Journal of Analytical and Applied Pyrolysis 101 (2013) 1–16

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Journal of Analytical and Applied Pyrolysis

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

Review

Liquefaction of waste tires by pyrolysis for oil and chemicals—A

review
Augustine Quek, Rajasekhar Balasubramanian ∗
Department of Civil and Environmental Engineering, Faculty of Engineering, National University of Singapore, Block E1A #02-19, 9 Engineering Drive 1,
Singapore 117576, Republic of Singapore

a r t i c l e i n f o a b s t r a c t

Article history: This article provides a critical review of past efforts over the last four decades in oil and liquids production
Received 23 July 2012 from the pyrolysis of waste tires. Experimental lab-scale and pilot-scale results from the pyrolysis of scrap
Accepted 27 February 2013 tires are included here. The various operating conditions under which pyrolysis of waste tires is carried
Available online 13 March 2013
out are reviewed. In addition to reactor conditions such as temperature and heating rates, other aspects
of the tire pyrolysis such as catalyst type, catalyst preparation, and their effects on oil yields are also
Keywords:
reviewed. Pyrolytic oil characteristics such as heating value, sulfur content and density are summarized.
Tires
The various issues with production of oil from tire pyrolysis such as sulfur content, gaseous combustion
Thermal
Pyrolysis
emissions, naphtha composition are also discussed in the review. Various methods for the analysis of the
Waste pyrolytic oil composition and its refining to produce valuable products are evaluated. The review revealed
Resource recovery that the pyrolytic oil could yield useful chemicals such as the aromatic benzene and limonene, in addition
Oil to fuel applications, depending on the type of waste tires pyrolyzed and the operating conditions of the
pyrolysis process.
© 2013 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Experimental conditions for oil production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Oil yields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.1. Yield increase with temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.2. Yield decrease with temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.3. Yield maxima/minima with temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.4. Effect of heating rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.2. Catalytic pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.3. Copyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.4. Other methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3. Properties and characteristics of pyrolytic oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.1. Composition of pyrolytic oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.1.1. Carbon compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.1.2. Sulfur compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.1.3. Nitrogenous compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.2. Emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4. Refining and upgrading of oil for direct applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.1. Desulfurization of pyrolytic oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.2. Production of chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

∗ Corresponding author. Tel.: +65 65165135; fax: +65 67744202.

E-mail address: ceerbala@nus.edu.sg (R. Balasubramanian).

0165-2370/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jaap.2013.02.016
2 A. Quek, R. Balasubramanian / Journal of Analytical and Applied Pyrolysis 101 (2013) 1–16

1. Introduction (c)

Waste tires are a significant part of the urban waste stream that
is growing in quantity. It was estimated that the European Com-
munity generated an estimated 4.5 million tons of new tires in
2010 [1], with 289 million tires being replaced that year [1]. In the
United States alone, approximately 500 million scrap tires were
generated in 2007, with about 128 million used tires already cur-
rently stockpiled throughout the country [2]. In Australia, around
52.5 million equivalent passenger unit (EPU) tires reached their
end of life (one EPU = 8 kg) in 2007–2008. Approximately 64% of
these tires went to landfill, or were illegally dumped or stockpiled,
while only 13% of them were recycled [3]. In 1998, the world pro-
duction and sales of tires were estimated to have attained a new
milestone by passing over the one billion mark, with 2007 esti-
mates reported at 1.3 billion tires [4]. Since it is generally accepted
that for every tire sold in the market another joins the waste stream,
approximately 1.3 billion tires reach the end of their life cycle annu-
ally.
Waste tires resist degradation due to the vulcanization pro-
cess during its production. The vulcanized rubber consists of long
chain polymers (isoprene, butadiene, and styrene–butadiene) that
are cross-linked with sulfur bonds and are further protected by
antioxidants and antiozonants [5]. In landfills, rubber tires are not
degraded easily, but tend to float to the top over time due to
trapped gases, thus breaking landfill covers [6]. Combustion of tires
produces toxic gases, which contain carcinogenic and mutagenic
chemicals [6,7], so tire incineration requires expensive air emis-
sions control systems.
The main constituents of a typical tire compound are natu-
ral rubber (NR), styrene butadiene rubber (SBR), polybutadiene
and butyl rubber, with small quantities of organic and inorganic
additives. Three examples of tire constituents as reported in the lit-
erature, spanning three decades, from the 1980s to the 2000s, are
shown in Table 1. Since tires are composed of mainly long-chain
hydrocarbons, reprocessing tires to obtain these hydrocarbons
could provide an economical way to treat this form of waste. Recov-
ering the valuable hydrocarbons from waste tires for energy and
chemical feedstock would reduce dependency on fossil fuels, which
would in turn help mitigate the threats of decreasing reserves of
fossil fuels and climate change.
A technically feasible way to treat tires and recover valu-
able products is pyrolysis. Pyrolysis is a process in which organic
materials are thermally decomposed into simpler constituent
components when subjected to high heat, under an oxygen-
free atmosphere [8]. Thus, pyrolysis of polymers is also known
as destructive distillation. One of the earliest studies on the
pyrolysis of rubber was done during the late 1920s, where
Midgley and Henne found that isoprene and dipentene were
the dominating products [9]. The production of these chemi-
cals and other liquids, especially oils, from pyrolysis of rubber
(a)
(b)
•
•
(a)
Fig. 1. Possible scission position for C C bond in the SBR chain during pyrolysis and
the resultant resonance aromatic structure for position (a).
has been studied over the years under many different conditions
[10–98].
Many attempts have been made to investigate the thermal
degradation mechanism of rubbers tires. Rubber polymers can
be depolymerized through chain scission and side-group scission.
Fig. 1 shows the possible areas of lysis in a styrene–butadiene rub-
ber polymer. In most cases, chain scission was found to be more
preferable during the pyrolysis of natural rubber [10], polybutadi-
ene [11], and styrene–butadiene rubber [12]. Chen and Qian [10]
found that ␤-scission was preferred in the pyrolysis of natural rub-
ber because of the low bond dissociation energy, leaving the allylic
radicals. Choi [12] showed that for styrene–butadiene rubber, scis-
sion was favored to occur at the position (a) than at (b) or (c), as
shown in Fig. 1. This is due to the higher stability of the resonance
forms due to the phenyl ring for the radical with the radical center
on styrene, formed from the bond at (a). The scission at position
(b) and (c) do not produce an aromatic compound with resonance
(Fig. 1). In addition, decomposition reactions also occur concur-
rently with depolymerization during pyrolysis, to produce short
chain hydrocarbons [10].
This review article critically examines the liquid products that
had been produced by the pyrolysis of tires as reported in the lit-
erature over the last three decades. The various liquid products
from the pyrolysis of waste tyres are discussed in terms of their
respective production conditions (temperature, heating rate, gas
flow rate, etc.), their composition and characteristics and the poten-
tial applications. An immediate application of the product liquid
oils would be to use as a fuel. Thus pyrolytic oil fuel characteristics
and emission performance are also discussed.
2. Experimental conditions for oil production
There are many variations in the pyrolysis conditions of waste
tires, with different optimal conditions for the production of oils
and liquids. The common parameters that researchers vary are
pyrolysis temperature, heating rate, tire particle size, gas flow rate
and pressure. These conditions are summarized in Table 2.

Table 1
Tire constituents as reported in the literature.

Source [10] [7] [86]

Natural rubber (SMR 5CV) 29.59 Styrene butadiene 46.78 SBR 43.5
Styrene–butadiene rubber (SBR 1507) 29.59
Carbon black (ISAF N220) 29.59 Carbon black 45.59 Carbon black 32.6
Stearic acid 0.59 Aromatic oil 1.74 Extender oil 21.7
Zinc oxide 2.96 Zinc oxide 1.40 ZnO and sulfur 2.2
Phenolic resin 2.37 Stearic acid 0.94
Compound name and mass %
Aromatic oil 2.37 Antioxidant 6C 1.40
IPPD (n-isopropyl-n -phenyl-p-phenylendiamine) 0.89
Sulfur 0.89 Sulfur 1.17
CBS (n-cyclohexyl-2-benzothiazol-sulfenamide), 0.89 Accelerator CZ 0.75
H-7 (hexamethylentetramine) 0.18
PVI (n-cyclohexylthio-phthalimide) 0.12 Wax 0.23
 A. Quek, R. Balasubramanian / Journal of Analytical and Applied Pyrolysis 101 (2013) 1–16 3

Table 2
Tire pyrolysis conditions for oil production.

Reference Tire size (mm) Time (min) Pyrolysis temperature (◦ C) Oil yield (%) Pressure (Pa) Other information

[26] n.a. 12–20 350 42.0 101,325 Fluidized bed pyrolysis

500 38.0 9.0–28 kg/h for 150 mm bed
600 18.0 28.0–68.5 kg/h for 300 mm bed

[85] 14–22 60 300 3.6 101,325 Nitrogen flow rate 0.11 L/min
420 40.0
720 54.8

[63] 6.35–12.7 n.a. 250 10.0 <3000 Vacuum pyrolysis

415 60.7 Oil yield percentages contains a small
percentage of water (<7%)
500 60.0
6.4–12.7 420 56.6 Vacuum pyrolysis carried out in a process
development unit in a semi-continuous
mode at 13 kg/h
150–400 420 58.4
6.4–12.7 513 54.0

[53] n.a. n.a. 500 61.0 10,300 Process development unit at feeding rate
of 12 kg/h

[23] 1.4–2.3 n.a. 700 48.0 101,325 Fluidized bed reactor, feed rate at 0.32 kg/h
800 29.0
900 30.0

[58] <0.3 30 500 65.0 101,325

700 66.0
900 67.0
400 51.0 27.6 × 106
55.0 24.1 × 106

[27] <13 50 200 350. 101,325

350 40.0
550 30.0

[66] n.a. n.a. 500 54.0 20,000 Vacuum pyrolysis

[55] ∼12.6 n.a. 500 97.3 800 Pure polyisoprene under vacuum pyrolysis
90.3 28,000
61.7 6400

[28] 60 380 15.0 101,325 Glass tube batch reactor

15 450 19.0 Nitrogen flow (20 ml/min)
15 550 12.0

[18] 0.9 30 375 42.0 10 × 106 Copyrolysis with 20% coal in hydrogen
atmosphere
400 42.0
425 37.0

[69] Whole tires 720–840 950 24.0 101,325

[22] 30–15 90 450 58.1 101,325

525 56.9
600 53.1

[54] 20 × 30 n.a. 550 56.0 10,000

100 × 120 500 47.0 7000
485 43.0 6000

[48] 0.5–4 60 400 23.0–44.6 n.a. Solvent is dichloromethane (DCM).

120 400 28.8–59.2

[17] 0.9 15 400 36 101,325

500 44
600 45

[74] n.a. 30 400 33.0–66.1 10 × 106 Hydrogen pyrolysis coal/tire mixture in

autoclave and tubing bomb

[80] 13.9 437 500 57.5 12,000

<15.6 780 500–570 56.5 13,000
600 510–570 40.9 10,000

[24] n.a. 143 500 65 101,325 Steam pyrolysis

[29] 0.2–1.6 30 350 18.1 101,325

500 55.4
700 36.6

[16] 20–30 30 300 4.8 101,325 Fluidized bed pyrolysis

500 38.0
700 38.5
4 A. Quek, R. Balasubramanian / Journal of Analytical and Applied Pyrolysis 101 (2013) 1–16

Table 2 (Continued)

Reference Tire size (mm) Time (min) Pyrolysis temperature (◦ C) Oil yield (%) Pressure (Pa) Other information

[41] 1.0–1.4 n.a. 450 42.0 101,325 Fluidized bed pyrolysis with CBV-400
Y-Zeolite catalyst catalyst to feed ratio 1:1
500 41.5 Fluidized bed pyrolysis with ZSM-5 zeolite
catalyst to feed ration of 1:1
600 40.0
450 49.0
500 45.0
600 40.0

[21] 0.9 15 750 58.5 2.5 × 106

30 750 58.0
60 750 58.0

[65] 13–15 198–246 450 43.0 81,000–91,000

550 44.6
650 42.9

[30] 20–30 30 300 4.8 n.a.

500 38.0
700 38.5

[15] n.a. 15 350 30 101,325

450 33
550 38

[61] <0.5 n.a. 500 42 n.a. 25% copper nitrate catalyst

700 39
900 36

[31] 2 n.a. 460 75.5 n.a.

6 460 66.5
10 460 60.5
16 460 60.0
20 460 64.0

[34] 25 × 30 60 500 56.6–60.1 n.a.

[47] 1.5–2.0 60 550 47.4–55.6 101,325

650 45.4–56.0
800 47.2–55.1

[72] 1.5–2.0 60 550 67.4–72.2 101,325 Copyrolysis with waste lubricant oil in 1:1
mass ratio
650 66.5–72.3
800 67.5–72.7

[32] 0.2–0.4 15 500 43.0 n.a.

30 500 45.0
60 500 46.0

[43] 5–10 n.a. 300 26 n.a. CaC2 catalyst

35 38
400 32

[57] 0.25–0.841 n.a. 450 36.5 3.5–4.0 kPa Vacuum pyrolysis with 3% Na2 CO3
500 42.0
600 48.5

[13] n.a. n.a. 400 49.6 8000 Vacuum pyrolysis

800 51.6 8000

[25] 0.8–1.6 mm 215 598 45.9 n.a. N2 fluidizing gas

180 601 46.8 Pyrogas fluidizing gas
175 600 46.0 Steam fluidizing gas

[14] n.a. 60 500 40.3 n.a.

600 42
700 43

[35] n.a. 60 500 40.3 n.a. HMOR catalyst

42.4 HMOR + 2% ITQ-24 catalyst
41.0 HMOR + 2% ITQ-21 catalyst

[36] 1.00–2.38 60 500 38 n.a. MCM-41 catalyst

25 Ru/MCM-41 catalyst

[37] 1.00–2.38 60 500 42 n.a. SBA-1 catalyst

38 1%Ru/SBA-1 catalyst

n.a., not available.

 A. Quek, R. Balasubramanian / Journal of Analytical and Applied Pyrolysis 101 (2013) 1–16
2.1. Oil yields
In the case of oil yields with pyrolysis temperature, results in
the literature do not show a definitive trend. There are three pos-
sible trend of oil yield with temperature. Some researchers found
an increasing yield with temperature [13–18,27,30,32] while some
found a decreasing yield [19–24,87,88]. Many researchers also
found either a maximum, or minimum yield at certain tempera-
tures [25–29,31,33,34,96]. The literature is evenly split among the
three trends.
2.1.1. Yield increase with temperature
Williams et al. [85] varied pyrolysis temperatures from 300 to
720 ◦ C and heating rates from 5 to 80 ◦ C/min for the pyrolysis of tires
under a nitrogen atmosphere in a fixed bed reactor. They found
that higher temperatures and heating rates produced higher oil
yields, with 3% yield at 300 ◦ C and 54.8% yield at 720 ◦ C when a
heating rate of 5 ◦ C/min was used. Rombaldo et al. [13] showed
that the three variables of temperature, pressure and heating rate
were significant to the pyrolysis oil yield, and that the interactions
between temperature and pressure, and heating rate and pressure
were significant. They also concluded that lower pressures, higher
temperatures and higher heating rates lead to higher oil yields. The
trend of higher pyrolysis temperatures producing higher oil yields
was corroborated by other researchers [14–17,30].
Mastral et al. [17] observed higher yields with higher pyrolysis
temperatures and lower heating rates, with an oil yield of below
40% at 400 ◦ C, and 45% at 600 ◦ C. Díez et al. [15] also found that oil
yield increased when tires were pyrolyzed higher temperatures,
with 30 wt% yield at 350 ◦ C and 38 wt% yield at 550 ◦ C. They also
found that the energy value of the oils increased with temperature.
Rodriguez et al. [16] was able to increase oil yields from 4.8 wt%
at 300 ◦ C to 38.5 wt% at 700 ◦ C. However, they found no significant
difference in the energy values of the pyrolytic oils obtained at dif-
ferent temperatures. In all cases, inert gas-swept fixed bed reactors
were used.
Laresgoiti et al. [30] pyrolyzed tires at various temperatures and
found significant increases in oil yields only up to 500 ◦ C. Yields
were 24.8% at 400 ◦ C, 38% at 500 ◦ C and 38.5% at 700 ◦ C. Similarly,
Murillo et al. [32] also found that tire conversion and oil yields did
not increase significantly above 500 ◦ C, as the polymer was com-
pletely reacted. Oil yields were 43% at 500 ◦ C and 45% at 600 ◦ C. No
significant differences were found with reactions times from 15 to
60 min, as the rubbers was also found to have completely reacted
in less than 15 min. Heating rates from 25 to 300 ◦ C/min were also
found to have very little effect. In both cases, batch reactors were
used under nitrogen atmospheres.
2.1.2. Yield decrease with temperature
This is in contrast to other studies which found decreasing oil
yields with increasing temperatures [19–24,87,88]. Mastral et al.
[21] found a continuous decrease in oil yields from 61% to 56%
when pyrolysis temperatures were increased from 450 to 950 ◦ C in
a nitrogen-swept fixed bed reactor. They attributed this observa-
tion to a stronger effect of thermal cracking on conversion products
at higher temperatures. Earlier, Cunliffe and Williams [22] found a
decrease in yields from 58.1% to 53.1% when pyrolysis tempera-
tures increased from 450 to 600 ◦ C in a static-bed batch reactor,
while corresponding gas yields increased from 4.5% to 8.9%, indi-
cating a gasification of the oils at higher temperatures. There is thus
a contradiction in oil yields with pyrolysis temperature, even when
similar reactor configurations were used.
Lee et al. [23] found a continuous decrease in oil yields, from 48%
to 25%, when temperature was increased from 700 to 880 ◦ C in a
fluidized bed reactor. Similarly, Kaminsky and Mennerich [24] used
an indirectly heated fluidized bed, and found decreasing oil yields,
5
from 65% to 51%, when pyrolysis temperatures were increased from
500 to 600 ◦ C.
For continuous pyrolysis, Lucchesi and Maschio [87] used a mov-
ing bed reactor with a countercurrent inert gas (nitrogen or carbon
dioxide). They found oil yields decreased from 48.5% and 48.9%
at 500 ◦ C to about 38% and 32% at 700 ◦ C for nitrogen and carbon
dioxide gas respectively. They cite a greater degree of cracking of
hydrocarbons into gaseous compounds.
Using a pilot scale rotary kiln reactor, Galvagno et al. [88]
pyrolyzed tires at a feed rate of 4.8 kg/h and nitrogen flow rate of
1.4 m3 /h. They reported decreasing oil yields from 38.12% at 550 ◦ C
to 31.82% at 680 ◦ C. This accompanied an increase in gas yields
with a constant char yield. Therefore, it was once again concluded
that increases in temperature promotes the secondary reactions
of the volatile fraction, under the same conditions, such that the
non-condensable fraction was increased.
López et al. [19] carried out continuous pyrolysis of tires in
a conical sprouted bed in a nitrogen atmosphere for tempera-
tures 425–600 ◦ C which produced 44.5–55.0 wt% of liquid fraction,
mostly in the C5 –C10 range of hydrocarbons. For their specific reac-
tor setup, they found higher yields of the liquid fraction when
operating under relatively low temperatures and short residence
times. The amount of liquid fraction yield showed little change
up to 500 ◦ C before decreasing at 600 ◦ C. When operating in the
batch mode, they noted a similar trend with temperature. How-
ever, the yield of C10 aromatic compounds was higher, and that
of tar was lower under continuous mode. One reason cited was
that while volatile components formed were removed immediately
from the batch reactor, thus limiting secondary reactions, the reac-
tion medium in the continuous process was a mixture of all the
pyrolysis products. They concluded that the liquid fraction was of
suitable quality for use as fuel or as feedstock for a refinery, since
the pyrolytic oil contained products in high concentrations such as
limonene, isoprene and benzene–toluene–xylene (BTX) fraction.
2.1.3. Yield maxima/minima with temperature
Some studies, however, found that oil yields either peaked,
or reach a minimum value as the temperature was increased
[25–29,31,33,34,96]. In an early work, Araki et al. [26] found a
maximum oil yield of about 50% at 450 ◦ C in a fluidized bed, using
pyrolysis temperatures from 350 to 600 ◦ C. They also saw a sharp
decrease in oil yields to below 20% at 600 ◦ C. Napoli et al. [28]
observed a peak in oil yields also at 450 ◦ C, with lower yields at 380
and 550 ◦ C, for tire pyrolysis in a glass tube continuously swept by
nitrogen gas. A peak oil yield was also observed by Chang [27], who
pyrolyzed tires at temperatures of 200–550 ◦ C in a nitrogen-swept
quartz tube reactor. A maximum yield of 40 wt% was observed at
350 ◦ C.
González et al. [29] used a nitrogen-swept stainless steel tube
reactor operated in batch mode, and found a maximum oil yield of
55.6% at pyrolysis temperatures 550–575 ◦ C, and observed a sim-
ilar trend for increasing heating rates, with a maximum of 55.4%
at 15 ◦ C/min. They attributed this observation to strong cracking at
higher temperatures, or rapid removal of the pyrolysis vapors from
the hot pyrolysis zone before significant secondary reactions could
occur. Using a similar setup, Unapumnuk et al. [33] pyrolyzed tires
at heating rates of 1, 5 and 10 ◦ C/min and with pyrolysis tempera-
ture of 500, 600, 800 and 1000 ◦ C. They also found a maximum yield
of oil of 40 wt% at 550–600 ◦ C and heating rate of 5 ◦ C/min. They
found that the carbon content in the oil decreased as temperature
increased from 600 to 1000 ◦ C, regardless of heating rates.
Barbooti et al. [31] carried out a series of experiments in a
nitrogen-swept steel tubular batch reactor, to evaluate the opti-
mum conditions for the production of pyrolytic oil. They varied
pyrolysis temperature, nitrogen flow rate and particle size. The
highest oil yield of 75.5 wt% was obtained at a temperature of
6 A. Quek, R. Balasubramanian / Journal of Analytical and Applied Pyrolysis 101 (2013) 1–16
430 ◦ C, nitrogen flow of 0.35 m3 /h and particle size of 2 mm. The
oil showed a minimum yield around 430–440 ◦ C. This was in direct
contrast Kar [86], who found a maximum oil yield of 60.02% at
425 ◦ C in nitrogen-swept fixed bed reactor. Therefore, the relation-
ship between temperature and oil yield is not clear, even when
reactor type and other operating conditions are the same.
Barbooti et al. [31] also proposed a mathematical model to
predict the yields of oil based on the pyrolysis parameters of
temperature, tire size and nitrogen flow rate. Their second order
response, nonlinear mathematical model was fitted to their pyrol-
ysis results to obtain the coefficients of the model. The oil yield, Yoil ,
was expressed as:
Yoil = 50.69981 + 2.24628X1 + 5.444965X2 − 2.288887X3
− 0.25X12 + 2.475X22 + 3.624999X32 − 0.8634658X1 X2
− 1.480167X1 X3 + 1.586681X2 X3 · · ·
where X1 is the pyrolysis temperature (◦ C), X2 is the nitrogen gas
flow rate (m3 /h) and X3 is the tire particle size (mm). Kyari et al.
[34] pyrolyzed seven different brands of tires, from different man-
ufacturers and countries of origin, in a fixed bed reactor at 500 ◦ C.
The oil yields from the tires ranged from 57.1% to 60.1%, with a
mean of 58.8%. The oils showed similar broad compositional prop-
erties in the form of functional groups, and molecular size ranges
(100–170 Da peak).
2.1.4. Effect of heating rate
In addition to temperature, heating rate is also expected to be
an important parameter in influencing the pyrolytic oil yield. How-
ever, the current literature does not provide consistent information
in this respect as discussed below.
One of the earliest works was done by Williams et al. [85]. They
studied tire pyrolysis in a stainless steel fixed bed reactor at tem-
peratures from 300 to 720 ◦ C with heating rates from 1 ◦ C/min
to 80 ◦ C/min. They found that oil yield increased with increased
heating rates at every final temperature without exception. They
explained that higher pyrolysis temperature volatilizes some of
the solid hydrocarbon content of the char. Gonzalez et al. [29] also
used a stainless steel fixed bed reactor and varied heating rates
from 5 ◦ C/min to 20 ◦ C/min with a final temperature of 600 ◦ C.
A maximum oil yield of 55.4% was observed at a heating rate of
15 ◦ C/min. This was attributed to the greater cracking of at higher
heating rates, which resulted in an observed higher gas yield. When
a thermobalance was used, Murillo et al. [32] found that at a final
temperature of 500 ◦ C, oil yields decreased with heating rates. Oil
yields decreased from 49% at 25 ◦ C/min to 44% at 100 ◦ C/min, and
remained at that level for higher heating rates up to 300 ◦ C/min.
In other studies, there was no particular trend for oil yields
with increasing heating rates. Unapumnuk et al. [33,77] used low
heating rates from 1 to 10 ◦ C/min and pyrolysis temperatures of
325–1000 ◦ C in a ceramic fixed bed reactor. Oil yields fluctuated
with both temperatures and heating rates with no discernible
trend. Instead, an overall maximum yield of oil of 40 wt% was found
at 550–600 ◦ C at a heating rate of 5 ◦ C/min. Rombaldo et al. [13]
studied the effect of pressure, temperature and heating rate in vac-
uum pyrolysis and concluded that temperature and pressure were
the parameters that exerted the most influence for oil yields. At
low heating rates (3–8 ◦ C/min), the oil yield obtained from tire
vacuum pyrolysis in a stainless steel batch reactor was not as statis-
tically well-correlated with heating rate as with temperature and
pressure.
As mentioned in earlier sections, different groups of researchers
found different trends for oil yields with varying temperatures.
Therefore, the inconsistencies appear to be due to heat and mass
transfer issues, which would give rise to different products, thus
affecting the overall oil yield. In the study of heat flow during tire
pyrolysis at various heating rates, it was concluded that the heats
of exothermic reactions decreased with increased heating rates
[97]. As these reaction heats actually reflect the enthalpy change
between the reactants and products, and the reactants are the same
at different heating rates, the variations of the heat of reactions
might be due to different products obtained by the reactions at
different heating rates. It was also observed that overall, the pyrol-
ysis becomes more endothermic at higher heating rates, as the
magnitude of the heat of vaporization is much larger than that of
the exothermic reaction heat. The reason was probably due to the
change of the pyrolysis products at different heating rates [97].
Therefore, it can be seen that the yield of pyrolytic oil from the
pyrolysis of tires is linked to not only the temperature and heating
rate, but also system specific parameters such as the size of reactor,
the efficiency of heat transfer from the hot reactor surfaces to and
(1) within the tire mass and gas residence time in the hot zone.
2.2. Catalytic pyrolysis
Catalytic pyrolysis is another major area of recent investiga-
tion and has become and an important parameter. In some cases,
the catalyst increased the cracking of hydrocarbons into shorter
chain lengths, effectively decreasing the liquids while increasing
the gases evolved. Several catalytic pyrolysis studies were carried
out by Dũng et al. [14,35–37]. They prepared and used two kinds of
zeolite-based catalysts, HMOR and HBETA, and pyrolyzed tire sam-
ples at 500 ◦ C, with the evolved volatiles carried by a nitrogen flow
through a catalyst packed bed.
Dung et al. [14] showed that increases in temperature not only
increased the yield of liquids, but also the amount of polar aro-
matics. When the catalysts HMOR and HBETA, were used, the polar
aromatics decreased by 30% and 50%, respectively. The higher activ-
ity of HBETA as compared to HMOR might be attributed to its
better cracking activity caused by the combination effects of its
higher total amount of medium and strong acid sites, its smaller
crystalline, and its large sinusoidal pore systems. The authors also
explained that the larger pore diameter of HBETA favors the dif-
fusion of larger molecules into inner pores, allowing a higher
amount of reactants including polar-aromatics to be cracked to
smaller compounds. While the non-catalytic pyrolysis products
were mainly distributed in the range of gas oil (boiling point
232–343 ◦ C) and vacuum gas oil (boiling point 343–371 ◦ C), the
catalysts altered the distribution of polar aromatics to a range of
lighter fractions in the kerosene range (boiling point 149–232 ◦ C).
Dung and co-workers later used ITQ-21 and ITQ-24 zeolites in
a mixture with HMOR in tire pyrolysis using the same apparatus
mentioned above [35]. The addition of the ITQ zeolites to HMOR
decreased the reduction of liquid yields due to HMOR. While HMOR
reduced the liquid yield to 40.3% from 44.0% for non-catalytic pyrol-
ysis, the addition of 2% ITQ-21 and 2% ITQ-24 gave liquid yields of
41.0% and 42.4%, respectively. However, adding ITQ-21 enhanced
the production of kerosene, but reduced the concentration of aro-
matics, whereas adding ITQ-24 was found to decrease the yield of
kerosene and increased aromatics. Adding the ITQ zeolites led to
the reduction of the selectivity of single-ring aromatics in the light
fractions. The differences in the effects of the two ITQ zeolites were
believed to come from their different acid properties and topology.
Several groups [36,96] also pyrolyzed waste tires using pure sil-
ica MC-41 and Ru/MCM-41 catalysts. The use of catalysts decreased
oil yields, with the Ru/MCM-41 producing the lowest oil yield.
The presence of MCM-41 was thought to promote cracking of
heavy compounds to lighter ones. While the high hydrogenation
activity of ruthenium clusters hydrogenated aromatics, produc-
ing hydrogenated compounds which could be rapidly cracked.
Dũng et al. [37] later studied the catalytic pyrolysis of waste tires
 A. Quek, R. Balasubramanian / Journal of Analytical and Applied Pyrolysis 101 (2013) 1–16
with Ru/SBA-1 catalyst. They found that the content of light frac-
tion (boiling point < 250 ◦ C) increased from approximately 50 wt%
to over 70 wt%, while also lowering the content of poly- and
polar-aromatic hydrocarbons (PPAH). It was explained that the ele-
ment, ruthenium, catalyzed hydrogenation reaction, and thus, it
might decrease PPAHs through conversion of pyrolytic intermedi-
ates to smaller molecules, or transforming them to other types of
molecules. Ruthenium also lowered saturates in the oils through
hydrogenolysis.
Many studies involved the use of ZSM zeolite catalytic pyroly-
sis [38–42,92–95]. Shen et al. [38,39] used zeolite USY and ZSM-5
in a two-stage fixed bed reactor in the pyrolysis of tires with cat-
alyst temperature from 300 to 500 ◦ C, where oil yields decreased
steadily with increasing catalyst temperature. However, oil yield
with USY catalyst was found to be lower than that with ZSM-5
catalyst. At a pyrolysis temperature and catalytic activation tem-
perature of 500 ◦ C, the oil yield for USY catalyst was 32.6 wt% with
catalyst/tire ratio of 0.5, while for ZSM-5 catalyst, the yield of oil was
40.4 wt% with catalyst/tire ratio of 1.0. For USY, catalyst/tire ratios
from 0.25 to 1 were also investigated. They found that at a pyrolysis
temperature of 500 ◦ C, oil yields decreased with increasing cat-
alyst amounts, without any exceptions. In contrast, a maximum
of 54.1 wt% oil yield was found for an uncatalyzed reaction at a
temperature of 600 ◦ C. The phenomenon of lower oil yield with
catalysts was again attributed to the cracking of larger molecules
into smaller ones. The larger pore size of USY (9.0 Å) ´ compared to
ZSM-5 (5.6 Å)´ allowed more hydrocarbons of large enough size to
enter the pore system and produced smaller and lighter hydrocar-
bon molecules. Williams and Brindle [40–42] also found decreasing
oils yields with increasing catalysts/tire ratio, for ZSM-5, Y-Zeolite
(CBV-400) and Y-zeolite (CBV-780) catalysts. Similar results were
also found when HZSM-5, HY and HBeta zeolites were used in a con-
ical spouted bed to pyrolyze tires [92,93]. Overall molecular weight
of the products decreased, with increases in the yield of gases and
light aromatic hydrocarbons occurring at the expense of a decrease
in the yield of non-aromatic hydrocarbons (such as limonene) and
tar.
The use of perlite as a catalyst in pyrolysis has also been investi-
gated [86]. Using a fixed bed reactor, the researcher pyrolyzed car
tires at 425 ◦ C using varying amounts of perlite. It was found that
oil yields peaked at perlite-to-tire mass ration of 0.1, at 65.11%,
compared to 60.02% for uncatalyzed pyrolysis. The higher yield
was attributed to the catalyst being able to prevent reploymer-
ization and the cracking effect on the heavy compounds (such as
asphaltenes) in the pyrolytic oil.
Shah et al. [43] used calcium carbide (CaC2 ) as the catalyst in
the pyrolysis of tires. Calcium carbide contains pi (␲) electrons
which vibrate at high temperatures, resonating with the vibrational
energies of tire rubber, and results in a random initiation to form
polymer radicals. They found a maximum yield of 38.55% of oil
at 350 ◦ C, 0.3 catalysts to feed ratio and 60 min of reaction time.
Temperatures higher than 350 ◦ C resulted in lower oil yields. Qu
et al. [44] also used zeolite catalyst (ZSM-5) in the copyrolysis of
lubricant base oil (LBO) with tires, in a one-stage process. The cat-
alyst contacts the tires directly at a temperature of 430 ◦ C, heating
rate of 10 ◦ C/min and a maximum liquid yield of 48% was obtained,
compared to 33.5% for uncatalyzed copyrolysis with LBO, or 33.3%
uncatalyzed and without copyrolysis. By copyrolysis with LBO, the
interactions between tires and catalysts are improved, which lead
to the increased catalytic activities of the catalysts. Wey et al. [45]
divided the pyrolytic oil from fluidized bed pyrolysis into five frac-
tions: gasoline, diesel, fuel oil, heavy oil, and residue. They found
that addition of 9% zeolite increased the gasoline and diesel frac-
tions, but decreased the other three fractions. Addition of 12.5%
CaCO3 increased the gasoline and diesel fraction even more than
7
zeolite, but decreased the fuel oil and heavy oil fraction, while
increasing the residue slightly. They also found that gasoline and
diesel yields increased with temperature up to 570 ◦ C, which was
controlled by the air factor in a fluidized bed reactor.
2.3. Copyrolysis
Ucar et al. [47] copyrolyzed passenger car tires and truck tires
with waste lubricant oil (WLO) in a fixed bed reactor at tempera-
tures from 550 to 800 ◦ C. Copyrolysis with WLO produced more oil
than pyrolysis of tires alone. Copyrolysis of passenger car tires with
WLO produced less liquid than that of copyrolysis of truck tires
with WLO. Although the researchers concluded that the addition
of WLO did not enhance the degradation of tires during pyroly-
sis, copyrolysis oils contained a higher amount of lighter fraction
than that of commercial diesel. They concluded that the addition of
scrap tires into WLO increased the degradation of heavy fractions
in WLO. They also observed that an increase in the temperature
had no effect on the product distributions of copyrolysis and the
composition of copyrolysis oils.
Conesa et al. [46] pyrolyzed waste tires with either waste engine
oil, or commercial mineral oil (INDUEX). They found that higher
temperatures, longer residence times and higher amounts of tires
in the oils resulted in higher weight losses. Although no figures for
yields were reported, they showed that the optimum conditions
were a temperature of 350 ◦ C, with a residence time of 10 min and
a tire to oil mass ratio of approximately 10%, which gave a low
weight loss of 8.7%.
Money and Harrison [48] depolymerized tires by mixing tire
crumbs with a process derived recycle solvent (PDRS), or tire pyrol-
ysis oil (TPO) in an autoclave at temperatures ranging from 360 to
400 ◦ C. They found that the tire crumbs showed lower dissolution
in TPO than in PDRS under comparable conditions. They explained
that retrograde reactions occurred due to the low H-donor capac-
ity of the TPO. However when mixed PDRS:TPO solvent systems
were used, retrograde reactions were suppressed. Hydrocracking
experiments showed reasonable conversions to lower boiling point
material, with higher conversions from TPO extracts. Bouvier and
Gelus [49] pyrolyzed two types of tire rubber (sulfur-SBR, peroxide-
SBR) in three types of oil medium (aromatic AO1, AO2, paraffinic
PO). They found that a temperature of 360 ◦ C and tire particle size
of 3 mm were sufficient to dissolve the tires within minutes for all
three types of oil.
In these cases of tire copyrolysis with waste oils, the waste oils
played the role of a medium in which decomposition of tire occurs.
Decomposition in this medium allows immediate dissolution and
incorporation of the liquids into the oils during processing, pre-
venting further aromatization of the liquids and producing lighter,
modified oil compared to pyrolyzed tire oil.
2.4. Other methods
Steam pyrolysis of tires for oil production was also investigated
by some researchers [24,50]. One of the advantages claimed with
steam pyrolysis of tires is the reduction of pyrolysis temperatures
needed by up to 150 ◦ C [50], compared with steam-free pyroly-
sis. This is due to the ability of steam to diffuse into the tires and
unclog pores and displace volatiles. The steam also reduced the
partial pressures of pyrolysis gases through dilution and improved
the concentration–diffusion gradient flow from the tires [50]. These
two mechanisms help to improve mass transfer of volatiles out of
the tires during steam pyrolysis.
Kalitko [50] modeled a commercial steam pyrolysis plant for
shredded tires to produce high-grade commercial carbon, liquid
pyrolysis fuel, and accompanying fuel gas. The model was based on
8 A. Quek, R. Balasubramanian / Journal of Analytical and Applied Pyrolysis 101 (2013) 1–16

an assumption that afterburning of gases could be done together

with waste steam, instead of the separating steam and gases done
previously. It was shown that the temperature required for heat-
ing was reduced from 900 ◦ C to 800 ◦ C, with a twofold increase in
volume of afterburning while reusing the steam that has been after-
burnt as an additional heat-transfer agent for generation of new
steam.
Vacuum pyrolysis was done by several researchers
[52–57,63,66,80,91]. Using multiple hearth furnaces with pressures
below 10.3 kPa and a maximum temperature of 500 ◦ C, a yield of
61% by weight of hydrocarbon type oil could be produced [53].
When a horizontal reactor at 13 kPa and 500 ◦ C was used, the oil
yield was 50% [91]. Later, Roy et al. [55] tried vacuum pyrolysis with
polyisoprene to investigate the effects of pressure on pyrolysis oil
yields and composition. They found that oil yields decreased with
an increase in pyrolysis pressure, while oil composition was also
changed. They attributed the decrease in oil yield to the increase Fig. 2. Energy yield and sulfur content of tire pyrolytic oil from literature data.
in residence time with increased pressure, as the pyrolysis gases
are withdrawn at a slower rate to provide the higher pressure.
amounts of copper nitrate. In pyrolysis and hydropyrolysis, Mas-
The longer residence times would allow cracking reactions more
tral et al. [17] observed no differences in total conversion and oil
time to occur, producing small, incondensable molecules in the
yield when either hydrogen or nitrogen was used as the pyrolysis
gas phase.
atmosphere. However, hydrogen pressure was the most impor-
However, Lopez et al. [56] found decreasing oil yield with
tant variable regarding oil composition, with much lighter products
decreasing pressure when pyrolyzed in a conical spouted bed under
being obtained at high pressure. In hydrocoproccessing of coal and
partial vacuum of 25–50 kPa at 500 ◦ C, varying from slightly above
tires, Mastral et al. [62] used 400 ◦ C and 10 MPa of H2 pressure,
60% yield to below it. This is consistent with the trend in the results
and varied the reaction time from 3 min to 1 h. They observed that
of other researchers. Pakdel et al. [80] obtained 57% at 10 kPa while
although the conversion increased with reaction time, a higher oil
Zhang et al. [57] obtained 33–42% at 3.2–4 kPa at the same temper-
yield was observed at lower reaction times due to a lower hydroc-
ature. The effect of vacuum on decreased oil yields was attributed
racking of the generated products.
to the increased gasification, enhanced diffusion of volatiles within
particles and primary products, reducing secondary reactions of
repolymerization and carbonization [54,80]. 3. Properties and characteristics of pyrolytic oil
When basic additives were used under vacuum pyrolysis, Zhang
et al. [57] found that the pyrolysis oil yield increased gradually to The composition of pyrolytic oil from waste tires has been
a maximum and subsequently decreased for all cases, irrespective shown to be rather complex, consisting of both short and long
of the type of additives and without additives. NaOH was found to chain carbon molecules, and single and multiple ring structures.
improve pyrolysis process, with a maximal oil yield of about 50% at The results of the pyrolytic oil characterization work done over the
480 ◦ C, compared to 48% at 550 ◦ C without additives, while Na2 CO3 decades are shown in Table 3.
addition did not improve the pyrolysis process. Two parameters can be used for a simple description of the qual-
Teng et al. [58] pyrolyzed granulated tire particles at 400 ◦ C ity of tire pyrolytic oil for use as a fuel: sulfur content (%) and energy
under high pressures of 24.1 and 27.6 MPa, under steam and helium yield (heat value (MJ/kg) × oil yield (%)). The energy yield represents
atmospheres respectively. They produced high oil yields of 51 and the amount of energy that can be obtained from each unit mass of
55% for steam and helium high-pressure pyrolysis, respectively. tire from a particular pyrolysis process. Twenty-two data sets con-
Bhatti et al. [59] decomposed shredded tires using toluene in the taining the energy yield and sulfur content could be obtained from
supercritical state for the purpose of oil recovery. Their optimized the reviewed literature and the results are shown in Fig. 2. There is
conditions were 308 ◦ C and 750 psi (5.17 MPa) to produce 94.2% no apparent relationship between the energy value per unit mass
decomposition. of tire and its sulfur content. Oils with a high energy value, but low
Jitkarnka et al. [60] found that aging of tires of less than 4 weeks sulfur content can be found at the bottom right of Fig. 2. Such oils
increased the liquid oil yield. At 4 weeks of aging, a nearly 10% drop include those from the group of Roy et al. [63] using vacuum pyrol-
in the oil yield was observed, with a corresponding 10% increase in ysis (sulfur content 0.8%, energy yield 26.1 MJ%/kg) and Williams
gas yield. They hypothesized that aging of tires causes an increase et al. [85] using conventional pyrolysis in a static batch reactor
in crosslink density involving C C, C S, and C O bonds (bond dis- (sulfur content 1.1%, energy yield 24.7 MJ%/kg). Further compari-
sociation energy 607, 699, 1079 kJ/mol respectively), resulting in son can be made between these two sets of values, by calculating
a decrease in the number of free chains, and the breaking down the energy yield per unit of sulfur (energy yield/sulfur content).
of polysulfidic bonds into di- and mono-sulfidic ones. This change The result reported by Roy et al. [63] gave a value of 32.6 (26.1/0.8)
makes the tire harder to decompose (crack), resulting in higher while Williams et al. [85] gave a value of 22.45 (24.7/1.1). Thus, it
yield of liquid oil. However, after 4 weeks of aging, the tires became can be concluded that vacuum pyrolysis can produced a low sulfur
heavily oxidized, forming more C O bonds, as well as reacting fuel with reasonably high yield from tires.
directly with mono- or di-sulfidic crosslinks, forming some sulfur
species such as sulfoxides and sulfenic acids. There is thus an abrupt 3.1. Composition of pyrolytic oil
increase in the crosslink density and hardness, resulting in less oil
yield but higher gas yield, instead. Roy et al. [63] did an elemental analysis for the pyrolytic oil,
Xie et al. [61] pyrolyzed tires with copper nitrate and found which contained 87.3% carbon, 10.5% hydrogen, 0.8% sulfur, 1.2%
decreasing yield of liquids with increasing temperatures. However, oxygen and 0.2% nitrogen. Laresgoiti et al. [30] found pyrolytic
they observed no significant changes in liquid yield when com- oils to contain a complex mixture of C6 –C24 organic compounds,
pared with tire pyrolysis without copper nitrate, or with varying mainly composed of aromatics (53.4–74.8%), some nitrogenated
 A. Quek, R. Balasubramanian / Journal of Analytical and Applied Pyrolysis 101 (2013) 1–16 9

Table 3
Characteristics of pyrolytic oil.

Reference Pyrolysis Other information Heat value (MJ/kg) Carbon content (%) Sulfur content (%) Specific gravity
temperature (◦ C)

[26] 400 Fluidized bed pyrolysis 41.8 n.a. 1.35 0.918

500 9.0–28 kg/h for 150 mm bed 1.46 0.926
550 28.0–68.5 kg/h for 300 mm bed 1.36 0.927

[49] 380 Co-pyrolysis with heavy oil n.a. n.a. 3.88–3.95 1.019–1.025
[63] Vacuum pyrolysis 43 n.a. 0.8 0.95
[85] 300–720 42 n.a. 1.1 n.a.
[53] 500 85.9 0.89 n.a.
[66] 500 n.a. 86.5 0.8 0.948

[28] 380 36.5 81.1 1.6 n.a.

450 83.5 2.2
550 84.9 1.8

[69] 950 42.1 88.0 1.45 1.45

◦
[22] 450 Flash point 14–18 C 42.6 84.6–87.9 1.4 n.a.
500 42.1 1.3
600 41.2 1.3

[54] 520 43.7 n.a 0.8 0.95

500 43.8 1.5 0.976
485 44.8 1.0 0.939

[29] 400 32.7 n.a n.a. n.a.

500 28.2 .
700 27.0 .

[16] 300 43.2 86.5 1.0 n.a.

500 42.1 85.6 1.4
700 42.3 86.0 1.2

[65] 450 41.9 84.3 0.97 0.941

550 41.0 84.6 1.26 0.987
650 41.0 86.1 1.11 0.982

[30] 300 43.2 86.5 1.0 n.a.

500 42.1 85.6 1.4
700 42.3 86.0 1.2

[15] 350 35.3–37.4 76.5 1.3 n.a.

450 36.3–38.5 78.2 1.4
550 38.7–40.8 84.9 1.6

[47] 650 Car tire 41.6 87.6 1.35 0.943

650 Truck tire 42.4 86.5 0.83 0.913

[72] 550 Car tire 45.9 86.1 0.78 0.89

550 Truck tire 44.9 86.3 0.56 0.88
Copyrolysis with waste lubricant
oil in 1:1 mass ratio

[43] 350 Pyrolyzed with CaC2 catalyst 42.1–41.0 n.a. 0.55 0.8727

[51] 500 Copyrolysis of tires with sawdust, 36.8 (20) n.a. 1.025
numbers in brackets is tire mass
(%) in the mixture
38.3 (40) 0.962
42.4 (60) 0.94
44.0 (100) 0.91

(2.47–3.5%) and some oxygenated compounds (2.29–4.85%), with
sulfur content in the range of 1.0–1.4%. Pakdel and Roy [68] identi-
fied ten major peaks of in the GC spectra, which included methyl-,
dimethyl- and ethylthiophene; trimethyl- and isopropylthiophene;
tert-butylthiophene and benzothiazole.
The general trend in the literature shows that the pro-
portion of aromatic and aliphatics varied with temperature
and pressure. Aliphatic compounds are more abundant in the
pyrolytic oil at lower pyrolysis temperatures, which are gradu-
ally converted to aromatic compounds at higher temperatures
[15,16,20–22,25,26,29,30,44,51–53,55,65,67,85,98] and pressures
[17,54,56,68]. The reason was that secondary aromatization reac-
tions, through Diels–Alder type and condensation reactions,
occur at higher temperatures, converting aliphatics to aromat-
ics, polyaromatics, hydrogen and methane [22,52,55,67,85]. Thus
higher gas yields were also observed for higher temperatures
[51,54,67,85]. The type of catalyst also influences the aromatic-
aliphatic oil composition [14,18,35–44,61,62,76,92–94,96], where
higher surface acidity was found to promote the formation of
aromatics. Despite the differences in aromatic and aliphatic pro-
portions, no changes in the H/C ratio and heat values of the oils
were found with varying pyrolysis temperature [15,30].
3.1.1. Carbon compounds
3.1.1.1. Fractionation of carbon compounds in pyrolytic oil. In an
early work, Ogasawara et al. [64] measured pyrolytic oil with an IR
spectrometer. The spectra showed that aliphatic hydrocarbons and
alkylbenzenes are the major components of the oil. They observed
the same results using 13 C NMR and l H NMR measurements. GC/MS
tests indicated that the average molecular weight of the aliphatic
10 A. Quek, R. Balasubramanian / Journal of Analytical and Applied Pyrolysis 101 (2013) 1–16
hydrocarbons was 164 while that of alkylbenzenes was 180. They
estimated these two components to be roughly C12 hydrocarbons.
Later, Roy et al. [63] distilled pyrolytic oil and yielded 8% of heavy
naphtha, 16% kerosene, 24% light gas oil, 35% catalytic feed and
17% bunker (% by volume). Distillation of the fraction boiling below
204 ◦ C which constituted 26.8% of the crude oils gave 24.9% paraf-
fins, 43.3% olefins, 6.6% naphthenes and 25.4% aromatics.
More recently, Laresgoiti et al. [30] distilled pyrolytic oil
obtained at 500 ◦ C, and found that about 20% of the oils distilled
under approximately 170 ◦ C, which corresponded to the limit boil-
ing point of light naphtha, and about 10% distilled between 160
and 200 ◦ C, which corresponded to heavy naphtha and about 35%
correspond to middle distillate (200–350 ◦ C). Li et al. [65] found
that pyrolytic tire oil derived from a continuous rotary kiln con-
tained 39.2–42.3 wt% light naphtha fraction (boiling point below
200 ◦ C), a 32.4–33.2 wt% medium fraction that is similar to diesel
oil (200–350 ◦ C), and a 25.5–28.5 wt% heavy fraction (>350 ◦ C).
Teng et al. [58] analyzed pyrolytic oil using FT-IR to elucidate
functional groups. From the numerous peaks in the spectrum, they
deduced the presence of alkanes, aromatics compounds, carboxylic
acids, ketones, or aldehydes, alkenes, hydrogen-bonded alcohols
or phenols, alcohols, ethers, and carboxylic acids. González et al.
[29] used gas chromatography to show that pyrolytic oils con-
tained alkanes such as decane, undecane, dodecane, tridecane,
octadecane and eicosane; the alkenes such as propylene, buta-
diene, 1-pentene, 1,4-pentadiene, isoprene, and octene; and the
aromatic compounds benzene, toluene, ethylbenzene, (m-, p-, o-)
xylene, styrene, naphthalene, phenanthrene and anthracene and
the hydroxyl compounds phenol, 3-methylphenol, and 2-ethyl-1-
hexanol.
Murillo et al. [32] found no relationship between functional
group composition of the oils determined by TLC-FID and pyrol-
ysis process variables of heating rate, flow rate, particle size and
temperature. However, they found that higher temperatures did
promote the formation of lighter products, such as gasoline and
kerosene, which increased with temperature. They attributed this
observation to the cracking of the primary volatile released during
pyrolysis.
Laresgoiti et al. [30] also found that major compounds in
pyrolytic oil included limonene, methyl- and ethyl benzene
(toluene and styrene) and dimethylcyclohexene. Cao et al. [51]
investigated the effects of various pyrolysis parameters on the com-
position of pyrolytic oil. They divided the oils into three fractions
based on boiling points, light (45–205 ◦ C), middle (205–300 ◦ C)
and heavy (>300 ◦ C). They found that water and CO2 as carrier gas
increased the light fraction compared to N2 . This was explained as
the ability of water and CO2 to quench the highly reactive free radi-
cals, thus avoiding recombination reactions. Increases in the carrier
gas flow rate also increased the light oil fraction, by reducing the
residence time of free radicals for reaction. Increases in temper-
ature also increased the light oil fraction. However, high heating
showed a reduction in light fractions, by reducing the residence
time of the tires for further cracking and decomposition. Further
analysis showed that higher pyrolysis temperatures, up to 800 ◦ C
lead to higher amounts of PAHs (polycyclic aromatic hydrocarbons)
in the oils.
Rodriguez et al. [16] observed an aromatic content in the
oil increased from 34.7% to 57.4%, when pyrolysis temperature
increased from 300 to 700 ◦ C, respectively. Conversely, the aliphatic
oil content decreased from 59.2% to 37.0%. They also showed that
30% of the oil had a boiling point between 70 and 210 ◦ C, which is
the boiling point range specified for commercial petrol. Also, 75 wt%
of the pyrolytic oils had a boiling point below 370 ◦ C, which is the
upper limit specified for the 95% of distilled product in diesel oils.
Chaala and Roy [66] carried out pyrolysis of tires using
PyrocyclingTM , a trademarked vacuum pyrolysis process, at 500 ◦ C
and 20 kPa to yield 54% of pyrolytic oil. This oil could be fractionated
into a naphtha fraction at a boiling point 204 ◦ C (27 wt%) and a light
oil fraction (204–350 ◦ C, 17 wt%) as well as a distillation residue or
heavy oil fraction (>350 ◦ C, 56 wt%). The heavy residual fraction was
further coked to produce naphtha, light and heavy gas oils, and a
coke that is low in sulfur, ash and metal contents, including a low
vanadium concentration. At the same time, Chang [27] categorized
the pyrolytic oil into four fractions according to molecular weights:
light oil (C3 –C8 ), diesel oil (C8 –C18 ), fuel oil (C18 –C30 ) and residual
oil (>C30 ), and found that the yield of residual oil decreased signifi-
cantly with the increase in pyrolysis temperature, while the fuel oil
had a maximum level up to 15% by weight at pyrolysis temperature
of 350 ◦ C, and decomposed rapidly above 400 ◦ C.
Kyari et al. [34] pyrolyzed a mixture of seven different brands of
tires and analyzed the oil produced by gas chromatographic/mass
spectrometric (GC/MS). The tire pyrolysis oil consisted of a sin-
gle ring and polycyclic aromatic compounds and their alkylated
derivatives. The oil contained mainly alkylated benzenes, alkyl-
ated naphthalenes, alkanes, and alkenes, with compounds such
as limonene, ethylbenzene, toluene accounting for a majority of
the molecules. There were also significant concentrations of naph-
thalene and methyl, dimethyl, and trimethyl naphthalenes. Higher
molecular weight compounds included phenanthrene and pyrene.
Alkanes including pentadecane, heptadecane, octadecane, nonade-
cane, eicosane, and other high molecular weight alkanes were
identified.
Roy et al. [55] also investigated variations of oil composition
with vacuum pressure, and found a decrease in limonene yield with
increased pressure. They postulated that the limonene precursors
reacted with other pyrolysis products, which are more abundant
at higher pressures, thus reducing the concentration of limonene
recovered. Roy et al. [54] later used a total pressure below 10 kPa
and temperatures of 480–520 ◦ C to produce oil which can be used
as a fuel, with an energy value of 44 MJ/kg. The high carbon content
and low metal contamination of the oils also led them to con-
clude that the oils can be used as make-up oil feedstock in various
petroleum refining processes such as fluid catalytic cracking (FCC)
to produce light fuels, thermal cracking process to produce olefin-
rich gases, and delayed coking process in order to produce light
products and coke. In vacuum pyrolysis in a multiple hearth reac-
tor, Pakdel et al. [52] found a higher aromatic hydrocarbon content
compared with the petroleum naphtha. Other compounds included
a high olefinic hydrocarbon content, dipentene, toluene and ben-
zene. The naphtha had a gross calorific value of 43.7 MJ/kg, which
was slightly lower than petroleum naphtha.
In static bed batch pyrolysis, Cunliffe and Williams [22] found
that the carbon to hydrogen ratio, nitrogen, chlorine and fluorine
content of pyrolytic oils to be higher than that found for petroleum
derived fuels. The polar fraction, as indicated by the ethyl acetate
and polar fraction, while consistently low in concentrations, was
also higher than petroleum derived fuels. They also found that an
increase in temperature caused a decrease in the percentage yield
of aliphatics (pentane fraction) and an increase in the yields of aro-
matics (benzene). They also found a high amount of limonene in
a racemic mixture that decreased with increasing temperature,
but increased its degradation products of benzene, xylene and
styrene. Napoli et al. [28] also found that the carbon content of the
oil increased while the dihydrogen content decreased with tem-
perature, corresponding to olefins and/or aromatics hydrocarbon
production.
William et al. [85] also found changes in the composition of
the oils as the temperature was increased. Aldehydes or ketones
reduced in concentration as the temperature was increased from
420 ◦ C to 720 ◦ C. This trend was also observed in the ethyl acetate
percentage fraction, which was reduced as the temperature was
increased for all the heating rates. The aromatic groups increased
 A. Quek, R. Balasubramanian / Journal of Analytical and Applied Pyrolysis 101 (2013) 1–16
in intensity as the temperature was increased, corresponding to
an increase in the percentage of the benzene aromatic fraction
with increased temperature. The alkenes and the alkanes showed a
decrease in concentrations as the pyrolysis temperature was raised
to 720 ◦ C.
This was corroborated by Unapumnuk et al. [33], who used FT-IR
to show that the main component of pyrolysis oil was a combi-
nation of the olefinic groups and the aromatic rings, which were
represented by the C C bond, the C H stretching vibration, and
the C H bending vibration. They used GC–MS to identify indi-
vidual compounds, and found that the majority of compounds
were methyl-substituted aromatic hydrocarbons with a number
of isomers. Of these compounds, cyclohexene (∼58%) and benzene
(∼26%) were the most abundant functional groups in the pyrolysis
oil. In addition, a maximum quantity for all compounds identi-
fied was found at 500 ◦ C and tended to decrease with temperature
increases. However, PAH compounds with more than three aro-
matic rings were not detectable.
Roy et al. [55] observed that the monomer and the dimer (dl-
limonene) were the most important products. They found that
the concentration of other products, mostly olefins and aromatics,
increased with increasing pyrolysis temperature. They proposed a
mechanism, in which dl-limonene was formed by a Diels–Alder
reaction from isoprene, with other products formed by reactions
of dl-limonene and isoprene in consecutive reactions. However,
they claimed that by reducing the pyrolysis pressure, consecutive
reactions could be limited. Their GC–MS spectra showed that in the
naphtha fraction, in addition to dl-limonene, a wide variety of other
compounds were formed. At both pressures the same compounds
were formed, but in different quantities. With increasing pyroly-
sis pressure, the concentration of aromatic compounds increased,
whereas the concentration of dl-limonene (peak C) decreased.
After polyisoprene pyrolysis at 28.0 kPa, most of the products in the
naphtha fraction were olefins and only small amounts of aromatics
and alkanes were formed.
In the hydrocoprocessing of coals with tires, Mastral et al. [70]
classified the pyrolytic oils collected according to the amount of
saturates, aromatics, and polar organic compounds obtained in
each experiment over the total amount of organic matter in the
feed. They observed an increase in the aromatic fraction at 375 ◦ C
and in the saturated fraction at 400 ◦ C, in both cases increasing
the oil yields. They used TLC-FID, nuclear magnetic resonance and
GC–MS to show that the oils are alkylaromatic in nature. They
concluded that there was a certain degree of synergy in the tire-
coal hydrocoprocessing, from the recombination and stabilization
of small radicals produced in thermal bond-breaking conditions
of the rubber network over heavy radicals from coal. Later, Mas-
tral et al. [62] observed that for short reaction times, there was
a decrease in aromatic compounds due to an increase in polar
compounds. For short reaction times, they hypothesized that the
combination of radicals from tire with radicals from coal gener-
ated oils with higher polarity, while with longer reaction times,
and due to a higher hydrocracking, the generated oils have a lower
polarity.
In the copyrolysis of tires with waste lubricating oil, it was found
that more than 40% of the oil was composed of olefins, with the
highest composition (45.4%) obtained when an aluminum chloride
catalyst was used [71]. In the copyrolysis of tires with lubricant
base oil (LBO) in the presence of ZSM-5 catalyst, Qu et al. [44]
found that the heavy components decreased while the percentage
of light oils (C ≤ 12) increased. The contents of aliphatic alkenes
and cycloalkenes also increased to 10.80% and 25.78% respec-
tively, compared with 5.46% for aliphatic alkenes and 13.58% for
cycloalkenes when tires where pyrolyzed with neither LBO, nor
catalysts. However, neither LBO nor the catalyst could lower the
nitrogen, sulfur and chlorine contents of the pyrolytic oils.
11
Ucar et al. [72] found that the naphtha and aromatic content in
oils from copyrolysis of car tires with waste lubricant oil was more
than that of truck tires with waste lubricant oils. The amount of
aromatic content in copyrolysis oils found to be less than that of
scrap tire derived oils. By comparing the copyrolysis oils with com-
mercial diesel, copyrolysis oils contained lighter fraction than that
of commercial diesel whereas the specific gravities and viscosities
of copyrolysis oils were higher than that of commercial diesel.
3.1.1.2. Aromatics in pyrolytic oil. The formation of various aro-
matic hydrocarbons from the pyrolysis of waste tire was reported
to occur through the Diels–Alders reaction and aromatization
[19,22,37,55,65]. In a early work on static bed batch pyrolysis, Cun-
liffe and Williams [22] found that the total concentration of PAHs
identified in the oil increased as temperature increased from 450 to
600 ◦ C. They attributed this trend to the occurrence of two types of
reactions: dehydrogenation and Diels–Alder reactions. Dehydro-
genation of cyclic alkene compounds with six carbon atoms can
occur to produce single ring aromatic compounds and as a result
of subsequent associative reactions leads to the formation of PAH.
Butadiene, from tire pyrolysis, can also combine with available
light alkenes such as ethene and propene to form simple aromatic
compounds such as benzene, toluene, ethylbenzene and styrene
via the Diels–Alder reaction. Higher molecular weight PAHs such
as anthracene and pyrene can then be formed by further reac-
tion between aromatic compounds and olefins, as temperature
increased.
One explanation is that at higher temperatures, more free radi-
cals are generated at a greater rate, producing more reactions.
As a consequence, more aliphatic chains link to polar-aromatic
structures, and these chains might undergo cyclization reactions
resulting in the production of much heavier polar-aromatic hydro-
carbons [14]. Higher aromatics with higher temperatures were also
reported, with an inverse relationship between the amount of aro-
matics and non-aromatics, with the former increasing and the latter
decreasing with increasing temperature [30].
Using pyrolytic oil from a rotary kiln reactor, Li et al. [65]
observed that increasing temperatures increased the concentration
of PAHs. As the temperature increased from 450 to 650 ◦ C, the con-
centrations of the phenanthrene homologues increased from 2.15
to 6.51 wt%, and those of the anthracene homologues from 1.13 to
2.15 wt%. For two-ring naphthalene and its alkylated compounds,
their concentrations first increased from 8.61 to 13.14 wt% as the
temperature increased from 450 to 500 ◦ C. However, there was a
drop from 13.14 to 10.06 wt% as the temperature further increased
to 650 ◦ C. The researchers deduced that two-ring alkylated naph-
thalenes might take an active part in Diels–Alder aromatization
to form a three-ring PAH such phenanthrene and anthracene
above 500 ◦ C. The naphthalene homologues included naphthalene,
methylnaphthalene, ethylnaphthalene, dimethylnaphthalene, and
trimethylnaphthalene. Other than temperature changes, the addi-
tion of CN was also found to change the distribution of PAHs
compounds, with most of the PAHs compounds slightly increased,
except for phenanthrene [61].
In the catalytic pyrolysis of tires with calcium carbide, Shah et al.
[43] found that aromatics comprised 45% of the oils, 35% aliphatics
and the remaining 20% comprising polar hydrocarbons. The major
aromatic hydrocarbons were benzene and alkyl substituted ben-
zene. These were attributed to the styrene–butadiene rubber (SBR)
in the tires. Williams et al. [69] found that the PAHs concentra-
tion in tire pyrolysis oil was much higher, 9.2 wt% compared to
diesel fuel which contained 3.1 wt%. The main constituents of the
tire oil were naphthalene, fluorene and phenanthrene and their
alkylated derivatives. In lower concentrations, there were biolog-
ically active PAHs: acenaphthene, acenaphthylene, fluoranthene,
pyrene, benzofluorenes, chrysene and benzopyrenes.
12 A. Quek, R. Balasubramanian / Journal of Analytical and Applied Pyrolysis 101 (2013) 1–16
In catalytic pyrolysis of tires with zeolites, aromatization of oils
can also occur in the pore system of catalysts [40,41,92]. Several
groups [41,92] found large concentrations of benzene, toluene and
xylenes were produced with the use of zeolite catalyst, with a
decrease in limonene. It was explained that the larger pore size
and lower acidity of USY provided the shape selectivity and cat-
alytic activity, respectively, to decompose limonene to aromatic
hydrocarbons. Another reason given was the promotion of double
bond formation by the catalysts (USY, ZSM-5), including conju-
gated bonds. This is because conjugated double bonds tend to form
chromatics after cyclization and non-conjugated ones tend to form
olefinic compounds. The reduction of cycloalkenes with the use
of catalysts was attributed to the formation of aromatic hydrocar-
bons in the presence of these zeolite catalysts. They observed a
reduction of cycloalkenes from 45.32 wt% in the light fraction of
the unanalyzed oil, to 36.67 wt% with ZSM-5 and 2.02 wt% with
USY catalyst. Similar results were observed in the catalytic pyrol-
ysis with expanded perlite, where increased aromatization (from
36.14% to 42.32%) and decreased olefins (21.18% to 14.47%) were
found due to catalytically active sites [86].
To obtain 3–4 ring structure compounds of PAHs, Cal-
lén et al. [74] hydrocopyrolyzed tires and coal together and
found that the resultant oils contained anthracene, fluoran-
thene, pyrene, as predominant compounds. While the majority
of the compounds identified were substituted naphthalenes and
phenols, they also detected the presence of alkyl benzenes,
alkyl naphthalenes (2, methyl; 2,3-dimethyl; 1,4-dimethyl; 1,6,7-
trimethyl; 1,6-dimethyl-(4,1-methylethyl)) and alkylphenols (3
propyl; 3,5-diethyl; 2,5-dimethyl). The presence of benzenes
was easily explained as a component of thermal decomposi-
tion of aromatic hydrocarbons (styrene) and was formed during
styrene–polybutadiene polymer depolymerization. Alkyl naph-
thalenes were explained as being produced in cyclization reactions
of the alkyl benzenes from rubber depolymerization and the
phenols were explained as being the most stable hydroxylated aro-
matic compounds.
3.1.2. Sulfur compounds
Sulfur is used as a cross-linking agent during tire manufactur-
ing process. During pyrolysis, some sulfur heteroatom-containing
compounds form free radicals, and polythiyl radicals from
polysulfide cross-linkages are thought to react by addition to
carbon–carbon double bonds, recombination and/or dispropor-
tionation. The reaction pathways change with the pyrolysis
conditions (temperature, pressure and residence time) and yield
different amounts of sulfur compounds in pyrolytic oil.
Using a fixed-bed reactor under a N2 or CO2 atmosphere, Teng
et al. [58] found that in the pyrolysis of granulated tires, 9% of the
sulfur in the tire was found in the oil, with the majority of sulfur
preferentially retained in the solid char. The overall concentration
of sulfur in the oil was only 0.3%, but no specific pyrolysis conditions
were given. In contrast, Benallal et al. [91] used vacuum pyrolysis at
13 kPa and 500 ◦ C, and found that 1.2% sulfur in the pyrolytic oil, the
same percentage as in the original tire. They also found that sulfur
compounds are concentrated mostly in the light naptha fraction
(distilled at 160 ◦ C), identified by GCMS as 2-methylthiophene, 3-
methylthiophene, 2-ethylthiophene, 2,5-dimethylthiophene, 2,4-
dimethylthiophene, 2,3-dimethylthiophene, 3-ethylthiophene, 2-
isopropylthiophene, 2-tert-butylthiophene and benzothiazole.
Several observations in literature have found that more sul-
fur partitions from the solid into the liquid products during
pyrolysis with increasing temperatures. Unapumnuk et al. [77]
investigated the influence of heating rates and pyrolysis temper-
atures (350–1000 ◦ C) on the sulfur content of the waste tires. They
observed that for the heating rates used (1–10 ◦ C/min), there was no
effect on sulfur content, while desulfurization of the tires increased
as temperatures increased from 350 to 400 ◦ C, but remained almost
constant above 400 ◦ C. They also observed that approximately half
of the original sulfur remained in the solid char rather than being
released as condensed vapor phase within the range of 350–850 ◦ C.
Díez et al. [15] also found increasing sulfur concentrations in the
liquids with increased pyrolysis temperatures. Greater amounts of
sulfur were found in the liquid fraction after the pyrolysis process
as the final temperature rises. They attributed the presence of the
increased sulfur contents to the fact that higher temperatures favor
the breaking of the C S bonds in the original tire.
Williams and Bottrill [67] investigated the sulfur-polycyclic
aromatic hydrocarbons (PASH) from pyrolytic oil produced from
bench-scale static batch reactor and fluidized bed reactor at three
heating rates to a final pyrolysis temperature of 700 ◦ C. Diben-
zothiophene and its alkylated derivatives from the reactor were
shown to have a small, but a significant increase in concentration
as the heating rate was increased. The concentrations of diben-
zothiophene and its alkylated derivatives in oil derived from the
fluidized bed showed an increase with an increase in temperature
of pyrolysis. Specifically, dibenzothiophene showed a small change
with increasing temperature of pyrolysis, whereas the C2 and C3
derivatives of dibenzothiophene increased significantly.
3.1.3. Nitrogenous compounds
Nitrogenous compounds in pyrolytic oil were investigated
by Mirmiran et al. [53]. They found many nitrogenous com-
pounds including aliphatic amines; amides and nitriles; pyri-
dine and alkyl derivatives, aniline and their alkyl deriva-
tives; pyrroles; indoles; quinolines and benzothiazoles. Pyri-
dine and their alkyl derivatives were identified as the most
abundant compounds among all the nitrogenous compounds.
The presence of nitrogenous compounds was attributed to
the thermal degradation of the accelerants incorporated in
tires, such as N,N-diisopropyl-2-benzothiazole-sulfenamide, 2-(4-
morpholinylthio)-benzothiazole,N,N-caprolactam disulfide, and
2-mercaptobenzothiazole. The researchers explained that pyridine,
␣, ␤, ␥-picoline and the other isomers of pyridine could be obtained
by the cleavage of the C C bonds of certain accelerators such
as 3,5-diethyl-1,2-dihydro-l-phenyl-2-propylpyridine. Cleavage of
the N S and C S bonds of N,N -caprolactam and benzothiazolic
additives produced caprolactam and benzothiazole in tire oils.
3.2. Emissions
An early work on the combustion emissions of pyrolytic oil was
done by Williams et al. [69] They investigated the emission of NOx
and SO2 from the combustion of tire pyrolysis oil and diesel fuel in
relation to excess oxygen levels. Emission levels of NOx and SO2
in the furnace emitted gases were higher for the tire pyrolysis
oil compared to diesel fuel combusted under identical combus-
tion conditions of excess air. The higher SO2 concentrations for
tire pyrolysis oil were directly related to the respective fuel sulfur
contents of tire pyrolysis oil at 1.45 wt% and diesel fuel at 0.2 wt%.
The higher NOx may also be explained in part by the higher fuel
nitrogen content of the pyrolytic oil. They also noticed PAHs (mainly
naphthalene and alkylated naphthalenes) in the particulate emis-
sions when the pyrolytic oil was combusted in excess oxygen.
In a more recent work, Ilkiliç and Aydin [95] conducted engine
test using pyrolytic oil with reduced sulfur content (∼0.9%). Exhaust
emission results showed that CO, unburned hydrocarbons, SO2 and
smoke opacity were all higher than diesel combustion, with CO, SO2
and hydrocarbons reaching levels three times higher than diesel
emissions at certain engine speeds. The main reasons for higher
hydrocarbon and CO emissions for pyrolytic oil were thought to
be the poor atomization, lower cetane number and longer igni-
tion delays. The higher density, of pyrolytic oil also caused more
 A. Quek, R. Balasubramanian / Journal of Analytical and Applied Pyrolysis 101 (2013) 1–16
amounts of fuel to be injected, causing rich combustion conditions
to occur, resulting in higher hydrocarbons and CO. The higher SO2
emission was due to the higher amount of sulfur in the pyrolytic oil.
NOx emissions were lower for pyrolytic oil only when the engine
was operating at lower speeds (<2000 rpm). The reason given for
this increase was the slower combustion of the pyrolytic oil that
results in a larger period of combustion.
4. Refining and upgrading of oil for direct applications
The composition of pyrolytic oils contained valuable fractions
and compounds such as naptha and aromatics, as detailed in the
previous sections. In addition to being a good fuel source, pyrolytic
oil contained aromatics such as benzene, and limonene could be
used as chemical feedstocks [75]. Therefore, a number of methods
to obtain chemicals and upgrade pyrolytic oil have been investi-
gated over the years. An early work on the upgrading of pyrolytic
oil was done by Bouvier and Gelus [49]. They showed that the ‘gum-
ming’ effect of heavy residual oil could be avoided by pyrolyzing
with contacting oil. The depolymerized gum was dissolved by the
contacting oil, and the resultant solution could be recycled as fuel
oil, with similar ash and sulfur content.
In the hydrocoprocessing of coals with tires Mastral et al. [18]
upgraded the obtained liquids using a pressurized hydrogen atmo-
sphere and temperature of 400 or 450 ◦ C with different catalysts.
They found that a combination of molybdenum supported by car-
bon black was the most active hydrocracking and heteroatom
elimination catalyst, being able to increase the amount of saturated
hydrocarbons while reducing the amounts of aromatics and polar
hydrocarbons significantly by the highest percentage.
4.1. Desulfurization of pyrolytic oil
The pyrolysis oil that is derived from waste tires is not appro-
priate for direct use in a combustion process due to its high sulfur
content. Therefore, desulfurization of pyrolytic tire oils is an impor-
tant part of the oil production process before it can be utilized. Ucar
et al. [76] upgraded pyrolytic oil from truck tires using pyrolytic
carbon black supported catalysts of Co–Ni, Co–Mo and Ni–Mo, at
350 ◦ C under hydrogen pressure of 7 MPa. All three metal loaded
catalysts could reduce the sulfur content, from an initial 0.77% to
a low of 0.57% for Ni–Mo catalyst. Ni–Mo also gave a maximum
yield of 55% naphtha (boiling point <172 ◦ C), 20% kerosene (boiling
point 172–232 ◦ C) and 25% vacuum gas oil (boiling point >232 ◦ C),
with 17.7% aromatics, 81.1% paraffins and 1.25% olefins. They also
experimented with DHC-8, a commercial catalyst containing non-
precious metals on a silica–alumina support. However, the results
from DHC-8 were not as good as Ni–Mo.
Dogan et al. [89] desulfurized and refined raw pyrolytic oil using
a five-stage process: (1) hydro-sulfuric acid (H2 SO4 ) treatment, (2)
activated bentonite–calcium oxide (CaO) treatment, (3) vacuum
distillation, (4) oxidative desulfurization,(5) Washing and drying.
The raw pyrolytic oil was stirred with 8 wt% of hydro-sulfuric acid
for 4 h at 50 ◦ C. The mixture partitions into a clear, viscous, oily top
layer and a bottom, non-viscous acidic sludge. The top oil layer was
then stirred with activated bentonite and calcium oxide for 4 h at
70 ◦ C. After filtration through filter-cloth, the filtrate was vacuum
distilled. The distilled pyrolytic oil was then treated with a mixture
of formic acid and hydrogen peroxide, stirred for 2 h at 60 ◦ C in the
oxidative desulfurization stage. Clear pyrolytic oil was then sepa-
rated out with a separation funnel and washed with distilled water,
and dried at 110 ◦ C for 30 min.
The refined pyrolytic tire oil contained 0.43% of sulfur and 1%
carbon residue, compared to 1.13% sulfur and 21.5% carbon residue
in raw pyrolytic oil [89]. It also had a lower heating value of
13
40 MJ/kg, and was then used as a fuel in engine test. The study
concluded that blending diesel with up to 70% of the refined tire
pyrolytic oil can be used in diesel engines without significant loss
in engine performance, while improving some engine emissions.
Bunthid et al. [78] used the naphtha fraction distilled from
the light oils obtained from the pyrolysis of tires for desulfur-
ization experiments. They showed that the maximum removal
of sulfur content was 41.5% and 47.6% when only H2 O2 and
pyrolytic tire char was used alone, respectively. When oxidation
and adsorption were used by having both H2 O2 and pyrolytic
tire char, the desulfurization increased to 57.8%. The highest sul-
fur removal at 75.2% was achieved using HNO3 -treated chars in
an aqueous medium of pH 4, adjusted using formic acid. Chen
et al. [79] used an ultrasound method to desulfurize pyrolytic oil.
The oils were mixed with tetraoctylammonium bromine (phase
transfer agent) and hydrogen peroxide solution containing phos-
photungstic acid (transition metal catalysis). The oils in the mixture
were then oxidized by irradiating with 20 kHz ultrasound for
20 min at a temperature of 88 ◦ C. The oils were subsequently
extracted with acetonitrile. They could remove up to 43.6% of
the sulfur content in the pyrolytic oil using this process. When
they coupled this ultrasound oxidation process with subsequent
alumina oxide adsorption, the removal rate increased to 68.2%
[79].
4.2. Production of chemicals
One major component of pyrolytic oil is limonene. Limonene is
used in the formulation of industrial solvents, resins and adhesives
and as a dispersing agent for pigments. It is also used as a feed stock
for the production of fragrances and flavorings, including, water-
based degreasers, natural lemon scented all-purpose cleaners, hand
cleaners and replacements for chlorofluorocarbon solvents to clean
electronic circuit boards [22].
Generally, limonene formation was found to be dependent
on the pyrolysis pressure, temperature and vapor residence time
inside the reactor, as well as sample size [54,60,80,92]. Pakdel
et al. [80] used vacuum pyrolysis in both the semi-continuous
and batch modes to produce pyrolytic oil, which were distilled to
produce limonene with yields from 0.8 to 9.8%. Low pyrolysis pres-
sure and temperature and short vapor residence time increased
the limonene yield, as higher temperatures (above 500 ◦ C) and
pressures were found to crack limonene molecules to trimethyl-
benzene, m-cymene and indane which had boiling points similar
to dl-limonene. They postulated that the major initial products of
pyrolysis were isoprene and dl-limonene and other dimers. This
is followed by a wide variety of compounds, such as aromatic
compounds, directly by polymer chain scission, or via degrada-
tion products of isoprene and dl-limonene, or partially at higher
temperatures, or long residence times via secondary reactions.
The enrichment of pyrolytic oil with limonene was later studied
by Stanciulescu and Ikura [75,81] in an attempt to reduce the odor
in the oil. The oils, obtained from tire pyrolysis at 550 ◦ C, were sub-
sequently distilled in two stages. The first stage obtained naphtha
with boiling points less than 190 ◦ C from the oils, and the second
stage to obtain limonene enriched naphtha. They found that the
naphtha from oils distilled at 190 ◦ C contained 23.8% m-xylene, 11%
toluene, 8% styrene, less than 3% benzene, with less than 0.43%
sulfur. Most of the terpenes in the naphtha was d-limonene at
16.3%. Other components were saturated and unsaturated hydro-
carbons with acyclic, or cyclic structures. However, they could
not successfully separate limonene (b.p. 176 ◦ C) from the naphtha
fraction. Therefore, they used limonene-enriched naphtha for cat-
alytic alkoxylation of limonene to ethers. Vacuum distillation of
the resulting mixture showed good separation between limonene
methyl ether and the reaction mixture.
14 A. Quek, R. Balasubramanian / Journal of Analytical and Applied Pyrolysis 101 (2013) 1–16
Williams and Brindle [40,41] studied the use of zeolite cata-
lysts in a two stage pyrolysis process to increase the single ring
aromatic content of pyrolytic oils. They found that in general,
increasing the catalyst/tire feed ratio increased these single ring
aromatic compounds. For example, toluene reached a maximum
value in the oil of 24 wt%, benzene 5 wt%, m/p-xylenes 20 wt%
and o-xylene 7 wt%. The concentrations of naphthalene and the
monomethyl-, dimethyl- and trimethylnapthalenes were also sig-
nificantly increased with the addition of these catalysts. However,
there was a complete loss of limonene with catalyst/tire more than
0.5. The Y-zeolite catalyst produced significantly higher concen-
trations of benzene, toluene, xylenes, naphthalene and alkylated
naphthalenes compared to the ZSM-5 catalyst [41]. When cata-
lyst temperature was increased from 430 to 600 ◦ C, benzene and
toluene showed an increase and xylenes a decrease for the Y-zeolite
while the zeolite ZSM-5 showed a general increase in benzene,
toluene and the xylenes. However, in the oils from tires pyrolyzed in
a multilevel reactor, Liu et al. [82] were able to concentrate toluene
from 7.65% to 68.52% and xylene from 10.09% to 65.20% through
fractional distillation under the temperature range of 85–110 ◦ C
and 123–145 ◦ C, respectively. One novel use of pyrolytic oil is in the
use of asphalt or bitumen in road pavements [83,84]. Yousefi et al.
[84] found improved performances over low and high temperatures
for polymer-modified asphalt prepared with recycled polyethyl-
ene (RPE) and used-tire-derived pyrolytic oil residue. It was also
observed that the residual oil slightly enhances the asphalt-RPE
compatibility.
5. Conclusion
The review presents the current status of research into the pro-
duction of oils and liquid chemicals from waste tires. A number of
studies have been performed to investigate the pyrolysis param-
eters of waste tires to oil. These include temperature, pressure,
particle size, inert gas flow rates, types of pyrolysis atmospheres,
reactor configuration and the use of catalysts. However, no general
agreement could be found among these studies on the relationship
between oil yields and these parameters, except that the use of
catalysts decease the oil yield in favor of gas yields.
The characteristics of the oils produced also varied widely due
to the different pyrolysis conditions. A large majority of oils pro-
duced have energy values in the range of 28–46 MJ/kg with sulfur
contents from 0.55% to 3.95%. The high energy value and sulfur
content implies that desulfurization of the pyrolytic oil is neces-
sary before its use as a fuel. The composition of the oils was also
highly varied, containing long and short chain, and ringed-structure
hydrocarbons. A main general finding was that tire pyrolytic oil was
rich in aromatics (benzene, toluene, etc., and non-aromatic ring
molecules (e.g. limonene). A higher degree of aromatization of the
oil was also found with higher temperatures, with more aromatic
molecules formed from the straight chain hydrocarbons through
Diels–Alder reactions.
There is a significant need for exploring more extensive use of
these tire-derived oils for a wider range of industrial applications,
such the use of tire oil-derived limonene for lemon scent and other
applications mentioned at the beginning of Section 4.2, benzene for
the production of plastics and resins, and toluene in the produc-
tion of pesticides and dyestuffs. A major improvement would be
to design a tire pyrolysis system that produces value-added prod-
ucts while using only the energy it produces in a self sustaining
manner.
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