J. Anal. Appl.

Pyrolysis 85 (2009) 539543

Contents lists available at ScienceDirect

Journal of Analytical and Applied Pyrolysis

journal homepage: www.elsevier.com/locate/jaap

Steam activation of pyrolytic tyre char at different temperatures

G. Lopez, M. Olazar *, M. Artetxe, M. Amutio, G. Elordi, J. Bilbao
University of the Basque Country, Department of Chemical Engineering, P.O. Box 644, E48080 Bilbao, Spain

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 27 May 2008
Accepted 4 November 2008
Available online 12 November 2008

Activation of tyre char has been carried out using steam as activation agent, and the effect of temperature
and activation time has been studied. The char samples used in the activation have been obtained by
continuous ash pyrolysis carried out in a conical spouted bed reactor at 500 8C. The activation has been
carried out at 850 and 900 8C in a xed bed reactor. During the process, a mesoporous structure is
developed, with a predominant pore diameter of around 500 A and BET surface areas above 500 m2/g for
both the temperatures studied. Moreover, sulphur content signicantly decreases during activation and
activated carbons with low sulphur content are obtained. This reduction in content may be the key for the
industrial application of tyre-derived-carbons, either as active carbons or as carbon blacks for tyre
manufacturing.
2008 Elsevier B.V. All rights reserved.

Keywords:
Active carbons
Steam activation
Tyre char

1. Introduction
Although they account for only 2% of the overall amount of
waste, tyres are of special concern in developed countries due to
the problems they may generate through inappropriate management. The world generation of used tyres in 2005 was over 2.5
million tonnes in North America, 2.5 million tonnes in Europe and
0.51.0 million tonnes in Japan, which means 6 kg (the approximate weight of a tyre) per inhabitant and year [1]. According to
estimates, this gure will increase to over 17 million tonnes per
year (approximately 1.4 billion tyres) by 2012, given that the gross
national product in developing countries encourages car demand
and tyre substitution as a measure for safe driving. These trends are
not offset by the measures adopted for prolonging tyre life [2]. The
increase in car sales in Asia, especially in China, will rapidly
increase the number of used tyres in this area, given that 85% of
tyres are from cars, and China will become the rst world producer
of used tyres (1 million tonnes in 2005, and according to the
estimates this gure will double by 2010, with a 12% annual
increase) [3].
Over the past 20 years, numerous pyrolysis plants have been
built at pilot and demonstration scale, based on the perspectives
that an industrial plant is economically protable by selling
recovered products when 81,000 tonnes of used tyres are
processed [4]. Nevertheless, these projects have not been

* Corresponding author.
E-mail address: martin.olazar@ehu.es (M. Olazar).
0165-2370/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2008.11.002

commercially successful due to the low price of fuel and carbon

black on the market [5]. According to the more recent studies [6],
economic viability is only obtained when pyrolysis processes are
not limited to primary products, but rather they include stages for
obtaining higher value added products, such as high quality carbon
black, active carbon or chemical compounds such as benzene,
xylene, limonene, and so on. The char or solid residue accounts for
3040% of the original tyre mass, which means that nding a
commercial application for that product is of great interest. In fact,
certain authors [79] state that the protability of the tyre
pyrolysis process at industrial scale depends on char application.
The most straightforward application of tyre char is its reuse as
carbon black for new tyre production [10,11], but the feasibility of
this option depends on char properties such as particle diameter,
surface morphology and sulphur content.
Activation is an alternative for producing high quality active
carbons from waste tyres. Chemical activation is commonly carried
out using KOH as activation agent [12] and this process allows for
integrating pyrolysis and activation in a single step. Physical
activation is commonly carried out by using steam or carbon
dioxide as activation agents, but it may also be suitably carried out
using NO and O2 [13]. Steam is considered to be more active than
carbon dioxide [1416] and, moreover, the carbons obtained with
steam have higher BET surface areas. This different behaviour may
be related to the smaller molecular size of water, which facilitates
diffusion within the char porous structure [17].
The active carbons obtained in the steam activation process are
mainly mesoporous with limited microporosity. In order to
increase microporosity, an acid pre-treatment has been applied

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G. Lopez et al. / J. Anal. Appl. Pyrolysis 85 (2009) 539543

to the char prior to activation [18,19]. Carbons with high surface

areas are obtained in the steam activation of tyre chars, although
important differences are found in the literature depending on the
different experimental devices and pyrolysis conditions used in the
process. Moreover, different trends have been observed in the
evolution of the surface area with burn-off. Some authors
[14,20,21] have observed a maximum in the BET surface area
with burn-off values of around 60% and an increase above these
values gives way to a decrease in BET surface area. Others
[16,22,23] have observed a continued increase in the surface area
up to burn-off values of 80%. Nevertheless, activation processes
with such a burn-off extension involve a major reduction in the
amount of product obtained.
The mesoporous carbons obtained in the activation process can
be applied to the adsorption of different pollutants in an aqueous
medium, such as phenols [18,19,24,25], mercury [26], pesticides
[27], chromium IV [28]. Moreover, the performance of tyrederived-carbons is also promising for their application in gaseous
phase, as is the case of SO2 retention in natural gas [29].
2. Experimental
The activation of tyre char has been addressed using steam as
activation agent. The char samples used in the activation have been
obtained by continuous ash pyrolysis carried out in a conical
spouted bed reactor described elsewhere [30,31]. Operating at

500 8C, char yield reaches 34%, which accounts for the total amount
of carbon black contained in the tyre. Pyrolysis conditions are an
important factor for porosity development during the activation
process. Some authors [32] report that a reduction in secondary
reactions and tar formation during the pyrolysis process improves
the subsequent activation process.
Fig. 1 shows a schematic representation of the activation unit
used in this study. The units main component is the xed bed
reactor where activation takes place. The reactor is placed inside a
radiant oven that provides the heat to operate at temperatures up
to 1000 8C. The unit is provided with a pressure meter to ensure
that pressure in the reactor during the activation reaction is not
higher than 1.2 atm. Both the reactor and the oven are located in a
hot box at 270 8C to ensure that water is vaporized before entering
the reactor. The heat in the hot box is supplied by two blowers
provided with four cartridges. Nitrogen is fed into the reactor by
means of a mass owmeter. The water owrate is controlled by a
high precision HPLC Gilson 307 pump.
2-g samples of tyre char have been used in each reaction. It is
noteworthy that the char particles obtained in the conical spouted
bed are the same size as the original tyre particles used in the
pyrolysis process, which are smaller than 1 mm. Furthermore, the
excellent gassolid contact of the conical spouted bed (and the
short gas residence time) avoids additional carbonaceous material
deposition on the original carbon black of the tyre. This is due to
the fact that gasparticle circulation in this bed is countercurrent

Fig. 1. Scheme of the steam activation unit used in this work.

G. Lopez et al. / J. Anal. Appl. Pyrolysis 85 (2009) 539543

541

Fig. 2. Effect of pyrolysis temperature over the char samples BET surface area.

in the annular zone and co-current but highly turbulent in the

spout, which allows for a very efcient contact.
The surface area of the tyre char obtained in the process of
pyrolysis in the conical spouted bed increases in a very pronounced
way with temperature, Fig. 2, from approximately 40 m2/g at
425 8C to 120 m2/g at 600 8C. The latter is even higher than that
obtained by Roy et al. [33] by operating in a moving bed reactor
under vacuum.
The char sample is heated in an inert atmosphere (nitrogen)
ow until the activation temperature is reached. Once this
temperature has been reached, nitrogen ow is maintained for
1 h in order to complete sample carbonization. The activation gas
mixture, which is made up of steam and nitrogen at a ratio of
75:25, is then continuously fed into the reactor. The gas owrate
used under both inert and activation conditions is 400 cm3/min
measured at normal conditions. When the reaction has nished,
the activation mixture is replaced by nitrogen and the reactor is
cooled. Finally, the sample is removed from the reactor and
weighed to determine the burn-off undergone in the activation.
Surface area, and pore volume and size distribution, have been
determined from nitrogen adsorptiondesorption isotherms carried out in a Micromeritics ASAP 2000. The technique based on Hg
porosimetry (Micromeritics Autopore II 9220) has been used to
characterize macropores.
The composition of the active carbon samples obtained in the
activation process has been determined in an LECO CHNS-932
elemental analyzer. Sulphur content is a parameter of great
relevance, given that its application as active carbon or reuse as
carbon black requires this content to be lower than 1%.
3. Results and discussion
Activation runs have been carried out at 850 and 900 8C for
several times. Fig. 3a shows the evolution of burn-off with
activation time for both temperatures. As observed, the pyrolytic
tyre char shows a high reactivity using steam as activation agent at
both studied temperatures, this high reactivity can be mainly
attributed to the catalytic effect of inorganic components [34] such
as zinc oxide. There is a clear increase in reaction rate with
temperature, given that it approximately doubles from 850 to
900 8C. For both temperatures studied, the evolutions of burn-off
with time are almost linear, Fig. 3a. The burn-off curves do not start
at zero, because there is a mass loss during the carbonization step.
These initial mass losses are 10.6% at 850 8C and 12.0% at 900 8C.
Moreover, the BET surface areas of the chars grow during
carbonization. Thus, the char obtained in tyre pyrolysis has a
BET surface area of 65.2 m2/g, but the samples carbonized at 850
and 900 8C have 89.5 and 93.2 m2/g, respectively.

Fig. 3. (a) Evolution of burn-off in the activation process at the two temperatures
studied. (b) BET surface area values of the active carbons obtained at different burnoff levels.

Fig. 3b shows the BET surface area values obtained for the
sample for different burn-off levels. As observed, the evolutions are
very similar, so temperature affects mainly the activation kinetics,
but not porous structure development. The maximum BET areas
for both temperatures studied are higher than 500 m2/g. Concerning the BET areas published in the literature, they vary in a
relatively wide range from 300 to 1000 m2/g. These differences are
a consequence of several factors, such as the experimental device
used for the activation process, the original tyre characteristics,
pyrolysis conditions (heating rate, secondary reactions) and other
factors that may affect the char porous structure and reactivity.
The BET area increases steadily with burn-off until levels of
around 60%, when the maximum BET surface area values are
obtained. For longer treatments, a reduction in surface area is
observed. This trend is observed at the two temperatures studied
in this paper.
The shape of the adsorption isotherms gives useful information
about the porous structure of the tyre-derived-carbons. Fig. 4a shows
a comparison between the isotherms of the original pyrolytic char
and the carbon obtained after 1-h activation at 900 8C. The active
carbon predominantly exhibits a type IV isotherm, which is characteristic of mesoporous materials. The initial adsorption capacity at
low relative pressures records limited micropore development.
Moreover, an important mesoporous structure is created, as is
evidenced by nitrogen adsorption at high relative pressures and by
the typical hysteresis loop of mesoporous materials [35].
Fig. 4b shows the evolution of the total pore volume and
micropore volume of the carbons obtained for different activation
times. The data presented correspond to the activation reactions
carried out at 850 8C, and both the trend and the values obtained

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G. Lopez et al. / J. Anal. Appl. Pyrolysis 85 (2009) 539543

Table 1
Elemental analysis of the original pyrolytic char and of active carbon samples
obtained with different burn-off levels and temperatures.

Fig. 4. (a) Comparison of adsorptiondesorption curves of the original tyre char

with those of the active carbon obtained for 1-h activation at 900 8C. (b) Evolution of
the micropore and total pore volume during the activation process carried out at
850 8C.

are similar to those obtained at 900 8C. As observed, the micropore

volume represents a small fraction of the total pore volume,
around 10% of the total pore volume. Both the total pore volume
and micropore volume reach the maximum for burn-off values in
the 5060% range and longer activation times give way to lower
values of these parameters. This trend is explained by the growth
and destruction of micropores walls to produce meso- and
macropores [14].
Fig. 5 shows the pore size distribution obtained for samples
activated at 850 8C for 1, 2.5 and 3 h. The results obtained for the

Sample

Carbon (%)

Hydrogen (%)

Nitrogen (%)

Sulphur (%)

Original char
850 8C, 1 h
850 8C, 3 h
900 8C, 0.5 h
900 8C, 1.5 h

86.92
87.23
77.29
86.49
78.22

1.17
0.89
1.10
1.00
1.10

0.51
0.12
0.06
0.10
0.08

3.34
1.26
0.57
1.25
0.34

activation carried out at 900 8C are very similar to those at 850 8C.
The BarrettJoynerHalenda (BJH) method [35] was used to
deduce the pore size distribution. As observed for all the carbons,
there is an important amount of pores of around 500 A, which is a
result observed by other authors [20]. Moreover, for long activation
periods, there is also an important amount of large pores of 1000 A.
This trend of increasing pore size with activation time has been
observed by other authors [16]. It suggests that the activation
process consists of micropore formation, followed by pore
enlargement.
Table 1 shows the elemental analysis of the original char and
carbons obtained for different activation times. The char
obtained by pyrolysis has a similar composition to coal, mainly
made up of carbon, with limited hydrogen and nitrogen contents.
The ash content is in all cases around 10%, which is mostly ZnO. In
fact, the starting material we used for pyrolysis is vulcanized
rubber without steel chords or other additives. The pyrolytic char
in the pyrolysis process has a considerable sulphur content due
to the addition of this compound as vulcanization agent. This
content is a problem for pyrolytic char reuse as carbon black,
given that sulphur content for this purpose must be lower than
1% [36]. Apart from the improvement of char surface properties
during the steam activation process, an important reduction in
sulphur content is attained, which has also been observed by
other authors [32,37] but has been scarcely commented in the
literature. It should be noted that sulphur content is a
specication of commercial active carbons, so the reduction in
sulphur content could be the key for the industrial application of
tyre-derived-carbons.
4. Conclusions
The steam activation of pyrolytic tyre char obtained in a conical
spouted bed reactor produces good quality active carbon.
Commercial active carbons are microporous materials, but those
obtained from fast pyrolysis of waste tyres are mainly mesoporous.
The presence of mesopores and macropores makes pyrolytic tyre
char suitable for the adsorption of large molecular size compounds.
The properties of the carbons obtained depend largely on
activation time, but temperature seems only to have a kinetic
effect. Steam activation has another important advantage, namely,
sulphur removal from the char during activation. This removal is
enhanced by the structure of the char obtained in the conical
spouted bed reactor. This reduction in sulphur content may be the
key for the industrial application of tyre-derived-carbons, either as
active carbons or as carbon blacks for tyre manufacturing.
Acknowledgements

Fig. 5. Pore size distribution for active carbons obtained at 850 8C for different
activation times.

This work was carried out with the nancial support of the
University of the Basque Country (Project GIU06/21), the Ministry
of Science and Education of the Spanish Government (Project
CTQ2007-61167) and of the Ministry of Industry of the Basque
Government (Project IE05-149).

G. Lopez et al. / J. Anal. Appl. Pyrolysis 85 (2009) 539543

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