Drying, Roasting, and Calcining of Minerals

Edited by: Thomas P. Battle, Jerome P. Downey, Lawrence D. May, Boyd Davis,
Neale R. Neelameggham, Sergio Sanchez-Segado, and P. Chris Pistorius
TMS (The Minerals, Metals & Materials Society), 2015

Thermo-Physical Properties of Petroleum Coke during Calcining

Graphitization Process

Mujun Long*1-1, Junhao Sheng1-1, Tao Liu1-1, Dengfu Chen1-1, Yi Yang2-1, Shikai Gong2-1, Chunmei
Chen 0

^ College of Materials Science and Engineering, Chongqing University, Chongqing 400044, P.R.
China. Email: longmujun@cqu.edu.cn
^ Guiyang Aluminium Magnesium Design & Research Institute Co., Ltd, Guiyang 50004, Gui
Zhou, P.R. China.

Keywords: Thermo-physical properties; Calcining; Graphitization; Petroleum coke

Abstract

The relationship between thermo-physical properties of petroleum coke and temperature is of

importance for determining of the operating parameters during the calcining graphitization
process. In this paper, the variations of thermo-physical properties of petroleum coke versus
temperature were investigated, such as the DSC-Tg curve, the specific heat capacity, the thermal
diffusion coefficient, the thermal conductivity, and so on. The thermal analysis curve of
petroleum coke showed synchronous thermal hysteresis at higher heating rates, indicating that a
larger heating rate will cause delay of thermal effects. The thermal diffusivity of petroleum coke
decreased during the calcining process. With increasing temperature, coefficient of heat
conductivity and specific volume heat of the petroleum coke increased with a decreasing
variation rate. The research provides a database for the calcining graphitization process of
petroleum coke.

Introduction

Petroleum coke is a by-product from oil refining, the residue after the cracking of heavy oil in a
delayed coking unit [1], Petroleum coke is widely used for prebaked anodes, graphite electrodes,
metallurgical carburant, and so on [2-10], The petroleum coke needs to be calcined and
graphitized before using. The thermo-physical properties of petroleum coke, such as the specific
heat, thermal diffusion coefficient, thermal conductivity and the thermal behavior during heating,
were important base parameters for the simulation and control of calcining graphitization process.
Generally, the physical properties of petroleum coke depend on the composition and
characteristics of the feedstock [11], Works have been performed to obtain the thermal properties
of petroleum coke [7,11,12], The thermo-physical properties of petroleum coke vary in different
calcining temperature, especially at different heating rates. Simulating the calcining
graphitization process, the specific heat, thermal diffusion coefficient, thermal conductivity and
the thermal behavior of petroleum coke were experimentally studied.

Experimental

Petroleum coke (A and B) obtained from two petroleum coke production enterprise were used as
raw materials in this research. The two petroleum cokes had been calcined at approximately
1100C. Chemical compositions of the two petroleum cokes are presented in Table 1.

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 Table 1 Chemical compositions of the petroleum cokes

Cokes S (%) N ( ) Si (%) Fe ( o)

Coke A 0.44 0.48 0.0065 0.028
Coke B 0.89 0.47 0.067 0.085

Thermal analysis experiments were conducted using a simultaneous thermal analyzer STA
(DSC/DTA-TG, NETZSCH, Germany) to monitor both the weight change and ex-endothermal
behavior of the samples during calcining process. The samples were heated from room
temperature up to 1400 C at constant heating rates of 10 : C/min and 20 : C/min in a nitrogen
atmosphere, respectively.
Thermal conductivity analysis (LFA-457, NETZSCH, Germany) was used to investigate the
specific heat, thermal diffusivity, and thermal conductivity. The testing was performed from
room temperature to 1000 C.

Results and Discussion

Thermal behavior of the petroleum cokes

Generally, the calcining process can be monitored by the change of heat and weight. DSC-TG
curves characterized the absorbing or releasing of heat and weight changes during the calcining
process. By studying the DSC-TG curves, the ex-endothermal behavior and volatile matter
removal of the petroleum cokes could be obtained.
Simulating the calcining process of petroleum coke, the ex-endothermal behavior and weight
loss of the two petroleum cokes at heating rates of 10 : C/min and 20 : C/min were studied with
the simultaneous thermal analyzer. Results of the petroleum cokes A and B are illustrated in
Figure 1 and Figure 2, respectively.

Temperature(C)
Fig. 1 DSC-TG curves of the petroleum coke A

194
 0 2 101
Tg-20 Cillllil
100
o.o Ta-10"C/min

209X 91

-1.2 -| i 1 i 1 i 1i 1 i 1 i 1 i 1 90
0 200 400 600 800 1000 1200 1400 1600

TemperaturefC)

Fig. 2 DSC-TG curves of the petroleum coke B

As shown in Figure 1 and Figure 2, the mass loss of the two petroleum cokes changed little
during the heating process, indicating that there were little emission of volatile matter and
moisture during the process. Since the petroleum cokes had been calcined at temperatures around
1100 C before the experiments, most of the volatile matter and moisture had already been
removed. There was a small weight loss for petroleum coke A at the heating rate of 10 : C/min, it
may owe to the absorption of moisture of coke A before the DSC experiment.
The DSC curves in Figure 1 and Figure 2 were smooth. Only some small exothermic peaks and
endothermic peaks were found at around 200 C and around 1000 C, which indicated again that
most of the volatile matter and moisture had already escaped at the temperature below 1100 C.
The temperature of the exothermic peaks and endothermic peaks were higher when the heating
rates were increased, indicating that a faster heating rate would delay the thermal effects[13],
such as the emission of moisture and volatile matters. As the heating rate increased from
10 : C/min to 20 : C/min, the endothermic peaks of coke A and B moved from 162 C to 210 C,
and 165 C to 209 C, respectively.

Heat capacities of the petroleum cokes

Specific heat (Cp) represents thermal properties of materials and relates to the status and the
types of materials. Specific heat is one of the important parameters for the heat transfer
simulation and temperature control during the graphitization process.
The variations of specific heat versus temperature for petroleum cokes A and B are presented in
Figure 3, showing higher specific heats with increasing temperature for both petroleum cokes.
The increasing rate of both specific heats were lower at higher temperature. From room
temperature to 1000 C, the Cp increased from 0.396 J/(g K) to 1.314 J/(g K) for petroleum coke
A, and from 0.416 J/(g K) to 1.45 J/(g K) for petroleum coke B. Therefore, compared with
petroleum coke A, more energy is needed for petroleum coke B to be calcined to the same
temperature. The difference of Cp between petroleum cokes A and B is bigger at higher
temperature.

195
 1.4 -

1.2-

F5
3 ce-
ci,
(j

0.6-

0.4-

0 2 -
Temperature (C)

Fig. 3 Variations of specific heat with temperature for petroleum cokes A and B

Thermal conductivities of the petroleum cokes

Figure 4 shows the thermal diffusion coefficients a (mnr/s) of petroleum coke A and B tested
from room temperature to 1000 C. As Figure 4 showed, the lower temperature, the higher the
thermal diffusion coefficients. The thermal diffusivity of petroleum coke A is higher than
petroleum coke B, especially at low temperature.

3.6-
coke A
coke B
32-

2.0-
9

j; 24-
"E -
E
V 20- ^ a B

1.6-

12- i 1 1 1 1 1 1 1 1 1 r
0 290 100 600 800 1000

Temperature (C)
Fig. 4 The thermal diffusion coefficients versus temperature for petroleum cokes A and B

As one of the important parameters for heat transfer, the thermal conductivity coefficient X
(w/(m -K)) can be calculated by
X = a C'p p (1)

196
where Cp is specific heat in J/(kg K); a is thermal diffusion coefficients in m 2 /s; and p is density
in kg/ni 3 .
With Eq.(l), the thermal conductivity coefficients for petroleum coke A and B were obtained, as
shown in Figure 5.

4.5-

4 0-

3 5-

|2.5

2 0-

1.5-

1.0-
Temperature ( X )

Fig. 5 The thermal conductivity coefficients versus temperature for petroleum cokes A and B

When the temperature increased, the number of phonons was larger, the specific heat capacity
was higher, hence the thermal conductivity coefficient was larger. Furthermore, the thermal
conductivity coefficient was larger at higher graphitization degree [14], As shown in Figure 5,
the heat conductivity coefficients of the both petroleum cokes increased with a decreasing
variation rate. From room temperature to 1000 C, the heat conductivity coefficient increased
from 2.002 w/(m K) to 4.236 w/(m K) for petroleum coke A, while from i. 184 w/(m K) to 3.215
w/(m K) for petroleum coke B. The heat conductivity coefficient of petroleum cokes A was
larger than that of petroleum cokes B.

Summary

The thermo-physical properties of petroleum cokes, such as the specific heat, thermal diffusion
coefficient, thermal conductivity, and the DSC-TG curve, were experimentally investigated.
Results indicated: (1) Higher heating rates will cause delay of thermal effects, such as the
emission of moisture and volatile matter. Most of the volatile matter and moisture had already
escaped at the temperature below 1100 C because the petroleum cokes had been pre-calcined. (2)
The thermal diffusivity of petroleum cokes decreased during calcining process. With increasing
temperature, the heat conductivity coefficient and specific heat of both petroleum coke increased
with a decreasing variation rate.

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 Acknowledgements

Authors would like to acknowledge the financial support of Guiyang Aluminum Magnesium
Design & Research Institute Co., Ltd. The technical assistant from the Analytical and Testing
Center of Chongqing University is gratefully acknowledged.

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