Carbon 42 (2004) 27892805

www.elsevier.com/locate/carbon

Production of active carbons from waste tyresa review

Edward L.K. Mui, Danny C.K. Ko, Gordon McKay

Department of Chemical Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong
Received 22 September 2003; accepted 26 June 2004

Abstract
A review of the production of activated carbons from waste tyres is presented. The eects of various process parameters, particularly, temperature and heating rate, on the pyrolysis stage are reviewed. The inuence of activating conditions, physical and
chemical, nature of the activation chemicals, on the active carbon properties are discussed. Under certain process conditions several
active carbons with BET surface areas over 1000 m2/g have been produced with extensive micropore volumes, over 40% of the total
pore volume.
A review is carried out of the reaction kinetic modeling applied to the pyrolysis of tyres and the chemical activation of tyres. The
models cover one step and two step pyrolysis models, plus more recent models which are based on the actual chemical components
such as natural rubber, SBR and other additives.

2004 Elsevier Ltd. All rights reserved.
Keywords: A. Activated carbons; B. Activation, Pyrolysis; C. Modeling; D. Reaction kinetics

1. Introduction
The disposal of tyres represents a major environmental issue throughout the world, since the same properties
that make them desirable as tyres, most notably durability, also make their disposal and reprocessing dicult,
they are almost immune to biological degradation. The
EU, the USA and Japan together were responsible for
the disposal of a total of 5 million tones of scrap tyres
per year [1].
The major aspects of tyre problems are listed as follows:

Tyres stockpiles provide breeding ground for mosquitoes and vermin, this in turn, causing serious disease
and aecting human health.

Corresponding author. Tel.: +852 2358 7133; fax: +852 2358 0054.
E-mail address: kemckayg@ust.hk (G. McKay).

0008-6223/$ - see front matter
2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2004.06.023

Fire hazards in large stockpiles that could consequently cause uncontrollable burning and air pollution.

The current conservation of natural resource concept, i.e. the reuse (retread) rst, then reuse of rubber prior disposal, does not accommodate the ever
increased dumping of tyres.

Due to the high cost of legal disposal for tyres, illegal
dumping may increase.

Disposal of tyres is becoming more expensive, while
this trend is likely to continue as landll space becomes more scarce.

Tyres take up landll space.
The production of pyro-oil from tyre pyrolysis as a
fuel source has generated considerable interest [13].
However, most research emphasis has been focused on
the identication of the pyro-oil components [38]. During the past 1015 years, several fundamental studies
have reported that carefully controlled tyre pyrolysis

2790

E.L.K. Mui et al. / Carbon 42 (2004) 27892805

Nomenclature
ai
A
A0
Aext
bi
E
Fi
k
k0
ks
K1/2
mi
n
p
ri
R
R1/2
S(Xc)
S0
t

order of reaction i, Eq. (7.3)

pre-exponential factor (min1)
pre-exponential factor (s1)
external surface area (m2)
order of reaction for oxygen in reaction i, Eq.
(7.3)
activation energy (kJ/mol)
weighting factor accounting for the ith reaction (dimensionless)
rate constant (min1)
rate constant (s1)
pore-size independent growth rate
overall
rate
constant
at
Xc = 0.5
(s1 atm1 O1
)
2
mass fraction of component i in sample
order of reaction
partial pressure of oxygen or carbon dioxide
(atm)
reaction rate of component i, Eqs. (10.1)
(10.3)
universal gas constant, 8.314 (J/mol K)
char reactivity at Xc = 0.5 (s1)
surface area per unit volume at conversion Xc
(m2/m3)
initial total surface area per unit volume (m2/
m3)
time (min or s)

can produce a number of valuable products. Most of the

literature refers to the production of active carbons from
coal [911] and details are discussed elsewhere [1113].
However, several studies have reported the production
of chars and activated carbons from waste tyres [14
19]. The potential of these products as possible adsorbents for various pollutants has been assessed and found
to be very successful, thus stimulating a serious research
interest. These active carbons have been used to adsorb
phenols, basic dyes and metals [20], phenols and p-chlorophenols [21], butane [22] and natural gas [23]. The
production, characterization and uses of carbon blacks
as printing inks bases and recycled tyre llers has been
studied [24,25]. A pyro-gas is generated from the tyre
pyrolysis and this gas has been analyzed by a number
of workers [2631] and shown to contain carbon dioxide, carbon monoxide, hydrogen sulde, methane,
ethane/ethene, propane/propene, butane/butene and
butadiene and possessing a gross caloric value in the
range of 3040 MJ/N m3.
The present paper reviews the current state of the
production and characterization of activated carbons
from waste tyres. The models used to describe the pyrolysis of waste tyres are described and discussed together

T
Vfi
Vi
W
Wo
Wf
Wi
Xc

temperature (K)
ultimate yield of volatile fraction i at t ! 1
accumulated fraction of volatile evolved at
time t
weight of sample at time t
weight of sample at t = 0
weight of sample at the completion of reaction
weight of component i in tyre rubber at time t
carbon conversion (dimensionless)

Greek symbols
a
mass fraction of decomposable portion,
Wo  W/Wo  Wf
aD
discreteness parameter
b
heating rate (K/min)

o
porosity at time = 0
j
summation index, Eqs. (9.1) and (9.3)
w
structural parameter (dimensionless)
wE
eective structural parameter
Subscripts
i
component number
o
initial, t = 0
f
nal
T
total
v
volatile

with the existing modeling theories for the activation of

tyre carbon chars.

2. Experimental conditions for carbon production from

tyres
Physical activation using carbon dioxide or steam as
oxidizing agents are the most commonly used processes
in the production of tyre carbons. The overall process
usually consists of two steps: thermal pyrolysis at a
relatively low temperature (typically 400700 C) in
the presence of nitrogen or helium to break down the
cross-linkage between carbon atoms, and activation
with activating gas at 8001000 C for further development of the porosity of tyre carbon.
Carbon characteristics are greatly inuenced by the
degree of the activation but also by the nature of the
activating agent (steam or carbon dioxide) and process
temperature. Table 1 presents a summary of characteristics of the tyre carbons activated by dierent conditions.
For the purpose of elevating the degree of burn-o, the
activation temperature is usually higher than 900 C to
maintain a suciently high reaction rate. When steam

Table 1
Pore and surface characteristics of tyre carbons activated under dierent conditions
Particle size of
tyre rubber
(mm)

Charring
conditions
(C, h)

Activation
conditions
(C, h)

Char burn-o
(%, ash content
incl.)

Chemical
treatment

Activating gas
ow rate
(ml/min)

BET surface
area (m2/g)

Vmicro
(cm3/g)

Ariyadejwanich
et al. [35]a

<0.595

500, 1

850, 4

77.5

Steam

680

1119

0.57

7.9

(1a) PH2O was 0.46 atm

(1b) Total pore volume was
2.19 cc/g
(1c) Heating rate was 5 C/
min

850, 3

68.6

1177

0.54

11.2

(2a) PH2O was 0.46 atm

(2b) Total pore volume was
1.76 cc/g
(2c) Heating rate was
20 C/min

900, 3

25.9

Steam

135

272

(1) H2O ow rate was

6.8 ml/min g char

875, 7

25.5

CO2

342

270

925, 10.7

63.2

Steam

400

1070

0.55

15.1

925, 9.3

56.1

1022

0.54

17.9

Helleur et al. [20]

San Miguel
et al. [36]

<0.42

550, 4

700,

Yield
(g activated
carbon/100 g
tyre rubber)

Additional information
(1 and 2 denote samples
1 and 2, respectively)

(2) CO2 ow rate was

17.1 ml/min g char
Activating gas ow rate was
4.9 ml/min g char

Hamadi
et al. [41]

900, 2

900, 2

CO2

832

Sainz-Diaz and
Griths [37]

1000, 5
1000, 7

58.0
94.0

CO2

431
284

33.0

Teng et al. [19]

0.20.3

700, 0

KOH/N2

100

474

0.23

16.0

(1a) Tyre/KOH ratio (w/w)

was 4
(1b) Total pore volume was
0.38 cc/g

411

0.19

12.0

(2) Total pore volume was

0.57 cc/g

800, 0

E.L.K. Mui et al. / Carbon 42 (2004) 27892805

References

2791

2792

Table 1 (continued)
References

Particle size of
tyre rubber
(mm)

Charring
conditions
(C, h)

Activation
conditions
(C, h)

Char burn-o
(%, ash content
incl.)

Chemical
treatment

Allen et al. [22]

50

800,

877,

41.0

Steam

700,
Cunlie and
Williams [18]b
Lehmann et al. [17]

Activating gas
ow rate
(ml/min)

48.0

Vmicro
(cm3/g)

Yield
(g activated
carbon/100 g
tyre rubber)

Additional information
(1 and 2 denote samples
1 and 2, respectively)

528

19.5

Char yield% was assumed to

be approx. 33 wt%

478

17.2

13.6

BET surface
area (m2/g)

450, 1.5

935,

64.0

Steam

146

640

23

850, 3

Steam

500

1000

0.44

4.0

600, 0.75

850, 3

978

0.48

4.6

Activating gas ow rate was

5.84 ml/min g char
(1a) Direct activation without pyrolysis
(1b) Total pore volume 2.23
cc/g
(2) Pyrolysis before activation

Sun et al. [34]

850, 1.5

KOH/N2

500

820

0.27

Tyre/KOH ratio (w/w) was 1

Sun et al. [34]

600, 0.75

900, 1

Steam

500

1031

0.28

Activating gas ow rate was

100 ml/min g tyre rubber

888

0.25

1031

0.28

10.0

Activating gas ow rate

varied from 181 to 271 ml/
min g tyre rubber

888

0.25

15.0

813

17.0

(1a) PCO2 = 0.16 atm

(1b) Tyre was pyrolysed under CO2

16.5

(2) O2 pre-treatment (140

C, 88 h) applied to
the second sample
prior to pyrolysis

850, 3
Brady et al. [23]

Teng et al. [16]

2.5

<0.3

600, 0.75

900,

850,

900,

Steam

CO2

542

793

Streat et al. [21]

800, 24
900, 18

Steam

200
100

346
155

Merchant and
Petrich [15]

10

530, 1

920, 1
850, 1.3

65.0
52.5

Steam

342

607
553

0.01
0.07

12.3
16.6

E.L.K. Mui et al. / Carbon 42 (2004) 27892805

30

Acid demineralization applied. Two to three grams of pyrolysed chars were immersed in 100 ml HCl (1 M) for 24 h under room temperature prior to activation.
Acid demineralization applied. Pyrolysed chars were heated in 5 M HCl to the boiling point for 90 min prior to activation.
b

Activating gas ow rate was 61 ml/min g tyre rubber

9.0
22.0

1260
600
61
Steam

900, 3
900, 0.5

445, 1.5

Merchant and
Petrich [32]
Ogasawara et al. [14]

25

850, 0.5

13.4

Steam

164

0.04

29.5

Activating gas ow rate was 1630 ml/min g char

E.L.K. Mui et al. / Carbon 42 (2004) 27892805

2793

is used as an activating gas, the apparent activation energy of gasication has been measured as 201 kJ/mol
[18]. In a study, in which the pyrolysis and activation
of tyre were carried out in a helium environment at
900 C with steam for 1 h, the product obtained had a
BET surface area up to 1260 m2/g, although the nal
mass yield of the product was as low as 9% of the initial
tyre mass [14]. A sharp increase in the surface area was
observed when the activation took place at a temperature of 770 C or above, and based on current technologies and literature results tyre char activation below
700 C looks impractical. Experimental results showed
that tyre rubber started to decompose at 450 C and this
phase was essentially completed at 500600 C [18,32,33]
giving char yields in the range of 3342% with very limited porosity development (<100 m2/g in specic area).
Previous studies suggested that the activation process
consisted of micropore formation, followed by pore
enlargement in which the resulting carbons had BET
surface areas up to 607 m2/g using a nitrogenwater mixture containing 40 mol% water [15]. At 40% burn-o,
the micropore volume reached the maximum, and beyond this point mesopores grew at the expense of micropores but exhibits an increasing trend in the BET surface
area. A similar phenomenon, reported by dierent
researchers, stated that pores developed on highly activated samples, with a burn-o of 8090%, were mainly
meso- and macroporous since steam activation both
widened existing pores and created new porosity
[17,23,34]. In one of the studies, tyre rubber was pyrolysed at 600 C under nitrogen for a period of 45 min,
followed by activation conducted at 850900 C with a
owing steamnitrogen mixture (50:50, v/v) for 0.53
h. The resulting carbons exhibited high specic surface
area up to 1031 m2/g with a decreasing trend in pore
diameters with activation [17]. It was found that the
and
average pore width decreased from 335 to 81 A
had a lower overall micropore volume. Carbon prepared
at 900 C for 2 h developed a micropore volume of 0.39
cm3/g, which also represented approximately 28% of the
total pore volume of 1.40 cm3/g.
Some metallic components in ash are considered to
have a signicant inuence on the rate of activation as
well as the formation of pores in the process of activation due to the presence of oxides on surface [17]. To
investigate the eect of ash on the reactivity of the
tyre-derived char, acid demineralization was attempted
to remove species such as calcium compounds prior to
the activation stage. It has been shown that the reactivity of char treated by 5 M hydrochloric acid was around
22% less than those samples without acid treatment in
steam activation [18], in which calcium ions in the char
catalyzed the gasication reactions, which, as a consequence decreases the importance of the watergas shift
reaction. Acid treatment was also found eective in
the removal of inert mineral matter, which blocked the

2794

E.L.K. Mui et al. / Carbon 42 (2004) 27892805

pore structure of the pyrolysed char, leading to an increase of micro- and mesopore volumes. The tyre-derived carbon had a specic area of 1119 m2 and 1.62
cm3/g mesopore volume, when the pyrolysed tyre char
was treated with 1 M HCl at room temperature for
one day prior to steam activation in which a mixture
of steam/nitrogen (77:23, v/v) was used [35].
The particle size of the tyre rubber was found to have
inuence on the porosity of the resultant carbon generated from steam activation. Both surface area and
micropore volume of carbons produced from powdered
tyre rubber (particle size < 0.42 mm) were 5% and 40%
higher than those carbons prepared from particles in larger size (particle size < 2.0 mm) [36]. It was believed that
smaller particles allowed better diusion of steam molecules into the structure, leading to a more homogeneous
activation of the carbonized precursor. For the process
in which tyre rubber was heated to 700 C, followed
by activation under 80:20 v/v steamnitrogen mixture
at 925 C for 640 min, the BET surface area and micropore pore volume of carbon were found to be 1070 m2/g
and 0.50 cm3/g, respectively [36]. However, it is worth
noting that other research yielded a dierent point of
view and suggested that particle size had only limited effect to the surface area development in CO2 activation
[16].
The oxidizing ability of steam (135 ml/min in nitrogen), carbon dioxide and 2% O2 in nitrogen under different activation temperature and holding times
were evaluated in a study which the tyre rubber was
carbonized at 900 C under nitrogen ow for 1 h, followed by the subsequent activation which the temperatures and gas ow rates were adjusted according to the
activating agent used. It was shown that O2 appeared
to be ineective in porosity development and activation using steam at 900 C for 3 h produced an activated carbon with a surface area only up to 302 m2/g
[20].
Carbon dioxide is considered as one of the potential
activating agents in the production of activated carbon
from tyre. Product prepared in 1 atm CO2 at 900 C
with a surface area of 813 m2/g at 50% burn-o was reported in literature [16], revealing that the surface areas
of tyre carbons were increased by performing activation
under a higher partial pressure of activating agent. This
is in agreement with the previous report of tyre carbon
activation by steam [14]. The surface area achieved in
carbon dioxide at a given temperature exhibited a linear
increase with increasing burn-o due to the relatively
lower level of CO and H2 at the initial stage of activation. However, the maximum surface area obtained
was slightly over 500 m2/g which was approximately
28% lower than that produced by steam in the linear region where the burn-o was 65 wt% [18]. Another study
reported a mass loss of 25.5%, and the CO2-activated
carbon was found to have a surface area of 270 m2/g,

while the carbon prepared via steam activation at similar burn-o (25.9%) was 302 m2/g [20].
It is interesting to note an exception reported by
Sainz-Diaz and Griths [37], which stated that longer
holding times led to a reduction in the surface area,
microporosity and adsorption of methylene blue. Comparing the BET areas of CO2 derived carbons at dierent holding times, the carbon activated in 5 h
exhibited higher surface area (431 m2/g) than the sample
obtained after 7 h of activation, in which the surface
area was only 284 m2/g [37]. It is consistent to a nding
which states that as the continuous burn-o of carbon
can start burning o walls between the adjacent pores
and turning more micropores into macropores, leading
to the decrease in BET surface area [9].
The eect of activation temperature in the CO2 activation process was investigated in a case where tyre rubber was heated to 700 C in nitrogen, when this
temperature was reached, the gas was substituted by carbon dioxide at a ow rate of 500 ml/min and further
heated to 9501100 C for 60640 min [38]. The results
showed that increasing temperature had little eect on
the characteristics of carbons in the temperature range
between 950 and 1100 C. This could be explained by
the limited diusion of gas molecules into the interior
of the carbon particles at higher reaction rates [39]. It
has been shown that, CO2 activated carbon exhibited
lower micropore volume in comparison with those obtained by steam activation at a higher degree of activation (burn-o 40% or above). It was also noted that CO2
produced carbons of slightly larger external surface
areas.
Chemical activation is an alternative process of the
production of activated carbon from tyres. It allows
both pyrolysis and activation to be integrated into a single, relatively lower temperature process in the absence
of oxygen. Although a wide variety of activating agents
are known, using KOH in making carbons has become
popular in recent studies. Sun et al. [34] mixed tyre rubber with KOH pellets in the mass ratio of 1:1, and activated at 850 C in nitrogen for 0.51.5 h. In this case, a
higher activation temperature was chosen for treating
samples so that a shorter activation period could be applied [34]. The activation period was set at 1.5 h, giving
the resultant carbon a specic area of 820 m2/g and
micropore volume up to 0.274 cm3/g. The authors also
reported that a smaller particle size (0.4 mm) of the tyre
rubber was used and was favorable as it would allow
good surface contact with KOH.
The eect of mass ratio between KOH and tyre
proved to be an inuencing factor to the pore development of carbon derived from tyre [19]. The experimental
results showed that the BET surface area increased as
the KOH/tyre mass ratio increased and reached the
maximum when the ratio is 4. Beyond that point, the
BET surface area declined signicantly in parallel with

E.L.K. Mui et al. / Carbon 42 (2004) 27892805

yield. It was shown that, at the activation temperature of

700 C and zero holding period, the carbon produced
had a maximum BET surface area of 474 m2/g with a
micropore volume of 0.23 cm3/g. Increasing the holding
period to 2 h would result in an increase of mesopore
volume but in return, micropore volume would go down
as the consequence of the collapse of micropore walls in
an extended heating process due to the hydrophobic nature of the tyre surface that prevented penetration of
KOH into the interior of the rubber matrix. Higher surface areas would be possible if the contact between
KOH and tyre particles could be improved.

3. Properties and characteristics of tyre carbons

3.1. Surface area
Surface area is one of the key indicators attributed to
the adsorptive properties of porous materials. The most
commonly used model in the determination of that
parameter was developed by Brunauer et al. which is
well-known as the BET equation [40]. The development
of surface area is shown to have a linear relationship
with the degree of burn-o, which is a function of dierent factors such as the activation temperature, gas pressure and holding time [14,15,18,23,36,38]. Generally,
increasing temperatures and holding time would result
in a rise of burn-o due to the burn-out of micropore
walls.
It appeared that most steam-activated carbons exhibited higher BET surface areas than those prepared from
carbon dioxide activation. The BET surface areas of the
steam-activated carbons are generally in excess of 1000
m2/g [14,17,23,3436,38] although CO2 activation also
gave products with good surface areas ranging from
270 to 980 m2/g [16,20,36,38,41]. This could be explained
by the molecular nature of steam because the water molecule is smaller than the CO2, giving faster diusion into
the porous matrix and micropores [38,39]. In other related studies in which dierent precursors were used,
steam activation has been found to be approximately
two to three times more rapid than CO2 activation
[42,43].
3.2. Pore size and volume
Pores in dierent sizes are important to the adsorbents overall capacity in adsorption processes. The presence of micro- and mesopores in activated carbons
enhance the adsorption of large adsorbates such as dye
molecules [4346]. When using steam as an activating
agent, pores in tyre carbons would be broadened
[34,39] and the adsorptive capacity of tyre carbons will
increase with increasing micropore volume in certain
gaseous adsorption processes due to the enhanced

2795

adsorption potential of gas molecules in small pores

[17,22]. Experimental data suggested that tyre chars
developed a very narrow microporosity during the initial
stages of the steam activation process (up to 1525%
burn-o). When the holding period was extended, continuous pore enlargement increased the porosity from
a predominantly micro- to a more mesoporous structure
[36].
It should be noted that chemical treatment of tyre
rubber before activation results in a change of porosity.
When the pyrolytic char was treated with 1 M hydrochloric acid prior to steam activation, the increase in
both micro- and mesopore volumes from 0.26 and 1.09
cm3/g to 0.57 and 1.62 cm3/g, respectively were observed
[35]. For a chemical activation process in which KOH
was used as an activating agent, literature values reported that the total pore volume rose in parallel with
the increasing amount of KOH impregnated. This phenomenon was due to the enlargement of micropores
developed at the initial stage of activation [19].

4. Applications and uses of tyre based active carbons

There is a wide range of applications of tyre chars
and carbons in dierent areas. Similar to other adsorbents, tyre carbons can be used in both liquid- and
gas-phase applications.
4.1. Liquid-phase applications
Activated carbons have long been used in the removal
of both organic and inorganic species from euents generated in industrial production processes [46]. Owing to
the high surface areas (ranging from 164 to 1260 m2/g)
and pore volumes (up to 1.62 cm3/g), tyre carbons are
considered as a potential adsorbent in the water treatment for the purpose of removing organic pollutants
such as phenol and p-chlorophenol. Experiment results
were found promising, as the amount of uptake was
comparable to conventional carbons derived from coal
and wood [21]. In the case of chemical activation tyre
carbons prepared from KOH activation could be used
in the removal of halogenated hydrocarbons and pesticides in drinking water [19]. Other examples of using
tyre-derived carbons in water treatment include the removal of chromium [41], lead, copper [20], dyes and phenol [20,21,33,35,38].
Tyre rubber carbonized at temperatures ranging from
450 to 800 C were tested for the adsorption eciency of
reactive dyes Procion Turquoise H-A and Procion Red
H-E3B, which high adsorption capacity for both dyes
(36 and 30 mg/g adsorbent, respectively) were reported
[33]. When the chars were further activated by steam,
the uptake of Procion Red was over 300 mg/g, showing
a high adsorption capacity for species of large molecular

2796

E.L.K. Mui et al. / Carbon 42 (2004) 27892805

weight [33]. Similar observation in which the steam-activated tyre carbons showed better adsorption capacity
for dye (Black 5) and slightly lower phenol adsorption
capacity in comparison with commercial carbons [35].
Tyre carbon prepared by CO2 activation had an
adsorption capacity of Cr6+ ions up to 48.2 mg/g in an
acidic environment (pH  2) [41]. Helleur et al. [20] also
suggested that, tyre char carbonized at 600 C had an
encouraging result for copper ion adsorption. The
capacity was three times as high as that for commercial
activated charcoal. Using CO2 as an activating agent,
tyre carbons adsorption capacity almost matched the
commercial products sorption capacity in both phenol
and methylene blue adsorption tests [20].
4.2. Gas-phase applications
Activated carbons provide an eective means for gasphase applications, such as the separation, storage and
catalysis of gaseous species. One example is the storage
of natural gas for automobiles, in which natural gas is
adsorbed on tyre carbons under high pressure as fuel
storage. Uses in similar areas, for instance, storage for
the purpose of transportation of natural gas or other
ammable gases (e.g. acetylene) have been found possible [17,22,23,34,39].
Tyre carbons may be used in air pollutant control in
ue gas treatment. In the adsorption of SO2, tyre char
exhibited an adsorption rate similar to a commercial lignite-based carbon [23]. Tyre carbon was also found
superior in the adsorption of mercury in comparison
with coal-derived activated carbon or even commercial
products [17].

5. Modeling of the activated carbon formation

The formation of activated carbon from tyre consists
of two steps: pyrolysis under nitrogen or other inert
gases to break down the cross-linkage between carbon
atoms, followed by activation in the presence of activating agents such as carbon dioxide or steam for further
pore development. With the aid of the thermogravimetric techniques such as thermogravimetric analysis
(TGA) and derivative thermogravimetry (DTG), a number of kinetic models have been developed for the study
of pyrolysis mechanism and kinetic parameters [16,47
57]. The rst-order reaction based on the Arrhenius
Theory is commonly assumed by researchers in the kinetic analysis of data for tyre decomposition, which
states



E
k A exp 
1:1
RT
in which k is the rate constant; A is the pre-exponential
factor, E is the activation energy, R and T are the uni-

versal gas constant and absolute temperature, respectively. Table 2 is a summary of models on tyre rubber
pyrolysis published in recent years, and the kinetic
parameters derived from dierent TGA/DTG studies
are given in Table 3.
The rate of decomposition may be expressed by
da
n
k1  a
dt

1:2

where a = fraction of reactant decomposed at time t and

n = order of reaction [47]. When the heating rate was b,
rearranging Eqs. (1.1) and (1.2) gives


Z a
Z
da
A T
E

exp
dT
1:3
b 0
RT
0 1  a
The right-hand side of Eq. (1.3) has no exact integral,
Coats and Redfern suggested an approximation as [47]






Z
A T
E
A RT 2
2RT
E
1
exp
dT
exp
b 0
RT
b E
E
RT
1:4
Some of the kinetic models published were established
on the basis above in modied form. Examples include
Eqs. (4.1), (4.2), (5) and (9.1) [16,50,54].
5.1. Kinetic models for pyrolysis
A derivative thermogravimetry (DTG) simulation
based on the rst-order Arrhenius equation separated
the decomposition into two overlapping processes,
namely, oil volatilization and elastomer decomposition
[48]. It has been shown that the processing oil decomposed prior to the decomposition of elastomers.
Assuming all decomposable fractions are converted
to volatile gas, the decomposition of a single elastomer
such as styrenebutadiene rubber (SBR), an expression
of reaction rate (in min1) was proposed as follows:



da
E
A exp 
2:1
1  a n
dt
RT
where a is the mass fraction of the volatiles emitted at
time t; A was a pre-exponential factor; E was the apparent activation energy; R was the ideal gas constant and
T was the absolute temperature. When the number of
elastomers involved was two, it was assumed that each
elastomer decomposed independently, giving a thermal
degradation rate as
da
da1
da2
m1
m2
dt
dt
dt

2:2

where m is the mass fraction of elastomers and the sum

of m was 1.
When the tyre rubber was heated to 720 C at dierent heating rates ranging from 5 to 80 K/min, two distinct decomposition processes were observed, giving an

E.L.K. Mui et al. / Carbon 42 (2004) 27892805

2797

Table 2
A summary of pyrolysis models developed in previous studies
References
Yang et al. [48]


da
E
A exp 
1  an
dt
RT

Williams and Besler [49]

dW
kW  W f
dt

(3)

Kim et al. [50]

n
n
X
X
dW
dW i


ki W i
dt
dt
i1
i1

(4.1)

"


)

2 #
A1 RT 2
2RT
RT
E1
1
4
exp 
W 1 W 1;0 exp 
E1
E1
bE1
RT

(2.1)

(
W 2 W 2;0 exp 

"


)

2 #
A2 RT 2
2RT
RT
E2
exp 
1
4
E2
E2
bE2
RT

(4.2)

(4.3)

Teng et al. [16]





V fi  V i
Ai RT 2
Ei
exp 
exp 
V fi
bEi
RT

(5)

Lin et al. [51]



X
Wi
Ai RT 2
1
bEi eEi =RT 
1  1  1  n
Ei ; T 
1  n
Fi
3

(6.1)

"

#
i i
i
X
X
RT Y
E; T

j 1
E
i0
j0

Chen et al. [52]

Conesa et al. [53]

W0 W
W0Wf


da
25; 380
1:320  1014 exp 
1  a0:6
dt
T

2
da X

k i 1  ai ai O2 bi
dt
i1


dm X
Ei

Ai exp 
mni
dt
RT
"

Leung and Wang [54]

#


 1
A RT 2
E X
2j
exp 
a 1  exp 
b E
RT j0 E=RT j

(6.2)

(7.1)

(7.2)

(7.3)

(8)

(9.1)

(continued on next page)

2798

E.L.K. Mui et al. / Carbon 42 (2004) 27892805

Table 2 (continued)
References
Leung and Wang [55]
Three-components

Three-elastomers

Senneca et al. [56]

Chen et al. [57]

Passenger car tyre

Truck tyre


3
3
daT X
dai X
Ei

1  ai
Ai exp 
dt
dt
RT
i1
i1

(9.2)


6
6
daT X
dai X
Ei

Ai exp 
W T0  W T1 j1 ai1  ai j
dt
dt
RT i
i1
i1

(9.3)


20; 300
mV
r1 1  1013 exp 
T

(10.1)


10; 000
mR
r2 1  104 exp 
T

(10.2)


20; 400
mV
r3 1  1012 exp 
T

(10.3)


da
17; 760
7:57  1010 exp 
1  a1:98
dt
T

(11.1)


da
17; 811
5:02  1010 exp 
1  a1:63
dt
T

(11.2)

expression for tyre decomposition as follows (in s1)

[49]:
dW
kW  W f
dt

where W is the weight of sample at time t; Wf is the

weight of residue at the end of the reaction, and k represented the rate constant dened by the Arrhenius equation (Eq. (1.1)). The tyre decomposition was found to be
a two-stage process, in which the natural rubber (NR)
decomposed at a lower temperature, followed by styrenebutadiene rubber (SBR) and polybutadiene rubber
(BR) at a higher temperature.
A rst-order, irreversible reaction model was developed on the basis of which each component is expected
to decompose separately in the pyrolysis process [50].
The relationship between overall weight loss and reaction time was described as
n
n
X
X
dW
dW i


kiW i
4:1
dt
dt
i1
i1
where Wi was the weight of the decomposable component i at time t and ki was the rate constant of component i with respect to t. The unit was mg/min.

The model further assumed that tyre rubber comprised two major degradable components, giving a
kinetic decomposition model of components 1 and 2 at
elevated temperature (in mg):
(
"

2 #
A1 RT 2
2RT
RT
1
4
W 1 W 1;0 exp 
E1
E1
bE1



E1
 exp 
4:2
RT
(
"

2 #
A2 RT 2
2RT
RT
W 2 W 2;0 exp 
1
4
E2
E2
bE2



E2
 exp 
4:3
RT
where W1,0 and W2,0 are the initial mass of components
1 and 2, respectively.
It has been shown that the amount of volatiles
evolved in the tyre pyrolysis process could be modeled
by dividing the overall evolution into three fractions,
each of which is represented by a single rst-order reaction based on an Arrhenius equation (dimensionless)
[16].

Table 3
Experimental conditions and kinetic parameters from dierent TGA/DTG studies
Materials

Pyrolysis
temperature (C)

Heating
rate (C/min)

Particle
size (mm)

Sample
weight (mg)

Gas ow rate
(gas, cc/min g)

Activation energy,
E (kJ/mol)

Pre-exponential
factor, A (min1)

Reaction
order, n

Yang et al. [48]

NR
NR
BR
SBR
SBR
SBR

30550

1
10
10
1
10
40

48

N2, 25,00050,000

207
207
215
152
152
139

3.89 1016
2.36 1016
6.32 1014
5.44 1010
4.15 1010
8.82 109

2
2
1
1
1
1

Williams and Besler [49]

Tyre A
Tyre B

720

<1

20

N2,

142.7
102.8
145.0
130.8
142.4

1.26 1010
5.58 109
6.60 109
7.20 109
1.20 1010

Tyre C

(low)
(high)
(low)
(high)

Kim et al. [50]

Tyre

50577

2.515

10

He,

203.9 (compound 1)
195.1 (compound 2)
42.1 (compound 3)

2.04 1014
2.08 1015
1.44 103

Teng et al. [16]

Tyre

700

3100

<0.3

He,

125.5 (reaction 1)
178.7 (reaction 2)
243.9 (reaction 3)

2.68 1011
6.78 1013
2.85 1017

1
1
1

Lin et al. [51]

SBR

127677

37

<1

N2, 12,500

52.2 (reaction 1)
150.6 (reaction 2)
169.4 (reaction 3)

2.30 103
1.50 1010
3.50 1010

2.09
1.28
1.90

Chen et al. [52]

SBR

1001000

220

N2/N2 + O2, 5560

211 (100% N2)

153176 (5% O2 + N2)

1.32 1014
5.75 108

0.6
0.480.56

Conesa et al. [53]

Tyre

100650

10

<1

57

N2 + O2,

83.6 (component 1)
245.6 (component 2)
201.7 (component 3)
223.2 (component 4)

1.70 108
2.78 1016
2.49 1016
2.27 1010

2.45
3.91
1.46
0.69

Leung and Wang [54]

Tyre

20600

10

0.3550.425

N2,

164.5 (low)
136.1 (high)
180.9 (low)
133.6 (high)
203.4 (low)
107.0 (high)
218.7 (low)
99.1 (high)

6.29 1013
2.31 109
1.32 1014
2.09 109
7.58 1015
3.34 107
1.13 1017
1.02 107

1
1
1
1
1
1
1
1

30
45
60

E.L.K. Mui et al. / Carbon 42 (2004) 27892805

Reference

2799

2800

E.L.K. Mui et al. / Carbon 42 (2004) 27892805

Reaction
order, n

1
2
1
1
1
1

1.98
1.63

Pre-exponential
factor, A (min1)

4.50 103
3.00 1014
2.30 103
7.10 1014
6.90 103
3.10 1010

7.57 1010
5.02 1010

Activation energy,
E (kJ/mol)

43.3 (NR, oil)

207.0 (NR, elastomer)
43.3 (BR, oil)
215.0 (BR, elastomer)
48.0 (SBR, oil)
152.0 (SBR, elastomer)

147.6 (passenger)
148.1 (truck)
N2, 5000
10
530
1001000

0.355 (Passenger)
2 (Truck)

N2,
8
0.3550.425
10
20600

Sample
weight (mg)
Heating
rate (C/min)
Pyrolysis
temperature (C)

Particle
size (mm)

Gas ow rate
(gas, cc/min g)

When temperature is T, Vfi is the ultimate yield of volatile fraction i as time goes to innity; Vi is the fraction of
volatile evolved at time t; R is the gas constant; Ai and Ei
are pre-exponential factor and activation energy of component i, respectively.
This model is consistent to a model of SBR pyrolysis,
which stated that three principle reactions were involved
in the entire decomposition [51]. The mass fraction of
degradable component in reaction i (Wi) at temperature
T and heating rate b were shown as (dimensionless)


Wi
Ai RT 2 Ei =RT X
1  1  1  n
e

Ei ; T
Fi
bEi
1
6:1

1  n
where
X

"

#
i i
i
X
RT Y
E; T

j 1
E
i0
j0

Tyre

Tyre
Leung and Wang [55]

Chen et al. [57]

Materials

6:2

and Fi = weighting factor accounting for the ith reaction

(0 6 Fi 6 1); n = order of reaction; i = reaction number
(1, 2 or 3) and j = product index based on i. The Eq.
(6.2) is dimensionless.
Other researchers [52] studied the thermal decomposition of SBR using a nitrogenoxygen mixture, giving a
global reaction as
k

SBR ! volatiles
The normalized conversion of tyre to volatile gases, a,
was expressed in a dimensionless form
a

Reference

Table 3 (continued)





V fi  V i
Ai RT 2
Ei
exp 
exp 
V fi
bEi
RT

W0W
W0Wf

7:1

where W0 = initial sample mass; W = sample mass at

time t, and Wf = residual mass at the completion of reaction. It was found that in pure nitrogen, only a one-stage
reaction would occur and the overall rate equation (in
min1) becomes



da
25; 380
1:320  1014 exp 
7:2
1  a0:6
dt
T
When oxygen was involved, the decomposition process
would turn to a two-stage reaction, giving a normalized
conversion rate equation (in min1) which took the oxygen content into account:
2
da X
a
b

k i 1  ai i O2 i
dt
i1

7:3

where ki is the rate constant of ith reaction; ai and bi are

reaction orders in reaction i and [O2] was the oxygen
concentration by volume.

E.L.K. Mui et al. / Carbon 42 (2004) 27892805

It appears that more reaction occurred in the case in

which oxygen was involved in the process and the number of reactions in a helium-oxygen pyrolysis at dierent
heating rates and oxygen content (from 10 to 20% v/v)
was up to four [53]. A dimensionless weight loss model
in mass fraction m was shown as



dm X
Ei

Ai exp 
8
mni
dt
RT
where Ai and n are the pre-exponential factor of component i and mass fraction of component i in the reaction
order n.
Leung and Wang [54,55] expressed the dimensionless
normalized weight loss ratio ai at temperature T when
the heating rate, b, was constant [54,55]:
"
#


 1
j
A RT 2
E X
2
ai 1  exp 
exp 
j
b E
RT j0 E=RT
9:1
where j represents the summation index of the decomposition process.
Experimental data showed that the overall degradation was less dependent on particle size but more sensitive to the heating rate. The authors further proposed
two models, namely, a three-component-simulation
model and a three-elastomer-simulation model, to predict the fraction weight loss and weight loss rate proles.
In the three-component model, tyre rubber was assumed
to be having of a mixture of oil, moisture, plasticizer and
additives, while components 2 and 3 consisted of NR,
BR, SBR and their combinations. Each component
decomposed at dierent temperature regions, giving
the overall normalized weight loss rate aT (min1) as



3
3
daT X
dai X
Ei

Ai exp 
9:2
1  ai
dt
dt
RT
i1
i1
In the three-elastomer model, the elastomers NR, BR
and SBR were considered as the three major components of tyre rubber, each of which had an oil component making the total number of components to be 6.
The kinetics of the pyrolysis process (in min1) then become
6
daT X
dai

dt
dt
i1

6
X
i1

primary pyrolysis
cyclization

2801
r1

A ! V1

r2

A!R

secondary pyrolysis

r3

R ! V2

where V1 and V2 are the volatiles generated in the pyrolysis; R is the cyclization product and the reaction rates
for all three reactions were presented (in min1):



20; 300
13
r1 1  10 exp 
10:1
mV
T



10; 000
4
r2 1  10 exp 
10:2
mR
T



20; 400
12
r3 1  10 exp 
10:3
mV
T
where mV and mR are the normalized mass of volatile
components (V) and intermediate (R) with respect to
the initial mass of the sample. Experimental data has
shown that a higher heating rate would result in a single
decomposition of tyre as a consequence of the decreasing extent of cyclization.
It appears that both passenger and truck tyres exhibited a similar pyrolysis behavior [57]. For each tyre, a
single equation (in min1) was suggested as an overall
pyrolysis rate model:



da
17; 760
1:98
7:57  1010 exp 
1  a
dt
T
for passenger car tyre

11:1


da
17; 811
1:63
5:02  1010 exp 
1  a
dt
T
for truck tyre

11:2

where a is a dimensionless ratio of volatile conversion to

gas, which is determined by
a

W0W
W0Wf

11:3

where W0 = initial mass of tyre rubber; W = mass of

sample at time t, and Wf = residual mass of the sample.
5.2. Kinetic models for activation


Ei
j1
j
Ai exp 
W T0  W T1 ai1  ai
RT i
9:3

where j is either 1 or 2 for each component.

The observation on the implication of tyre particle
sizes to the pyrolysis was consistent to the nding reported elsewhere. A three-reaction pyrolysis pathway
was suggested [56]:

Having limited porosity, char generated from waste

tyre requires further oxidization in an environment
where steam or carbon dioxide are present in order to
enhance the extent of pore development. From the process design viewpoint, it is critically important to know
the reaction kinetics and pore structure evolution.
Although few models regarding the kinetics of tyre char
activation are currently available, dierent models proposed for chars derived from various precursors have
been found valuable in understanding the gassolid

2802

E.L.K. Mui et al. / Carbon 42 (2004) 27892805

reaction kinetics between oxidizing gas and char particles.

Using burn-o data from previous studies, a series of
carbon conversiontime (Xct) expression for dierent
tyre char activation processes under isothermal conditions in the presence of steam were estimated and listed
in Table 4.
These simple expressions did not take into account of
the activating gas concentration as well as structural
characteristics such as porosity and surface area over
the char particles. It further conrmed that activation
temperature is not a sole factor aecting the reactivity
of tyre char owing to the signicant dierence in dXc/
dt at 900 C, in which case the value calculated on the
basis of experimental data published by Ogasawara et
al. was 10 times higher than the value based on data reported by Helleuer et al. [14,20].
The activation process of coal-reject char using CO2,
H2 O and air yielded a model (in s1) for carbon conversion (X) with respect to time (t):



dX c
E
k 0 exp 
14
SX c
RT
dt
where k 0 is the surface reaction rate constant; S(Xc) is
the transient specic surface area which is a function
of the active surface area of the particle. Data predicted
by this model were shown to have good agreement with
the experimental data obtained in the CO2 and H2Oactivation [58].
Alvarez et al. [59] described the overall rate constant
(K; in s1 atm1) of pre-oxidized char during activation
in terms of the intrinsic properties plus initial char surface area (K0) as well as a dimensionless function of conversion, U(Xc). The coal particles were rst oxidized at
temperatures between 150 and 270 C in air for periods
of time between 6 h and 15 days, then pyrolysed in nitrogen up to 600850 C at the heating rates of 60100 C/
min for 1 h (maximum) prior to activation at 500 C. At
Xc = 0.5, the equation can be dened as
K 1=2 K 0 U0:5

R1=2
pO2

15

where R1/2 is the char reactivity at X = 0.5 and pO2 is the

partial pressure of oxygen [59].

A similar prole of coal char in an environment

where the O2 content varied between 9.1 and 21.0%
v/v was proposed [60]. In this study coal particles were
carbonized for 30 h at 1000 C to give a very compact
char with a BET area 0.5 m2/g, then activated in the
temperature ranged from 877 to 1097 C in dierent
oxygen levels. Known as the shrinking-core model, the
change of mass (W) with respect to time (t) was described in terms of kg/s as
dW
k 0 Aext P nO2;s
dt

16

where k 0 = A 0 exp(E/RT) is the reaction rate constant,

Aext is the external surface area of the particle and PO2
is the partial pressure of the oxygen.
Lee and Kim [61] determined the activation rate of
tyre char in the presence of CO2 in a thermobalance
reactor. The char was prepared by heating the shredded
tyre particles to 900 C at 6.7 C/min for 1 h, and subsequently activated in CO2 for 15 min. The experimental
data was found to be independent of the char size for
sizes less than 0.65 mm and the initial sample mass less
than 1.0 g, showing a chemical-controlled reaction between activating gas and char. In this case, the rate of
conversion (dXc/dt; in min1) of tyre char under CO2
was expressed in terms of the partial pressure of CO2
(PCO2) as [61]



dX c
238700 0:68
8
1:49  10 exp 
17
P CO2 1  X c
RT
dt
It should be noted that the ash content of tyre char was
considered as separate entity, and the carbon conversion
in this study was dened as
Xc

WoW
WoWf

18

where Wf was the mass of ash in char.

A modied discrete random pore model by Bhatia
and Vartak [62] was designed for predicting the reaction
rate of chars in which micropores were predominant.
Taking dierent structural evolution parameters into
consideration, the rate of conversion (dXc/dt; in s1)
was demonstrated as

Table 4
Carbon conversions for steam-activated chars from tyre
References
a

Ogasawara et al. [14]

Merchant and Petrich [15]b
Helleuer et al. [20]
Ariyadejwanich et al. [35]
San Miguel et al. [38]
a
b

Activation temp. (C)

Linear expression

dXc/dt (min1)

Correlation coecients

900
850
900
850
925

Xc = 0.0125t + 0.0002
Xc = 0.0061t + 0.0338
Xc = 0.0010t + 0.0607
Xc = 0.0025t + 0.1906
Xc = 0.0009t + 0.0733

0.0125
0.0061
0.0010
0.0025
0.0009

0.99
0.91
0.92
0.98
0.99

Yield of char was assumed to be 35.6 wt% relative to the initial mass of tyre rubber.
Valid up to Xc  0.5.

E.L.K. Mui et al. / Carbon 42 (2004) 27892805

p
dX c
ksS0

1  X c 1 aD 1  wE ln1  X c
dt
1  e0
19
where ks = pore-size independent growth rate; S0 = initial total surface area per unit volume;
o = initial porosity; aD was the discreteness parameter and WE was the
eective structural parameter [62].
A similar model was adopted in the prediction of the
char activation using oil-palm shell as precursor. In this
study crushed oil-palm shells were heated to 600 C and
held for 3 h, followed by an activation at 500900 C for
1060 min under owing CO2. When the ash content
was assumed to be negligible, the overall reactivity (in
s1) can be expressed as
p
dX c
k 0 1  X c 1  w ln1  X c
dt

20

where k 0 is the reaction rate constant and w is the structural parameter. This kinetic study showed that the activation reaction rate was dependent on both the initial
pore structure of the char and the transient pore structure which was developed progressively during the activation process [63].
The implications of kinetic variables, such as structural parameter and transient pore structure, on the
process of tyre char activation remains unclear. In the
case where dierent activating agent (e.g. steam) is used,
the variation in reactivity of tyre char also requires more
investigation. A global model that consists of both tyre
pyrolysis and activation could be benecial to the understanding of the entire activation process.

6. Conclusions
This review presents the current status of research
into the production of active carbons from environmental applications using waste tyres. Several active
carbons have been produced with BET surface areas
over 1000 m2/g using steam activation. Although several studies report the production of tyre derived activated carbons using carbon dioxide, these generally
have surface areas in the range of 270980 m2/g. Wet
chemical activation using KOH has achieved a surface
area of 820 m2/g at an activation temperature of 850
C.
A number of studies have been performed to investigate the pyrolysis of waste tyre to carbon char. These
developed from a generic rst-order Arrhenius model
to a multireaction step model based on the chemical
composition of the waste tyre and generating a high
correlation between model and experimental pyrolysis
studies.

2803

Only one modeling study has been reported specically relating to the activation of tyre char. There is a
need for considerable developing in the modeling of tyre
char activation processes.
There is a signicant need for more extensive applications testing of these tyre-derived active carbons for a
wider range of industrial pollutants in wastewaters and
also for gas-phase applications. It would be a signicant
development to determine if nanocarbon can be prepared from waste tyres, giving rise to an extremely high
value added product.

Acknowledgments
The authors (E.L.K. Mui and D.C.K. Ko) would like
to extend their thanks to the Environmental Conservation Fund in Hong Kong, Green Island Cement Company Limited, the Innovation Technology Fund and
the Research Grants Council, Hong Kong, for the provision of funding for this research.

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