Light Metals 2009 Edited by: Geoff Bearne

TMS (The Minerals, Metals & Materials Society), 2009

ANODE REACTIVITY: EFFECT OF COKE CALCINATION LEVEL

1

M. J. Chollier-Brym1, A. Gagnon1, C. Boulanger1, D. Lepage1, G. Savard1, G. Bouchard1, C. Lagac2, A. Charette2

Rio Tinto Alcan, Arvida Research and Development Centre, 1955, Mellon Boulevard, Jonquire (Qubec), G7S 4K8, Canada
2
Universit du Qubec Chicoutimi, 555 boul. de lUniversit, Chicoutimi (Qubec), G7H 2B1, Canada
Keywords: Coke Calcination, Under-Calcination, Anode Baking, Anode Reactivity, Binding Phase Reactivity
Abstract
Air reactivity measurements related to coke and corresponding
anode pastes were performed using a LECO 701
thermogravimetric analyser (TGA). The tests were conducted
under isothermal conditions. Samples were protected from
oxidation during the heating period (20C/min) using argon.
Cokes calcined at the semi-industrial scale were used to
manufacture the anode pastes. They were prepared by mixing
ultra-fine coke particles (-450 mesh) and pitch (50/50 wt.%) to
simulate the anode binder phase. The green pastes were then
baked at 1100C and held at this temperature for 19h.
Microstructural analysis was conducted using an LEICA optical
microscope equipped with a CLEMEX VISION software for
image treatment.
The coke calcined in the semi-industrial rotary kiln was also used
to manufacture the bench scale anodes. These anodes were
manufactured according to a plant recipe, baked in an industrial
furnace and submitted to CO2 reactivity tests.

Coke properties and anode performance are affected by the coke

calcination level. Predictions of anode performance have
traditionally been based on evaluation of coke reactivity. Using
these methods, the use of a higher calcination temperature, up to
the point where desulphurization occurs, is preferred. Undercalcined cokes have, however, been shown to be beneficial to
reduce anode consumption in industry. Changes in coke quality,
such as increased sulphur, may affect the optimum calcination
level for an individual coke. Improved laboratory techniques are
required to define the industrial calcination level that will
minimize anode reactivity. In this work, different methods for
coke calcination and anode reactivity testing have been
investigated. The effect of the coke calcination level on anode
reactivity was studied as a function of the anode baking level. A
procedure for the evaluation of anodes, which reproduces
industrial results, has been developed. The study has also
confirmed that, for the coke used, calcination at a lower level will
reduce anode reactivity.

Results
Introduction
Effect of the Calcination Temperature on Coke Properties

For many years, the tendency was to seek the highest VBD and
therefore the highest anode density as possible. It is known that
higher calcination levels improve coke VBD (up to
desulphurization). Therefore, high Lc targets (27 to 30 ) were
previously set by Rio Tinto Alcan.
More high sulphur cokes are available on the market, due to the
degradation of coke quality and a tight coke market. The loss of
sulphur during the calcination step increases as the calcination
temperature and the coke sulphur level increases [1].
Desulphurization leads to creation of porosity which increases the
pitch demand and affects the anode reactivity. Current calcination
targets may be too high for cokes available on the market. In
addition, industrial trials performed with under-calcined coke tend
to show that under-calcined coke is beneficial to decrease anode
dusting [2].
In the following, different calcination methods were evaluated
with attempt to reproduce the effect of industrial calcination
conditions on coke properties. In addition, the effect of the coke
calcination level on coke and anode paste reactivity and
microstructure was investigated and compared to that of
laboratory anodes.

Table 1 shows the properties of coke calcined at different levels in

a semi-industrial rotary kiln. The crystallite size (Lc) increases as
the calcination temperature increases, as expected. The sulphur
content of the coke decreases very slightly with increasing
calcination temperature. VBD increases with increasing
temperature up to 1315C.
Table 1. Properties of Coke Calcined in a Semi-Industrial Rotary
Kiln
Coke Calcination
Lc ()
S (%)
VBD
Temperature (C)
(g/cm3)
1060
1125
1220
1315
1380

17.2
19.8
24.6
31.6
28.4

3.21
3.22
3.15
3.12
2.89

0.897
0.901
0.910
0.911
0.883

Comparison with Industrially Calcined Coke. The distribution of

the pore volume of the coke calcined in the semi-industrial rotary
kiln at 1315C is similar to the industrially calcined coke
(Figure 1). Porosities were estimated from the VBD values,
apparent density and real density (Figure 2). As calcination
temperature increases, the microporosity (accessible to He)
increases. Besides, one can also observe that the coke industrially
calcined (squares) develops essentially the same type of porosity
accessible to helium and mercury as the coke calcined at the semiindustrial scale.

Experimental Section
A high sulphur coke was calcined at different temperatures using
different calcination procedures:
- Calcination in a semi-industrial rotary kiln,
- Flash calcination in a high temperature furnace,
- Slow calcination in a laboratory anode baking furnace.

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Table 2. Properties of Coke (< -325 meshes) Calcined at the

Laboratory Scale
Flash
Slow
Calcination
Calcination
Coke Calcination
Lc
VBD
S
Lc
S
Temperature (C)
()
(g/cm3)
(%)
()
(%)
900
15.3
0.877
2.96
1100
18.6
0.877
2.90 a22.7 a2.87
b
25.2 b2.51
1200
23.9
0.854
2.85
b
1250
35.4 b2.25
1315
29
0.855
2.83
1380
32.9
2.80
a
plateau duration= 5h ; bplateau duration = 19h

0.050
Semi-industrial Calcination
Industrial Calcination

0.045
0.040

dV/dlogR (cm /g)

0.035
0.030
0.025
0.020
0.015
0.010
0.005
0.000
1.E+01

1.E+02

1.E+03

1.E+04

1.E+05

1.E+06

Pore Radius ()
3.00

Figure 1. Distribution of Porous Volume as a Function of Pore

Radius

2.95
2.90
2.85

80

2.80
S (wt. %)

Intra-particle porosity,
accessible to Hg

Porosity [%]

60

2.75
2.70
2.65

Intra-particle porosity,
accessible to He, but
not to Hg

40

2.60
2.55
2.50

20

(+4)

Intra-particle porosity,
not accessible to He

20

25

30

35

(-8+65)

(-325)

Coke Granulomletry (mesh)

Figure 3. Evolution of Sulphur Content as a Function

of the Coke Granulometry During Slow Calcination

0
15

(-4+8)

40

Lc []

Coke and anode paste microstructure and reactivity

Figure 2. Type of Porosity Developed by the Coke Calcined in a

Semi-Industrial Rotary Kiln as a Function of the Coke Calcination
Level

The air reactivity of cokes and anode pastes was investigated by

thermogravimetric analysis. An Arrhenius plot is presented in
Figure 4 for cokes calcined at different levels, at the semiindustrial scale. The activation energy was calculated using the
linear part of the curve and was found to be comprised between
153 and 176 kJ/mol, which is close to values reported in the
literature for air oxidation of anode-grade coke [3-5].

Laboratory Calcination. Table 2 summarises the properties of the

coke calcined at the laboratory scale. Fast calcination leads to
lower VBD and higher sulphur loss than the semi-industrial
calcination.
The most important desulphurization occurs with slow calcination
(sulphur loss = 22.3% at Lc = 25.2 ). In addition, as the particle
size of the coke sample decreases, desulphurization becomes more
important (Figure 3).
These results show that the semi-industrial calcination procedure
is the most suitable to reproduce industrial calcination conditions
and is a more effective method to be used in the evaluation of
cokes.

1
Tc = 1060 C
Tc = 1125 C
Tc = 1220 C

-1

k (min )

0.1

0.01

0.001
1.32

1.34

1.36

1.38

1.4

1.42

1.44

1.46

1000/T (K-1)

Figure 4. Evolution of the Rate Constant for the Coke-Air

Reaction, as a Function of the Oxidation Temperature Expressed
as (1/T)

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Figure 5 shows the evolution of the rate constant for the coke-air
reaction, as a function of the coke calcination level. The coke
reactivity decreases as the coke calcination level increases, as
expected. However, in the testing of anode pastes, the opposite
trend is observed (Figure 6): the anode paste reactivity decreases
as the calcination level of the coke decreases. This could be
explained as follows: the lower the calcination level of the coke is,
the more the coke and the pitch are transformed together during
the baking, which minimizes the anode paste reactivity.
Microstructurtal analysis was performed on cokes and anode
pastes in order to verify if a better contact between coke and pitch
is achieved when the coke is under-calcined. Microstrucrural
analysis reveals that the microstructures of anode pastes prepared
with coke calcined at 1060 and 1380C are quite different (Figure
7 and 8). In the anode paste prepared with a coke calcined at
1380C, the coke particles can be distinguished from the pitch.
Moreover, the coke particles are not well bonded into the
surrounding pitch, so that the exposure to air could lead to
preferential oxidation of pitch. On the other hand, the anode paste
manufactured with the low calcined coke displays a homogeneous
structure, which could minimize the preferential oxidation of
pitch.

Figure 7. Microstructure of Anode Paste Manufactured with a

Coke Calcined at 1380C

0.07
Tc = 1060 C
Tc = 1125 C
Tc = 1220 C

0.06

-1

Rate Constant (min )

0.05

0.04

0.03

0.02

0.01

Figure 5. Evolution of the Rate Constant for the Coke-Air

Reaction, as a Function of the Coke Calcination Level
(oxidation at T = 460C)
0.04

0.035

Figure 8. Microstructure of Anode Paste Manufactured with a

Coke Calcined at 1060C
Anode Reactivity

green coke
Tc = 1060 C

There have been conflicting reports in the literature regarding

laboratory studies related to the effect of coke calcination level on
anode performance [6-12]. The anode recipe and the baking level
may vary from one study to another, which could affect the
conclusions. In the following,
In the following, two lots of anodes were manufactured with the
coke calcined at 1125 C and 1270 C, according to the plant
recipe and baked into a industrial closed furnace. It was thus
possible to have access to different baking levels. These anodes
were introduced in the stubholes of industrial anodes at different
locations in the pit (Figure 9, black circles). Results related to
industrial baking are presented in Figure 10 and 11. It can be seen
that under-calcined coke reduces anode dusting in a wide range of
anode baking temperatures, which confirms that under-calcined
coke is beneficial to decrease the binding phase reactivity as
reported by other authors at the plant scale [2]. Moreover, the
more the anodes are under-baked, the more the under-calcined
coke is efficient to reduce anode dusting.

Tc = 1125 C

-1

Rate Constant (min )

0.03

0.025

0.02

0.015

0.01

0.005

Figure 6. Evolution of the Rate Constant for the Anode Paste-Air

Reaction, as a Function of the Coke calcination Level
(oxidation at T = 500 C)

907

Equivalent
Temperature
Temprature
quivalente

Pit rows

Results obtained on cokes and pastes have shown that:

- The coke reactivity decreases with calcination temperature (up
to desulphurization), as expected,
- Under-calcination is beneficial to decrease the reactivity of
anode pastes.
Microstructural analysis of anode pastes demonstrated that the
interaction between pitch and coke is improved and that the
structure of the composite is very homogeneous when the coke is
under-calcined.
Industrial baking of laboratory anodes confirms the reactivity test
results obtained on anode pastes, namely that under-calcined coke
is beneficial to reduce anode dusting.

1200-1225
1175-1200
1150-1175
1125-1150
1100-1125
1075-1100
1050-1075
1025-1050
1000-1025
975-1000
950-975
925-950
900-925

References
1
90
92
95
97
10
11
12
50
75
00
25
0
5

1.
L. Edwards, K. Neyrey. L. Lossius, A Review of Coke
and Anode Desulfurization, Light Metals, (2007), 895-900.

Pit columns

2.
B. Samanos, C. Dreyer, Impact of Coke Calcination
Level and Anode Baking Temperature on Anode Properties,
(2001), 681-688.

Figure 9. Distribution of Baking Temperatures in a Pit

CO2 Reactivity (Dust)

3.
K.N. Tran, S. Bhatia, A. Tomsett, Air Reactivity of
Petroleum Cokes: Role of Inaccessible Porosity, Ind. Eng. Chem.
Res., 46 (2007), 3265-3274.

14

Lc = 19.7 A

Lc = 26.7 A

12

Dust (%)

10

4.
R.J. Tyler, Intrinsic Reactivity of Petroleum Coke to
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8
6

5.
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4
2

6.
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Aluminium, Light Metals, (1971), 385-408.

0
975

1050
1100
Equivalent Anode Baking Temperature (C)

1200

Figure 10. Evolution of the CO2 Dust as a Function of the Anode

Baking Temperature and Coke Calcination Level

7.
E. A. Kolodin, V.Ya. Nikitin, Effect of Coke Properties
and its Calcination Conditions on Anode Consumption During
Aluminum Electrolysis, Tsvet. Met., 8: 44-45, (1982), 365-370.

CO2 Reactivity (Rsidue)

8.
Q. C. Nguyen, Properties of Laboratory Green Coke
Anodes, Light Metals, (1985), 903-913.

100
90

Lc = 19.7 A

Lc = 26.7 A

9.
T. Mftolu, R. Fernandez, The Effect of Feedstock
and Coke Calcination Degree on the Properties of Bench Scale
Anodes, Light Metals, (1990), 511-519.

80

Rsidue (%)

70
60
50

10.
D. Belitskus, Effects of Petroleum Coke Calcination
Temperature and Anode Baking Temperature on Anode
Properties, Light Metals, (1991), 557-563.

40
30
20

11.
L. Lavigne, L. Castonguay, Prediction of Anode
Performance from Calcined Coke Properties, Light Metals,
(1993), 569-573.

10
0
975

1050
1100
(C)
Equivalent Anode Baking Temperature

1200

Figure 11. Evolution of the CO2 Residue as a Function of the

Anode Baking Temperature and Coke Calcination Level.

12.
R. Fernandez, B. Steine, T. Mftolu, Improving
Calcined Coke Quality for Better Anode Performance, Light
Metals, (1997), 137-147.

Conclusions
Acknowledgments
The financial support of CRSNG (ref. RDCPJ 340506-06) and of
FQRNT-NSERC (ref 124512) is gratefully acknowledged.

In evaluation of coke, the calcination procedure affects coke

properties. Semi-industrial calcination is the most suitable method
to reproduce industrially calcined coke properties.

908