Energy & Fuels 2007, 21, 2669-2672 2669

Catalytic Effect of Metallic Oxides on Combustion Behavior of High

Ash Coal
X. G. Li,* B. G. Ma, L. Xu, Z. T. Luo, and K. Wang
Key Laboratory for Silicate Materials Science and Engineering of Ministry of Education,
Wuhan UniVersity of Technology, Wuhan 430070, Hubei, China

ReceiVed January 29, 2007. ReVised Manuscript ReceiVed May 16, 2007

By means of thermogravimetric analysis, the catalytic effect of metallic oxides (CuO, Fe2O3, and ZnO) on
the combustion behavior of high-ash coal was investigated under nonisothermal conditions. Experiments were
conducted from ambient temperature to 1000 °C at a heating rate of 20 °C‚min-1. The ignition temperature,
burnout performance, and exothermic behavior were used to evaluate the catalytic effect. Moreover, the kinetics
parameters (activation energy and pre-exponential factor) were determined using the Coats-Redfern method.
It is indicated that, compared with the combustion characteristics of high-ash coal, the ignition temperature of
the samples with metallic oxides decreases by 8-50 °C. Metallic oxides can speed up the combustion rate and
burnout of the fixed carbon. The exothermic values of samples incorporating metallic oxides increase by 15-
30%, which may be due to the catalytic effect of metallic oxides on fixed carbon combustion. The activation
energies of the samples decrease, and there is a linear connection between the activation energies and pre-
exponential factors (ln A ) 0.2683 × E-12.807).

1. Introduction
In China, the production and consumption of coal is very
great and most of the raw coals mined every year are directly
used as fuels. It is very important and necessary to improve the
burning of the raw coals so as to save energy and control
environmental pollution. In addition, how to fully utilize low-
rank coals such as high-ash coal (HAC), which occupy many
lands and pollute the environment, is a problem that has to be
solved. In rotary kilns, low-ash coal burns well. However,
compared with soft coal, there are severe problems such as
ignition, combustion rate, and burnout if high-ash coal is used
to produce cement in a rotary kiln or in a precalciner.
In recent years, many more investigations on the coal burning
process and catalytic combustion were performed successively
to promote combustion efficiency and meet pollution emission
requirements. The ignition temperature and activation energy
of fly ash coal due to the incorporation of alkali metal salt
decrease.1-3 The catalytic effect of coal-burning additives can
increase the combustion rate and decrease the activation energy
of coal.4-5 The action of catalysts on fuel ignition can be
explained by the enhancement of volatiles emissions. It can be
assumed that alkali causes weakening of the intermolecular inter-
* Corresponding author. Tel./fax: +86-27-87160951; e-mail: lxggroup@
163.com.
(1) Altun, N. E.; Hicyilmaz, C.; Kok, M. V. Effect of different binders
on the combustion properties of lignite, TG/DTG study, Part I. effect on
thermal properties. J. Therm. Anal. Calorim. 2001, 65 (2), 787-795.
(2) Yaman S.; Kucukbayrak, S. Effect of oxydesulphurization on the
combustion characteristics of coal. Thermochim. Acta 1997, 293 (2), 109-
115.
(3) Matsuzawa, Y.; Mae, K.; Hasegawa, I. Characterization of carbonized
municipal waste as substitute for coal fuel. Fuel 2007, 86 (1-2), 264-
272.
(4) Hsisheng, T.; Yung-Fu, H.; Ying-Tsung, T. Reduction of NO with
NH3 over carbon catalysts-the influence of carbon surface structures and
the global kinetics. Appl. Catal., B 1999, 20 (2), 145-154.
(5) Tan, Z. C.; Wang, S. D.; Li, L.; Wu, D Y. Thermogravimetric study
about the accelerating effect of coal burning additive on combustibility of
coal and gangue. Chin. J. Catal. 1999, 20 (3), 263-266 (in Chinese).
action of the polymeric chains and, at the same time, catalyzes
not only intralink dehydration but promotes the processes of
retro-aldol cleavage and condensation of the products produced.6
The catalyst Cu/V/K is reported to produce a strong increase
in the rate of carbon combustion and a marked decrease in the
apparent activation energy.7 The activity of different metal
oxides in the catalytic combustion of diesel soot having any
amount of adsorbed hydrocarbons has been investigated.8 How-
ever, these findings were only used in applications of electricity
generation; the type and quantity of the chemical additives were
not completely suitable for cement production. Therefore, in
order to widely use HAC in the precalcining kiln and to widen
the selection scope of the coal used in the cement industry,
fundamental research work on the catalytic and accelerating
effect of metallic oxides on combustion characteristics should
be carried out in order to give scientific guides to the application
of HAC and catalysts in the cement and other industries.
Thermogravimetric analysis (TGA) profiles contribute to
enhancing the knowledge of this process and, therefore, to
establishing the optimum operational conditions to develop it.
Accordingly, several authors have studied the behavior of the
pyrolysis, combustion, and kinetics of soft coal, anthracite, and
other carbonaceous materials by TGA.9-14
In this paper, the catalytic and accelerating effects of metallic
oxides such as CuO, Fe2O3, and ZnO on the ignition and burnout
characteristics of HAC are investigated by TGA, and the calori-
(6) Rustamov, V. R.; Abdullayev, K. M.; Samedov, E. A. Biomass
conversion to liquid fuel by two-stage thermochemical cycle. Energy
ConVers. Manage. 1998, 39 (9), 869-875.
(7) Ciambelli, P.; Coro, P.; Gambino, M. Catalytic combustion of carbon
particulate. Catal. Today 1996, 27, 99-106.
(8) Neri, G.; Bonaccorsi, L.; Donato, A. Catalytic combustion of diesel
soot over metal oxide catalysts. Appl. Catal., B 1997, 11 (2), 217-231.
(9) Hurt, R. H.; Lunden, M. M.; Brehob, E. G. Kinetic model of carbon
burnout in pulverized coal combustion. Combust. Flame 1998, 113 (2), 181-
197.
(10) Kök, M. V. An investigation into the thermal behaviour of coals.
Energy Sources 2002, 24 (10), 899-906.

10.1021/ef070054v CCC: $37.00 © 2007 American Chemical Society

Published on Web 08/31/2007
2670 Energy & Fuels, Vol. 21, No. 5, 2007
fic values of the coal samples are also determined by differential
scanning calorimetry (DSC). The kinetic parameters of coal
samples due to the catalytic effect are also determined according
to the Coats-Redfern method. The results may be used to
enhance the understanding of the characteristics of high-ash coal
and also provide a useful basis for further applying high-ash
coal in cement kilns or other industries with high efficiency.
2. Experiments
2.1. Materials and Sample Preparation. For the investigation,
a high-ash coal with a Mad (moisture content) of 1.4 wt %, Vd
(volatile matter) of 8.50 wt %, Ad (ash) of 44.22 wt %, and FCd
(fixed carbon) of 46.18 wt % was used, where Mad (moisture) was
the weight loss percentage on a dry air basis at 75 °C, Ad (ash)
was the residue percentage on a dry basis after complete combustion
at 800 °C, Vd (volatile) was the weight loss percentage on a dry
basis after devolatilization at 700 °C for 10 min under a scarce
oxygen atmosphere, and FCd (fixed carbon) was calculated by
difference. A coal with a particle size of <80 µm was used.
In order to investigate the influence of metallic oxides on the
combustion behaviors of HAC, CuO, Fe2O3, and ZnO were used,
which were provided by the Tianjing Chemical Reagent Plant.
Metallic oxides of 6 wt % were added to the HAC and ground for
about 10 min; the samples with a particle size of <80 µm were
controlled. The materials were stored in the laboratory under dry
conditions.
2.2. Combustion Experiments. Experiments on the combustion
characteristics were performed with a NETZSC STA-449C ther-
mogravimetric analyzer. The 20 mg samples were spread uniformly
on the bottom of a crucible made of alumina. In an air flux of 20
mL/min, the furnace temperature was increased from ambient
temperature to 1000 °C using a heating rate of 20 °C‚min-1. The
weight of the sample was monitored continuously as a function of
temperature or time.
2.3. Kinetics Analysis. In this work, the activation energy (E)
and pre-exponential factor (A) of the coal samples are determined
by the Coats-Redfern method from an analysis of the thermo-
gravimetric (TG) curves.
The combustion rate is shown as
dR
) kf(R) (1)
dt
Where R is the fraction of coal combustion and k is the rate constant,
given by the expression
E
k ) A exp -( RT ) (2)
For coal combustion, f(R) can be expressed as follows:
f(R) ) 1 - R (3)
If the temperature rises at a constant rate β ) dT/dt, eq 1 becomes
Then, eq 4 can be integrated as
dR A E
) exp -
dT β RT (
(1 - R) ) (4)
[
ln -
ln(1 - R)
T2 ] [
) ln
AR
βE (
1-
2RT
E )] - RTE (5)
(11) Marshak, Y. L.; Artemev, Y. P.; Mironov, S. N. Means of improving
combustion of low-grade anthracite fines at power stations. Therm. Eng.
(Transl. of Teploenergetika (Moscow)) 1988, 35 (9), 487-496.
(12) Emre, A. N.; Cahit, H.; Suat, B. A. Influence of coal briquette size
on the combustion kinetics. Fuel Process. Technol. 2004, 85 (11), 1345-
1357.
(13) Yamamoto, Y.; Ohe, T.; Naruse, I. Ignition characteristics and its
mechanisms in pulverized coal combustion. Nippon Kikai Gakkai Ronbun-
shu, B-hen. 1994, 60 (570), 649-655.
Li et al.
In general, RT/E , 1, so eq 5 becomes
[
ln -
ln(1 - R)
T2 ] [ ]
) ln
AR
βE
-
E
RT
(6)
The curves of TGA can be used to calculate ln[-ln(1 - R)/T2]. It
was plotted against 1/T according to eq 6, and linear regression
was used to determine E and A.
3. Results and Discussion
3.1. Combustion Process. The TG/DTG profiles of the coal
samples containing different metallic oxides (CuO, Fe2O3, and
ZnO) are presented in Figure 1a and b.
The characteristic parameters of the coal samples with
different metallic oxides and pure HAC are shown in Table 1.
The most important characteristic parameters for measuring
the reactivity of the sample are the ‘‘maximum combustion rate
[(dw/dt)max]” and the ‘‘peak temperature”. The rate of weight
loss at the burning profile peak temperature is called the
‘‘maximum combustion rate [(dw/dt)max]”; the corresponding
temperature of (dw/dt)max is called the ‘‘peak temperature”. The
maximum combustion rates of the pure HAC and the coal
samples containing CuO, Fe2O3, and ZnO were calculated as
4.77, 8.55, 7.07, and 7.75%/min, respectively (Table 1). These
temperatures were found as 587.9 °C for the pure HAC,
451.3 °C for HAC with CuO, 515.9 °C for HAC with Fe2O3,
and 496.7 °C for HAC with ZnO (Table 1). The differences
between the maximum combustion rates and peak temperature
of the samples with or without the metallic oxides can be
attributed to the catalytic and accelerating effect of metallic
oxides on the combustion process. The relative active sequence
of the catalytic effect of metallic oxides on the reactivity can
be described as follows: CuO > ZnO > Fe2O3.
3.2. Influence on Ignition Temperature. A number of
parameters are known to influence the ignition temperature and
ignition mechanism; these include the sample mass, particle size,
volatile matter yield, and oxygen concentration. In addition to
these variables, a number of system parameters related to the
experimental conditions are important for the ignition behavior.
Clearly, therefore, the ignition temperature is not a physical
property of a fuel.15 Our aim was not to propose a method for
ignition temperature evaluation. This study was based on a
comparison attempt; that is, we kept the same burnoff procedure
for virgin and modified samples to see the metallic oxides’
impact. In this investigation, the ignition temperature is
determined according to the literature.16-17
It is shown from Table 1 that the ignition temperature (Ta)
of HAC is 458.5 °C; the ignition temperatures of the coal
samples with 6% CuO, Fe2O3, and ZnO decrease by 50, 8.4,
and 19.2 °C, respectively. It is also indicated that the metallic
oxides used in this study can catalyze and accelerate the ignition
of HAC. The active sequence of catalysts relative to the ignition
temperature can be described as follows: CuO > ZnO > Fe2O3.
(14) Chen, Y.; Shigekatsu, M.; Wei-Ping, P. Studying the mechanisms
of ignition of coal particles by TG-DTA. Thermochim. Acta 1996, 275 (1),
149-158.
(15) Pranda, P.; Prandova, K.; Hlavacek, V. Combustion of fly-ash
carbon. Part I: TG/DTA study of ignition temperature. Fuel Process.
Technol. 1999, 61, 211-221.
(16) Nie, Q. H.; Sun, S. Z.; LI, Z. Q. Thermogravimetric study on the
combustion characteristics of brown coal blends. J. Combust. Sci. Technol.
2001, 7 (1), 72-76.
(17) Li, X. G.; Ma, B. G.; Xu, L. Thermogravimetric analysis of the
co-combustion of the blends with high ash coal and waste tyres. Thermo-
chim. Acta 2006, 441 (1), 79-83.
Catalytic Effect of Metallic Oxides Energy & Fuels, Vol. 21, No. 5, 2007 2671

Figure 2. DSC profiles of combustion of the coal samples.

Table 2. The Exothermic Values and Kinetics Parameters of the

Coal Samples Containing Metal Oxidea
peak temperature exothermic value E ln A
no. °C J/g KJ‚mol-1 s-1
a 517.9 6480 58.79 2.97
b 519.7 5375 60.79 3.50
c 514.6 5596 62.14 3.87
d 547.3 4932 66.53 5.04
a a: HAC + 6% CuO. b: HAC + 6% Fe O . c: HAC + 6% ZnO. d:
2 3
HAC.

3.3. Influence on Burnout Performance. When the weight

loss in TG curves was close to zero, the corresponding
temperature or time was considered as the burnout temperature
or time of the samples. As shown in Table 1, the influence of
coal on the burnout time (tf) is slight, so the burnout time cannot
completely reflect burnout performance of the samples. In this
Figure 1. TG-DTG profiles of combustion of the coal samples. study, the burnout index is used to evaluate the burnout
performance, which can be described as follows:19
Table 1. The Ignition and Burnout Behavior of the Coal Samples (dw/dt)max
Containing Metal Oxidea Df )
∆t1/2tptf
Ta ta (dw/dt)max Tp ∆t1/2 tp tf Df
no. °C min % min-1 °C min min min ×10-4
where (dw/dt)max is the maximum combustion rate, ∆t1/2 is the
a 408.5 18.68 -8.55 451.3 5.46 20.70 30.46 24.84 time zone of (dw/dt)/(dw/dt)max ) 1/2, tp is the corresponding
b 450.1 20.86 -7.07 515.9 6.86 24.10 30.25 14.14
c 439.3 20.13 -7.75 496.7 5.76 23.04 33.10 17.64 time of (dw/dt)max, and tf is the burnout time.
d 458.5 20.99 -4.77 587.9 9.63 27.83 34.20 5.20 It is shown that the burnout indexes (Df) of the pure HAC
a a: HAC + 6% CuO. b: HAC + 6% Fe O . c: HAC + 6% ZnO. d: and the coal samples containing CuO, Fe2O3, and ZnO were
5.20 × 10-4, 24.84 × 10-4, 14.14 × 10-4, and 17.64 × 10-4,
2 3
HAC. Tp is the corresponding temperature of (dw/dt)max; Ta and ta are the
ignition temperature and the corresponding time; tf and Df are the burnout respectively (Table 1). Compared with the burnout character-
time and the burnout index. istics of the samples, it has been shown that the burnout indexes
of the samples with CuO, Fe2O3, and ZnO increase by 378%,
The reduction of ignition temperature is due to the catalytic 172%, and 239%, respectively. Moreover, when a catalyst has
effect of metallic oxides on the enhancement of the emission been added (excluding the mass of the catalyst), the final masses
of volatile matters from HAC. To a certain degree, the catalytic of the control and the samples with CuO, Fe2O3, and ZnO are
effect promoted the coal decomposition reaction, resulted in the 42.6%, 38.2%, 39.9%, and 38.9%, respectively. The active
oxidative and transformed reaction of the matter which is sequence of catalysts relative to the burnout performance can
difficult to oxidize and transform, accelerated and eased the be described as follows: CuO > ZnO > Fe2O3.
decomposition of the tar and the crude benzene, and increased The catalytic effect on burnout performance may be a carrier
the release of the coal volatile matter.18 of oxygen that promotes the oxygen transfer to the char of HAC.
Metallic oxides are deoxidized to metal or low-valency metallic
(18) Shen, B. X.; Qin, L. Study on MSW catalytic combustion by TGA. oxides (M2O) by carbon; then, metal or low-valency metallic
J. Fuel Chem. Technol. 2005, 33 (2), 189-193.
(19) Xie, J. L.; He, F. Catalytic combustion study of Anthracite in cement oxides absorb oxygen and turn into metallic oxides; this process
kiln. J. Chin. Ceram. Soc. 1998, 26 (6), 792-795. circulates between oxidation and deoxidization. Due to the
2672 Energy & Fuels, Vol. 21, No. 5, 2007
oxygen transfer from the metal to the carbon atom, the diffusion
of oxygen is accelerated, which contributes to the burnout and
combustion of the fixed carbon.
3.4. Influence on the Exothermic Value. According to the
DSC profile, the relation between the exothermic value and peak
area can be described as follows:
∆Q ) k ∫c∞ [∆H - (∆H)c] dτ ) kS
where ∆Q is the exothermic value of coal combustion, in joules
per gram, k is a constant, ∆H is the enthalpy difference between
the sample and the reference, in milliwatts per milligram, τ is
the heating time, in minutes, and S is the peak area between
the DSC profile and baseline.
The exothermic behaviors of the coal samples with or without
metallic oxides according to the DSC profiles are reported in
Figure 2. The exothermic values and the peak temperature of
the samples are shown in Table 2.
It can be seen that, compared with that of the pure coal, the
peak temperature of DSC can be decreased about 30 °C with
the incorporation of the metallic oxides; moreover, the exo-
thermic value of the samples can be increased by 15-30%,
which may be due to the catalytic effect of metallic oxides on
the fixed carbon combustion.
3.5. Influence on Kinetics Parameters. According to the
TG-DTG profiles of the coal samples containing different
metallic oxides, the activation energies (E) and pre-exponential
factors (A) are determined by the Coats-Redfern method. The
results are shown in Table 2.
As can be seen from Table 2, compared with those of the
HAC, metallic oxides can decrease the activation energies of
HAC, and these activation energies were found as 66.53
Li et al.
KJ‚mol-1 for the pure HAC, 58.79 KJ‚mol-1 for HAC with
CuO, 60.79 KJ‚mol-1 for HAC with Fe2O3, and 62.14 KJ‚mol-1
for HAC with ZnO (Table 2), respectively. Moreover, there is
a linear connection between the activation energies and pre-
exponential factors; the connection can be described as the
following equation: ln A ) 0.2683 × E-12.807.
4. Conclusions
The ignition temperature of the coal samples with 6% CuO,
Fe2O3 and ZnO decrease by 50 °C, 8.4 °C and 19.2 °C,
respectively. The active sequence of catalysts relative to the
ignition temperature can be described as follows: CuO > ZnO
> Fe2O3.
The burnout indexes of the samples with CuO, Fe2O3, and
ZnO increase by 378%, 172%, and 239%, respectively. The
active sequence of catalysts realtive to the burnout performance
can be described as follows: CuO > ZnO > Fe2O3.
The peak temperature of DSC can be decreased about 30 °C
with the incorporation of the metallic oxides; moreover, the
exothermic value can also be increased by 15-30%, which may
be due to the catalytic effect of metallic oxides on the fixed
carbon combustion.
The activation energies of the samples containing CuO, Fe2O3,
and ZnO decreased to some extent. Moreover, there is a linear
connection between the activation energies and pre-exponential
factors; the connection can be described as the following
equation: ln A ) 0.2683 × E-12.807.
Acknowledgment. This research was carried out at the Key
Laboratory for Silicate Materials Science and Engineering of
Ministry of Education, Wuhan University of Technology. The
financial support from the Key Laboratory of Silicate Materials
Science and Engineering (Wuhan University of Technology),
the Ministry of Education of China (No. SYSJJ2007-01), and
the hi-tech research and development program of China (No.
2002AA335050) are greatly acknowledged
EF070054V