 and sample inside the penetrometer

RESULTS AND DISCUSSION

Density and Porosity

The density and porosity are important properties of the carbon anode. Higher density means a reduced porosity
and a reduced permeability that should extend the operational life of the anode. However, excessive density will lead
to poor thermal shock resistance and fracturing of the anode upon first use in an electrolysis cell 8. There are
different definitions of density, with the simple definition of density being the mass of an object divided by its
volume. The mass measurement itself is straightforward, but it is the determination of the material volume that
makes the density value different, as depicted in Fig. 4. Bulk volume is measured as the volume within the whole
particle, while apparent or skeletal volume is the bulk volume minus the open pores and true volume is both the
open and closed pore volume subtracted from the bulk volumes.

FIGURE 4. Comparison of different volume determination 16

Results from anode carbon samples show good agreement that density is inversely proportional to percent
porosity as shown in Fig. 5. Despite the bulk density and skeletal density of L-26 being lower than L-44, it shown
that L-44 has larger percent porosity due to a significant difference in skeletal density. Furthermore, bulk density
and percent porosity values from each technique are in a close proximity.

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 3.00

2.50

2.00

1.50

1.00 2.17 2.02

1.76 1.60 1.86 1.70 1.77
1.52 1.61
0.50

0.00
L44 L26 Graphite

Skeletal Density MIP Bulk Density MIP Bulk HM

FIGURE 5. Density measurement comparison between MIP and hydrostatic method

Interestingly, the percent porosity results for graphite sample from hydrostatic method were significantly lower
than percent porosity measurement with MIP as presented in Figure 6. The range measurement of hydrostatic
method is from 0.1 to 1000 μm thus giving the porosity result difference. It can be assumed that graphite sample has
a smaller pore size that it is very difficult for water to penetrate into without applied pressure. Another a major
source of error in hydrostatic method is blotting, when the sample is blotted a bit hard it can bring out the water from
the pores which can give variable results 17.

25.00

20.00
% Porosity

15.00

10.00
18.10 18.35 17.86 17.18
15.91
5.00 11.28

0.00
L44 L26 Graphite
MIP HM

FIGURE 6. Comparison of percent porosity measurement between MIP and hydrostatic method

MIP measurements for each sample were done in triplicate to evaluate the repeatability of MIP. Ideally, a
repeatability test should be carried out on the same piece of sample. However, this is not possible in the case of MIP
test because the sample is contaminated with mercury after MIP test. As a result, we choose three representative
samples from the same rock block to check the repeatability of MIP. For anode L-44, we obtained the porosity as
18.10 ± 17.58%; for anode L-26, the porosity is 17.86 ± 7.31% and for graphite is 15.91 ± 10.07%. Considering the
inherent heterogeneity of carbon anode and graphite, this result is acceptable and the repeatability of MIP is verified.
The error of the instrument is monitored by calibration measurement using standard material. This error is negligible
compared the heterogeneity of the sample.

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 Pore Volume Distribution by Pore Size
The plot of incremental intrusion volume versus pore entrance diameter provides the size distribution of pore
size and which is dominated. Figure 7 presents the incremental pore volume distribution versus pore entrance
diameter. From the graph, it can be seen that most of the measured porosity on carbon anode L-26 and L-44 are
located in the range of 1 to 8 ߤm while the graphite pore size distribution is concentrated with high intrusion volume
in the range of 5 to 8 ߤm. This size distribution result for anode carbon is in a good agreement with the results
obtained from Sadler and Algie 8 and Engvoll 9. The repeatability of mercury porosimetry experiment is better than
1% standard deviation despite the various assumptions and experimental factors affecting the absolute accuracy of
the data. In general, results from the experiments are useful in comparative studies of similar materials.

50 Graphite (1)
45 Graphite (2)
Incremental Intrusion (mm3/g)

40
Graphite (3)
35
L44 (1)
30
L44 (2)
25
L44 (3)
20
L26 (4)
15
L26 (2)
10
5 L26 (1)

0
0.001 0.01 0.1 1 10 100 1000
Pore Entrance Ratio (ߤm)

FIGURE 7. Incremental pore volume distribution (a) L-44 (b) L-26 (c) graphite

The possible explanation for the different size distribution between carbon anode samples and graphite lies in the
production of the sample. Anode carbon is made by approximately 65 % petroleum coke, 20% anode butts and 15 %
that makes the pore size is not uniform. Furthermore, Azari et al 18 concluded that the optimum mixing time and
temperature improve the distribution of coke, pitch and porosity and penetration of binder matrix, leading to
enhanced anode density. These synthetic graphite normally follow a production process similar to that of baked
carbon (forming, impregnation, rebaking) but require an additional process step, that of graphitization where
temperatures of around 3000 °C are achieved.

Gas Transport in Porous Media

Following anode characterization and defining the important properties that affecting the diffusion in porous
solid, this data will be utilized to incorporate with the theoretical prediction.
Knudsen number is a dimensionless number that will be used to predict the diffusion mechanism in porous solid.
The Knudsen number is evaluated using average pore size and the gas mean free path as shown in Eq. (2). Two
forms of gas diffusion within pores are Knudsen diffusion and molecular diffusion. Figure 8 illustrates the Knudsen
number calculation derived from average pore sizes obtained from MIP for the next diffusion in porous solid
experiment temperature range (293.15-1233.1 K). If the Knudsen number is higher than 10 it implies that mean free
path of the gas molecule is much larger than the pore diameter it passes through, then the collision of the gas
molecules with the pore walls (i.e., Knudsen diffusion) will be the dominant process. In contrast, if the Knudsen
number is lower than 0.1, the mean free path is much smaller than the pore diameter, the collisions between gas

040001-7
molecules (molecular diffusion) will control the diffusion process. The transition diffusion regime where Knudsen
and molecular diffusion occur together approximately to 0.1 < Kn < 10 19. Knudsen number obtained from MIP is
calculated in the transition regime (0.1 < Kn < 10) which both Knudsen diffusion and molecular diffusion are taken
into calculation. This information can be used to determine the appropriate formula for predicting gas diffusion
coefficient and further compared with the diffusion in the porous solid experiment. Furthermore, this diffusion
coefficient data become a fundamental key that is required to understand and plays an important role in bubble
behaviour modelling in Hall-Héroult cell to minimize the bubble effect and improve energy efficiency.

Mixed
Diffusion

FIGURE 8. Knudsen number estimation

CONCLUSION
The MIP and hydrostatic method were used to characterize density and porosity data that relates to anode
performance. Graphite was introduced in the test to compare the homogeneity of the carbon sample and its
behaviour. Considering the inherent inhomogeneity of carbon anode and graphite, this result is acceptable and the
repeatability of MIP is verified. The hydrostatic can be used for measuring rough porosity differences before and
after anode diffusion experiments. The pore volume and size distribution obtained in this study are in agreement
Sadler and Algie 8. In their study, the PER measurement reported in the range of 0.002 to 100 Ɋm with most of the
measured porosity located in the range of pore radius around 1 to 5 Ɋm. Engvoll 9 observed similar porosity
identification in the range 0.0037- 80 Ɋm with Sadler and Algie 8. The Knudsen number obtained from MIP is
calculated in the transition regime (0.1 < Kn < 10) which both Knudsen diffusion and molecular diffusion are taken
into account rather than assume which mechanism is controlling. The contribution of each mechanism can be
estimated by the Bosanquet equation in further experiment.

ACKNOWLEDGMENT
The present work was supported and financed by Hydro Aluminium and the Research Council of Norway.
Permission to publish the results is gratefully acknowledged.

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