Powder Technology 203 (2010) 272276

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Powder Technology
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p ow t e c

The non-isothermal kinetics analysis of the thermal decomposition of kaolinite by

Efuent Gas Analysis technique
Petr Ptek , Frantiek oukal, Tom Opravil, Magdalna Noskov, Jaromr Havlica, Ji Brandtetr
Institute of Materials Chemistry, Faculty of Chemistry, Brno University of Technology Purkyova 464/118, Brno, CZ-612 00, Czech Republic

a r t i c l e

i n f o

Article history:
Received 11 February 2010
Received in revised form 15 April 2010
Accepted 14 May 2010
Available online 21 May 2010
Keywords:
Kaolin
Kaolinite
Non-isothermal dehydroxylation
Activation energy
Heterogeneous kinetics
Efuent Gas Analysis

a b s t r a c t
The thermal decomposition of kaolin with high-content of the medium ordered kaolinite was studied by
Efuent Gas Analysis (EGA) under non-isothermal conditions. This technique enables to distinguish two
overlaying processes during the thermal decomposition of kaolin: oxidation of organic compounds and
dehydroxylation. The kinetic of non-isothermal dehydroxylation of kaolinite is controlled by the rate of the
third-order reaction. For the given reaction mechanism, the overall activation energy (EA) and preexponential (frequency) factor (A) values are 242 kJ mol1 and 2.21 108 s1, respectively.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Kaolin is an important raw material for the industrial production.
Washed kaolin is mainly used for manufacturing porcelain and
sanitary ceramics, whereas reclay refractory products are fabricated
using the crude kaolin. Beyond the ceramics, kaolin is utilized as lling
agent for paper, plastics, rubber, cosmetics, etc. Metakaolin, produced
by thermal decomposition of kaolin, has found applications in foodprocessing industry, oil shale processing and ceramics [14].
Furthermore, kaolin is very promising raw material for waste
management [5,6] and preparation of geopolymers and geopolymer
based composites [711], zeolites [1214] and intercalates [1517].
Kaolinite (Al2Si2O5(OH)4) is an essential component of kaolin.
However, there will always be certain amount of other phyllosilicates
such as smectite (e.g. montmorillonite), mica group minerals (e.g.
illite) and tectosilicates (e.g. feldspars). The kind and amount of
impurities depend on conditions of aluminosilicates (mainly feldspars) weathering and applied industrial purication (washing
process). Furthermore, quartz (-SiO2), rutile (TiO2), hematite (Fe2O3), ilmenite (Fe2O3TiO2), zircon (ZrO2SiO2), carbonates (e.g.
FeCO3), sulphides (e.g. FeS2) and various kinds of ferrous and alumina
hydroxides or oxo-hydroxides (goethite, gibbsite, boehmite) are
the most common accessory minerals of crude kaolins [1,1820].
Kaolinite as well as other clay minerals can interact with organic

Corresponding author. Tel.: + 420 541 149 389; fax: + 420 541 149 361.
E-mail address: ptacek@fch.vutbr.cz (P. Ptek).
0032-5910/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.powtec.2010.05.018

compounds, e.g. humic and fulvic acids, consequently there is always

certain content of an organic compounds in the kaolin [21,22].
The thermal treatment of kaolinite leads to formation of
metakaolinite (Eq. (1)), AlSi cubic spinel, amorphous silica phase
(Eq. (2)) and thermodynamic stable phases and mullite and
cristobalite, are formed above 1050 C (Eqs. (3) and (4)).
The whole process can be described by the following reactions [4,2325]:
450700 C
Al2 O3 2SiO2 2H2 O Al2 O3 2SiO2 + 2H2 Og

9251050 C
2Al2 O3 2SiO2 2Al2 O3 3SiO2 + SiO2amorphous

1050 C
32Al2 O3 3SiO2 23Al2 O3 2SiO2 + 5SiO2

1200 C
SiO2amorphous SiO2cristobalite

Simple Eqs. (1)(4) are unable to describe the process complexity

and non-stoichiometric composition of originating phases, predehydroxylation process [26,35], gradual disappearing of residual hydroxyl
groups [35] and mullite formation processes (mullitization) [27].
Process is also inuenced by many factors, much-frequently degree of
disorder of the kaolinite structure [28], pressure and partial water
vapour pressure [29,30], heating rate [23,30], mechanical treatments
and ultrasound processing of sample [31,32] are mentioned.

P. Ptek et al. / Powder Technology 203 (2010) 272276

273

kaolinite guaranteed by producer is higher than 90 wt.% with equivalent

grain diameter median in the range 1.21.4 m. The main impurities are
mica group minerals and quartz. The colorant oxide contenthematite
(-Fe2O3) and tetragonal TiO2 (rutile), is lower than 0.85 and 0.2 wt.%,
respectively. The initial state, properties and chemical composition of
applied kaolin is described elsewhere [37].
2.2. Efuent Gas Analysis

Fig. 1. Efuent Gas Analysis of kaolinite using heating rate 10 C min1.

In published literature [28,29,3236,41,42] an extensive attention

is given to the mechanism and kinetics of thermal decomposition of
kaolinite and clay mineral in general. The process was investigated by
a broad-spectrum of methods, including molecular spectroscopy
[28,29], electron microscopy [33] and thermal analysis techniques
[32,3436].
The aim of the present paper is the investigation of two
overlapping processes which take place during thermal decomposition of kaolin, i.e. dehydroxylation of kaolinite and combustion of
organic compounds. Furthermore, the mechanism of dehydroxilation
and pertinent kinetic parameters (overall activation energy and preexponential factor) will be determined on the basis of EGA experiments and compared with TGA results.
2. Experimental procedure
2.1. Kaolin
Washed kaolin Sedlec Ia from the region Carlsbad (Czech Republic)
produced by the company Sedleck kaolin a.s. was used for the study of
thermal decomposition of kaolinite. This high quality kaolin, originally
mined in open-cast mine near Sedlec, is commercially available since
1892 and it is often considered as be world's standard. The content of

The 40 m undersize of kaolin with specic surface 20 m2 g1

(Chembet 3000) was used for the EGA experiments. The 20 mg of
sample was introduced into alumina cup and arranged in a uniform
layer. The crucible was inserted into TG-DTA analyzer Q600 (TA
Instruments) connected with measuring cell (TGA/FT-IR Interface,
Thermo Scientic) of FT-IR spectrometer Nicolet iS10 (Thermo
Scientic) through heated capillary (200 C). The sample was heated
at heating rate 10 C min1 under ow of argon (100 cm3 min1) to
1200 C.
The set of 651 infrared spectra was collected in wavenumber region
from 400 to 500 cm1 for either assessment. The 32 scan spectrum with
resolution 16 cm1 was taken every 11.82 s. The applied setting means,
that temperature was increasing for 1.97 C within the range of
sampling interval.
3. Results and discussion
The typical Efuent Gas Analysis plot of kaolin is shown in Fig. 1. The
carbon dioxide and water vapour were detected in the purging gas
during thermal treatment of sample. It stands to reason that both gas
producing processes have reached the maximum rate at different
temperature, but their temperature intervals are overlapping. The
combustion of organic compounds starts at 370 C and the highest
concentration of CO2 was detected at 400 C. The dehydroxylation takes
place approximately at the same temperature and the formation of
volatile phase continues over next 270 C. The maximum concentration
of water vapour, i.e. maximum rate of process is located at 500 C.
Furthermore, the mutual inuence of both processes was observed.
Water vapour, which is evolved during dehydroxylation of kaolinite,
slows down combustion of the carbon compounds from the sample and
the end of process is shifted to higher temperatures. The carbon dioxide

Fig. 2. TG-DTA results of thermal analyzer gathered together infrared spectrometer. The part of TG curve reconstructed from determined kinetic data is plotted by solid line.

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P. Ptek et al. / Powder Technology 203 (2010) 272276

Fig. 3. Baseline corrected infrared spectrum of gas phase generated during EGA of kaolin at 400 C, 500 C and 600 C.

bands can be recognized in the spectra up to 600 C. The dehydroxylation process is almost complete at this temperature (Fig. 3).
The TG-DTA results of EGA apparatus (Fig. 2) show that burning of
organic compounds is also detectable on the derivate of mass loss curve
(DTG) like the shoulder of dehydroxylation peak. However, heat effect
on DTA curve is overlaid by the endothermic peak of dehydroxylation at
511 C. The mass loss of sample attains 12.69 wt.%. The second sharp
exothermic peak at 986 C belongs to the formation of cubic spinel
phase (Eq. (2)). Including an initial drying process, the mass of the
sample was reduced at about 13.30 wt.% to the 1200 C.
Although the burning of organic compounds during thermal
decomposition of kaolinite can be detected by DTG, the EGA techniques
can easily distinguish the individual running processes via using time
dependence of absorbance for some of spectral bands of monitored
compounds. Fig. 4 shows the GramSchmidt reconstruction expressing
the relative spectral response changed over the duration of the EGA
experiment. This curve is in many respects analogous with DTG, because
all gas products can be in this case detected by IR spectroscopy. Further
intensities of antisymmetric as(+
u ) and symmetric 2(A1) stretching
bands of carbon dioxide and water during analysis are plotted,
respectively.
The great advantage of EGA is the possibility of evolved CO2
monitoring separately from water vapour, even within temperature
interval of dehydroxylation. That offers wide area for further research,
because some manufacturing defects in ceramics are derived from
overlaying of dehydroxylation and burning of organic impurities or
plasticizers of working mixtures. The examples are formation of black
cores and undesirable coloration of ceramic body [38] due to changes
in the course of redox processes.

Fig. 4. Complete GramSchmidt reconstruction and intensity of water and carbon

dioxide bands in the time dependence of spectra.

Time dependence of 2(A1) was used to investigation the

dehydroxylation of kaolinite. Integration of the peak enables to
express the degree of conversion as:
y=

It
:
I

There It and I are integrated intensities for instantaneous and nal

time of reaction. Calculated time dependence of y is shown on Fig. 5.
The most probable mechanism and kinetic parameters of the process
was identied by using logarithmic form of modied Coats and
Redfern equation:
ln




 


g y
AR
2RT
E 1
AR
E 1
1
ln
;
= ln
2
E
E
R T
E
R T
T

where g(y) is an integral form of kinetic function. The straight line

over wide interval of y was obtained by plotting ln[g(y) / T2] versus
reciprocal temperature (T1) for proper mathematical model g(y) of
the reaction mechanism. The overall activation energy and preexponential factor were calculated from the slope and intercept with
y-axis of the plot, respectively. Applied theory of non-isothermal
kinetic is described in works [39,40].
The most probable mechanism of the dehydroxylation, e.g.
mathematical expression of g(y) function, was evaluated using
mathematical models published in works [39,40] including processes
handled by the rate of chemical reaction, nucleation, reaction on the
phase boundary, diffusion and some other kinetic function with
unjustied mechanism. Values of the linear regression coefcient (R2)
were calculated for y from 0.25 to 0.90 using kinetic equations for
more than different 30 mechanisms. Among all applied kinetic

Fig. 5. Time and temperature dependence of degree of conversion during experiment.

P. Ptek et al. / Powder Technology 203 (2010) 272276

275

Table 1
Evaluation of the most probably mechanism of dehydroxylation based on calculation of R2 in the conversion range of 0.25 y 0.90.
Equation name

One-third order
Second order
Third order
Avrami-Erofeev eq., n = 1
Avrami-Erofeev eq., n = 2
Avrami-Erofeev eq., n = 3
Parabola law
Valensi equation
Jander equation
Ginstling-Brounstein eq.
Power law-shrinking disk
Power law-shrinking cylinder
Power law-shrinking sphere

Symbol
of g(y)
F1/3
F2
F3
A1 , F 1
A2
A3
D1
D2
D3
D4
R1, F0, P1
R2, F1/2
R3, F2/3

Reaction rate determining step

2/3

Chemical reaction

Random nucleation and subsequent

growth of nuclei
One-dimensional diffusion
Two-dimensional diffusion
Three-dimensional diffusion
Four-dimensional diffusion
Reaction on the phase boundary

functions, Table 1 shows results only for the most probable

mechanism (marked by bold) and several common or frequently
published kinetic functions. The rate of third-order chemical reaction
(F3) was evaluated as the most probably mechanism of the
dehydroxylation (Fig. 6). Determined values of overall activation
energy and frequency factor are 242 kJ mol1 and 2.21 108 s1,
respectively.
Reaction mechanism and values of pertinent kinetic parameters (EA
and A) found by the EGA were veried using thermogravimetric data
(Fig. 2) collected by thermal analyzer, which is connected with an
infrared spectrometer. Both applied methods of thermal analysis show
the best t for process handled by the rate of third-order chemical
reaction (Table 1). Corresponding values of EA and A are 239 kJ mol1
and 8.55 107 s1, respectively. Results imply that the good agreement
between both experimental techniques, as well as previous published
results of isothermal assessment [37], was achieved.
Furthermore, collected information about kinetic of thermal
decomposition of kaolinite was used for reconstruction of TG curve.
Thermogravimetric curve calculated from the kinetic data is plotted in
Fig. 2. The good agreement between experimental and reconstructed
TG curve indicates that determined kinetic data satisfactorily describe
the course of thermogravimetric experiment within the wide interval
of the fractional conversion.

Expression of g(y)
function
1 (1 y)
(1 y)1 1
(1 y)2 1
ln(1 y)
[ln(1 y)]1 / 2
[ln(1 y)]1 / 3
y2
y + (1 y)ln(1 y)
[1 (1 y)1/3]2
1 (2y / 3) (1 y)2/3
y
1 (1 y)1/2
1 (1 y)1/3

R2 for TA method
EGA

TGA

0.893
0.993
1.000
0.956
0.939
0.912
0.877
0.908
0.940
0.921
0.844
0.912
0.929

0.876
0.989
0.999
0.946
0.925
0.891
0.861
0.895
0.929
0.908
0.823
0.897
0.916

isothermal conditions and results were compared with simultaneous

thermogravimetric experiment. Efuent Gas Analysis provides possibility to distinguish two concurrent processesthe burning of organic
impurities and dehydroxylation. Formation of water vapour slows
down the combustion of organic compounds in kaolin and temperature interval of process is broadened. On the contrary, the inuence
of burning of organic substances on the course of dehydroxylation is
undetectable, due to its low content in the applied kaolin.
Dehydroxylation of kaolinite is under applied condition handled
by the rate of third-order reaction (F3). The overall activation energy
and frequency factor correspond to 242 kJ mol1 and 2.21 108 s1,
respectively. The determined value of EA is placed within the most
frequently published interval from 140 to 250 kJ mol1 [30,34,41,42].

Acknowledgments
This paper arose out of the research project supported by the
Ministry of Education, Youth and Sports No. 1M06005 and project No.
CZ.1.05/2.1.00/01.0012 Centres for Materials Research at FCH BUT
supported by the operational program Research and Development for
Innovations.

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4. Conclusion
The thermal decomposition of industrial treated (washed) kaolin
process was investigated by Efuent Gas Analysis under non-

Fig. 6. Graphical determination of the reaction mechanism and kinetic parameters.

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