J. Anal. Appl.

Pyrolysis 71 (2004) 917–934

Characterization of the liquid products

obtained in tyre pyrolysis
M.F. Laresgoiti, B.M. Caballero∗ , I. de Marco, A. Torres,
M.A. Cabrero, M.J. Chomón
Escuela Superior de Ingenieros de Bilbao, Alda. Urquijo s/n, Bilbao 48013, Spain

Accepted 9 December 2003

Abstract

Cross-section samples (2–3 cm wide), representative of a whole car tyre, have been pyrolysed under
nitrogen in a 3.5 dm3 autoclave at 300, 400, 500, 600 and 700 ◦ C. Over 500 ◦ C there is no effect of
temperature on gases and liquids yields (≈17 and 38%, respectively). Tyre pyrolysis liquids have been
characterized, including elemental analysis, gross calorific value (GCV), gas chromatography/mass
spectroscopy (GC/MS) and distillation.
Tyre derived liquids are a complex mixture of C6 –C24 organic compounds, with a lot of aromatics
(53.4–74.8%), some nitrogenated (2.47–3.5%) and some oxygenated compounds (2.29–4.85%). They
have GCV (42 MJ kg−1 ) even higher than those specified for commercial heating oils, but sulphur
contents (1–1.4%) near or slightly over the law limit value. Significant quantities of valuable light
hydrocarbons such as benzene, toluene, xylene, limonene, etc. were obtained. The concentration of
these compounds increase with temperature up to 500 ◦ C and then decrease. There are an important
proportion of polycyclic aromatics such as naphthalenes, phenanthrenes, fluorenes, diphenlys, etc.;
their concentration as well as that of total aromatics increases significantly with temperature.
Distillation data of the 500 ◦ C oils showed that ≈20% have the boiling range of light naphtha
(<160 ◦ C), ≈10% of heavy naphtha (160–204 ◦ C) and ≈35% of middle distillate (204–350 ◦ C). As
far as distillation data are concerned, the tyre oil fractions with the same boiling range as commercial
automotive diesel oils and heating diesel oils fulfil the present specifications of such commercial
products.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Recycling; Pyrolysis; Thermolysis; Tyres

∗ Corresponding author. Tel.: +34-46017775; fax: +34-46014179.

E-mail address: iapcaigb@lg.ehu.es (B.M. Caballero).

0165-2370/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2003.12.003
918 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 71 (2004) 917–934

1. Introduction

The disposal of used tyres is a major environmental problem in nowadays. It is estimated

that 2.5 × 106 t per year are generated in the European Union, 2.5 × 106 t in North America
and 1 × 106 in Japan [1]. The complex nature of tyres makes it difficult to recycle them.
On the one hand the main component of tyres, rubber, is a chemically cross-linked polymer
and, therefore, is neither fusible nor soluble and, consequently, cannot be remoulded into
other shapes without serious degradation. On the other hand, tyres are a complex mixture of
very different materials, which include several rubbers, carbon blacks, steel cord and other
organic and inorganic minor components.
Along the years, different alternatives for tyre recycling, such as retreading, reclaim-
ing, incineration, grinding, etc., have been used. However, all of them have significant
drawbacks and/or limitations [2,3]. Tyre pyrolysis is at present an interesting and chal-
lenging area of research. In the pyrolysis processes (heating to moderate temperatures in
an oxygen-free atmosphere), the volatile organic part of tyres, mainly the rubber poly-
mer/s, is decomposed to gases and liquids, which can be useful as fuels or sources of
chemicals. The inorganic components, mainly steel, and the non-volatile carbon black re-
main as a solid residue, relatively unaltered and, therefore, can be recycled in worthwhile
applications.
Previous studies published by the authors [4] show that tyre pyrolysis gases are mainly
composed of methane and C4 (butenes and butanes) together with some other light hy-
drocarbons, and also contain a low proportion of CO, CO2 and H2 S. Tyre pyrolysis gases
have very high gross calorific values (GCVs) (68–84 MJ m−3 ) and could widely provide
the energy requirements of the process plant. Concerning the tyre pyrolysis solid, it is a
piece of equal dimensions and shape as the original tyre portion, but easily disintegrable
into black powder and steel cords and filaments. The analysis, characteristics and potential
uses of the black powder have been discussed elsewhere [5].
There are a number of studies in the literature related to tyre pyrolysis. Very differ-
ent experimental procedures have been used including thermogravimetric analysers [6,7],
fixed bed reactors [4,5,8–10], fluidised bed pyrolysis units [11–13], vacuum pyrolysis units
[14–23], spouted bed reactors [24], etc., and ranging from laboratory to commercial scale
plants. Such studies have been focused on different items of the pyrolysis process, such
as kinetics, reactor design, products characterization, economics, etc. Pyrolysis yields and
characteristics of the products obtained depend not only on the feedstock and operating
conditions used for the experiments, but also on the specific characteristics of the system
used, such as the size and type of reactor, the efficiency of heat transfer, the residence time,
etc. Therefore results from different authors are many times difficult to compare. Moreover
sometimes contradictory data can be found in the literature. For instance, results about the
influence of such an important parameter as the temperature in tyre pyrolysis yields vary
from some studies to the others.
The authors of this paper have carried out pyrolysis tests from 300 to 700 ◦ C every 100 ◦ C,
and have found that solid yield decreases while gas and liquid yields increase from 300 to
500 ◦ C, but not from 500 to 700 ◦ C [5]. Similarly Roy et al. [18] studied tyre pyrolysis in the
range 350–700 ◦ C, and found no influence of temperature on pyrolysis yields over 500 ◦ C.
On the contrary Cunliffe and Williams [8] and Lucchesi and Maschio [25] found that oil
 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 71 (2004) 917–934 919

yield decreases and gas yield increases from 450 to 600 ◦ C. In the same way Williams et al.
[9] studied pyrolysis from 300 to 720 ◦ C and observed that char and gas yields decrease
while liquids increase in the whole temperature range, although the effect of temperature
was slighter over 600 ◦ C, and varied depending on the heating rate used. Similarly Kaminsky
and Sinn [11] found an increase in char and gas yields and a decrease in oil yield as the
temperature was raised from 640 to 840 ◦ C. It is therefore obvious that not only the influence
of temperature, but also the pyrolysis yields and the characteristics of the products obtained
will vary from some authors to the others.
The present paper is centred in the characterization of tyre pyrolysis liquids. There
are several papers in the literature devoted to the study of such liquids, and each one
presents its particular experimental procedure and objectives. For instance Cunliffe and
Williams [8] studied pyrolysis from 450 to 600 ◦ C and carried out an exhaustive charac-
terization of tyre liquids; they separated the oils by sequential elution chromatography,
and analysed by gas chromatography/mass spectroscopy (GC/MS) only the aromatic frac-
tion. Mirmiram et al. [14] pyrolysed tyres in a continuous vacuum process development
unit, distilled the liquids at atmospheric pressure, analysed by GC/MS and GC/AED, just
the naphtha fraction (30–204 ◦ C), and identified only the nitrogenous compounds. Be-
nallal et al. [19] pyrolysed tyres under vacuum at 510 ◦ C, also distilled the liquids and
characterized by GC/MS, capillary column GC and elemental analysis, just the light naph-
tha fraction (bp <160 ◦ C), which is only 20% of total tyre liquids. Pakdel and Roy [20]
characterized tyre oils by GC/MS and FTIR, but also analysed only the naphtha fraction
obtained under 510 ◦ C vacuum pyrolysis. Other authors such as Chaala and Roy [16],
Aguado et al. [24], etc. present also information about tyre pyrolysis liquids but poorly
detailed.
The authors present in this paper a detailed characterization of the whole of the tyre
pyrolysis liquids obtained at 300, 400, 500, 600 and 700 ◦ C. GC/MS analyses, elemental
analyses, gross calorific values and distillation data are included; the later are compared
with petroleum derived fractions distillation data.

2. Experimental

2.1. Characteristics of the samples pyrolysed

Tyres are composed of very different components (rubbers, carbon blacks, steel, fillers,
etc.), which additionally are heterogeneously distributed along the tyre. Therefore in or-
der to dispose of invariable and representative samples of the whole tyre, cross-section
pieces of 2–3 cm wide (≈175 g) of a commercial car tyre (Firestone 155R13, F-570) were
used in the pyrolysis experiments. The amount of steel in such samples was quantified
after the pyrolysis experiments, separating it manually from the solid residue left, and
weighing it.
In order to characterise the tyre pieces used for the experiments, a representative sample
was prepared grinding the steel-free rubber once frozen in liquid nitrogen. Thermogravi-
metric analyses (TGA) were carried out with the prepared samples using a LECO TGA-500.
(1) In nitrogen atmosphere to quantify the amount of rubber and other organic components
920 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 71 (2004) 917–934

Table 1
Main components (wt.%) of the tyre section used for the experiments
Rubber and other organic compounds 58.8
Carbon black 27.7
Steel 9.6
Other inorganic compounds 3.9

such as accelerators, extender oils, etc., which decompose in inert atmosphere. (2) In oxygen
atmosphere to quantify the carbon black. The solid residue left after both TGAs correspond
to other inorganic fillers of the tyre. The weight percent of the main components of the
tyre, derived from the TGA results are presented in Table 1. The amount of organic matter
(58.8%) should correspond to the amount of gases + liquids to be obtained in the pyrolysis
tests, while the amount of carbon black + steel + other inorganics, which add up to 41.2%,
should coincide with the solid residue remaining after pyrolysis. On the other hand, the ele-
mental composition and gross calorific value of the prepared tyre samples were determined
using a LECO CHN-600 and a LECO SC-132 automatic determinators, and a LECO AC
300 automatic calorimetric bomb. The results are presented in Table 2.

2.2. Pyrolysis experiments

Pyrolysis experiments of automotive tyres were carried out at 300, 400, 500, 600 and
700 ◦ C in nitrogen atmosphere, using an unstirred stainless steel 3.5 dm3 autoclave. In a
typical run a cross-section tyre portion of about 175 g is placed into the reactor, which is
sealed. Then nitrogen is passed through at a rate of 1 dm3 min−1 and the system is heated
at a rate of 15 ◦ C min−1 to the desired temperature, and maintained there for 30 min. It has
been proved by the authors that after 30 min no more pyrolysis products evolve from the
autoclave. All through the run the vapours leaving the reactor flow to a series of cooled
gas–liquid separators where the liquids are condensed and collected. The uncondensed
products were normally vented to the atmosphere except in a few experiments specifically
devoted to analyse pyrolysis gases, whose results have been presented elsewhere [4].
Solid and liquid pyrolysis yields were determined in each experiment by weighing the
amount of each obtained and calculating the corresponding percentage.

Table 2
Elemental composition (wt.%) and gross calorific value (GCV) (MJ kg−1 ) of the tyre section used for the experi-
ments
C 74.2
H 5.8
N 0.3
S 1.5
Oa 4.7
Non-combustible matterb 13.5
GCV 31.8
a Calculated by difference.
b Steel + other inorganic compounds.
 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 71 (2004) 917–934 921

2.3. Liquids characterization

The pyrolysis liquids elemental composition was determined using a LECO CHN-600
and a LECO SC-132 automatic determinator, and their gross calorific value using a LECO
AC-300 automatic calorimetric bomb.
On the other hand the pyrolysis oils were analysed in an Agilent HP 6890A gas chro-
matograph equipped with an Agilent HP 5973N mass selective detector, using a 50 m ×
0.2 mm × 0.33 ␮m HP-5MS capillary column (5% diphenyl, 95% dimethyl siloxane). The
following temperature program was used: initial and final temperatures were 40 and 280 ◦ C,
respectively, times at initial and final temperatures were both 10 min and the heating rate
was 8 ◦ C min−1 . The injector temperature was 280 ◦ C and the sample was injected with an
Agilent 7683 injector. The carrier gas was He of 99.999% purity. The MS detector operated
in scan mode and its mass-range was 50–550 amu.
Additionally a distillation test at atmospheric pressure of a mixture of the pyrolysis
oils obtained in several experiments performed at 500 ◦ C was carried out. The oils were
distilled from room temperature to the temperature at which no more distilled products were
collected.

3. Results and discussion

3.1. Pyrolysis yields

The solid, liquid and gas yields (wt.%) obtained in the tyre pyrolysis experiments carried
out at 300, 400, 500, 600 and 700 ◦ C are presented in Table 3. The results presented in the
table include the mean value and the standard deviation of at least five pyrolysis runs carried
out at the same temperature.
At 300 and 400 ◦ C pyrolysis was incomplete, while at 500, 600, and 700 ◦ C, solid yields
are almost equivalent and somewhat higher than the value obtained in TGA analysis (41.2%).
It has been proved by the authors [26] and by other research groups [12,13,27–30] that a
certain amount of char or coke like carbonaceous material is formed in the pyrolysis of
many polymeric materials, due to secondary repolimerisation reactions among the polymer
derived products. Since at 500–700 ◦ C longer reaction times do not decrease solid yields
either, it can be concluded that tyre decomposition is completed, and that 3–4% of char or
carbonaceous material has been formed.

Table 3
Pyrolysis yields (wt.%) (mean value ± standard deviation)
Pyrolysis temperature (◦ C)

300 400 500 600 700

Solid 87.6 ± 7.8 55.9 ± 5.5 44.8 ± 0.6 44.2 ± 0.6 43.7 ± 0.4
Liquid 4.8 ± 3.9 24.8 ± 6.0 38.0 ± 1.8 38.2 ± 0.5 38.5 ± 1.2
Gasa 7.6 ± 3.9 19.3 ± 2.2 17.2 ± 1.8 17.6 ± 0.8 17.8 ± 1.2
a Determined by difference.
922 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 71 (2004) 917–934

Table 3 shows that there is a lack of influence of temperature in liquids and gas yields
over 500 ◦ C, which is in accordance with what has been found by other authors [18].
Therefore 500 ◦ C seems to be the optimum temperature for recycling tyres by pyrolysis,
since decomposition is complete and the same yields are obtained as at higher temperatures.

3.2. Characteristics of tyre pyrolysis liquids

The liquids obtained in tyre pyrolysis, which are usually termed oils, are dark-brown-
coloured products, which resemble petroleum fractions. The elemental compositions, H/C
atomic ratios and GCV of the tyre pyrolysis oils obtained at every temperature are presented
in Table 4. The results presented in the table include the mean value and the standard
deviation of at least five pyrolysis runs carried out at the same temperature.
It can be seen that there is almost no effect of pyrolysis temperature on the composition
of the oils. They all have H/C atomic ratios around 1.4, which may be an indicator that
such oils are a mixture of aromatic and aliphatic compounds, corresponding to the source
polymeric materials (styrene–butadiene rubber (SBR), and other rubbers).
The GCVs of the oils are rather high (≈42 MJ kg−1 ), even higher than those specified
for commercial heating oils. Concerning S, the EU has limited the S content in commercial
oils in less than 1 wt.% since 1 January 2003. Tyre-pyrolysis liquids have sulphur contents
(1.0–1.4 wt.%), slightly over the law limit value; therefore they would require a mild hy-
drotreating in order to be possible to use them directly as fuel oil; otherwise it would be
necessary to mix them with another commercial oils, previous to their use as fuel oils.
Almost coincident results concerning elemental composition and GCV of tyre 450–600 ◦ C
pyrolysis liquids were obtained by Cunliffe and Willians [8]. Also Roy et al. [21] obtained
similar elemental compositions in 450 ◦ C pyrolysis oils.
Table 4 shows that there is no effect of pyrolysis temperature in the elemental composition
of the oils, which is in agreement with the results presented by Cunliffe and Williams [8].
On the contrary Lucchesi and Maschio [25] found a decrease in H/C ratio with temperature.

3.2.1. Gas chromatography/mass spectroscopy (GC/MS) analysis

GC/MS analyses were carried out with the pyrolysis oils obtained at every temperature.
The objective was to get an idea of the nature and type of compounds of such oils, in

Table 4
Pyrolysis liquid elemental composition (wt.%) and GCV (MJ kg−1 ) (mean value ± standard deviation)
Pyrolysis temperature (◦ C)

300 400 500 600 700

C 86.5 ± 0.7 85.9 ± 0.7 85.6 ± 0.5 86.2 ± 1.0 86.0 ± 0.9
H 10.7 ± 0.2 10.6 ± 0.3 10.1 ± 0.1 10.2 ± 0.1 10.2 ± 0.2
N 0.3 ± 0.04 0.3 ± 0.06 0.4 ± 0.03 0.4 ± 0.03 0.4 ± 0.04
S 1.0 ± 0.2 1.1 ± 0.2 1.4 ± 0.2 1.2 ± 0.1 1.2 ± 0.2
O + others (by difference) 1.5 ± 0.8 2.1 ± 0.8 2.5 ± 0.5 2.0 ± 0.9 2.2 ± 0.9
H/C atomic ratio 1.49 1.49 1.42 1.41 1.42
GCV 43.2 ± 0.4 42.6 ± 0.4 42.1 ± 0.3 42.2 ± 0.3 42.3 ± 0.4
 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 71 (2004) 917–934 923

order to establish the possible ways of reusing or treating and reusing them. Fig. 1 show, as
an example, the GC/MS chromatogram obtained with the 700 ◦ C pyrolysis oils: Fig. 1(a)
shows the whole chromatogram, while Fig. 1(b)–(f) correspond to enlarged fragments of
it, in which all the identified peaks have been numbered. The chromatograms of the oils
obtained at the other temperatures were rather similar to this one, except that of the 300 ◦ C
oils, which contained quite less peaks.
The parameters for the integration of the chromatograms were chosen so that the signal-to-
noise ratio was higher than five; this criterion provided around 300 peaks, from which more
than the half was not properly identified. Peaks identification was made by the PBM search of
their spectra. Those identification results of match quality higher than 90% were considered
valid, once confirmed that their tentative assignments where in agreement with published
GC/MS data of similar products [8,20,31–33]. The isomeric structures of the compounds
have not been determined, due to the limitation of the GC/MS identification procedure
to differentiate among isomers. Anyway, such identification is beyond the scope of this
paper.
Table 5 shows the tentative compounds assigned and the percentage quantified area for
every identified peak. It can be seen that, as expected, tyre pyrolysis oils are a very com-
plex mixture of organic compounds of 6–24 carbons. There are such a great number of
compounds in tyre oils that the peak areas are very low. The most abundant products,
with peak areas around or greater than 1%, are toluene, dimethylcyclohexenes, ethylben-
zene, xylenes, styrene, methyloctene, ethylmethylbenzenes, methylethenylbenzenes and
limonene. It is worth mentioning that these compounds peak areas are comparables to those
obtained by Benallal et al. [19]. For instance they obtained 15.7% toluene, 21.2% xylenes,
6.9% limonene, etc. in the light naphtha fraction, which was only ≈20% of total 510 ◦ C
pyrolysis oils. The peak areas obtained in this study with the 500 ◦ C pyrolysis oils are
4.40% toluene, 3.48% xylene, 5.12% limonene, etc., but correspond to total pyrolysis oils.
These concentrations are greater than those obtained by Cunliffe and Williams [8] (1.77%
toluene, 3.10% limonene, 1.68% xylenes, etc.), and those presented by Pakdel et al. [34]
(1.86% toluene, 1.60% xylenes, 4.00% limonene). These volatile hydrocarbons are consid-
ered valuable products, which give a potential high value to tyre pyrolysis oils. Limonene
(tR = 22.71 min) is the one present in the highest concentration. Several researchers have
reported that limonene decreases as the pyrolysis temperature is increased [8,34–36]. Table 5
also shows a very important decrease of limonene concentration with temperature (from
≈21 to 3%). However it must be taken into account that oil yields at 300 and 400 ◦ C are
rather low. The limonene percentages in Table 5 represent 1.01, 2.04, 1.94, 1.22 and 1.27%
with respect to tyre, at 300, 400, 500, 600 and 700 ◦ C, respectively. Therefore there is not
a continuous decrease of the amount of limonene obtained with pyrolysis temperature, but
an increase from 300 to 400 ◦ C and then a decrease. Cunliffe and Williams [8] have re-
ported that increasing the pyrolysis temperature up to 525–560 ◦ C causes an increase in
benzene, toluene and xylene, while over such temperature a decrease is observed. Simi-
larly in this study such hydrocarbons increase from 300 to 500 ◦ C and then decrease over
500 ◦ C.
Every compound in Table 5 has been classified as aromatic (Ar), non-aromatic (NAr), oxy-
genated aromatic (ArO), oxygenated non-aromatic (NArO), nitrogenated aromatic (ArN)
or nitrosulphurated aromatic (ArNS). It can be seen that at every temperature tyre pyrolysis
924 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 71 (2004) 917–934

Fig. 1. GC/MS chromatogram of the 500 ◦ C tyre pyrolysis oils. (a) Total chromatogram, (b) 0–17 min, (c)
17–24 min, (d) 24–31 min, (e) 31–38 min, and (f) 38–50 min. Peak labels correspond to serial numbers in Table 5.
M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 71 (2004) 917–934 925

Fig. 1. (Continued ).
926 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 71 (2004) 917–934

Table 5
Tentative GC/MS characterization of tyre pyrolysis oils (percentage area)
Peak tR (min) Tentative assignment Tyre pyrolysis temperature (◦ C) Type of
number compound
300 400 500 600 700

1 7.57 Methylcyclopentene 0.29 0.07 NAr

2 7.99 Methylcyclopentene 0.21 0.23 NAr
3 8.42 Benzene 0.47 0.98 0.52 0.29 Ar
4 10.61 Methylhexadiene 0.16 0.20 0.10 0.13 NAr
5 11.02 Trimethylpentane 0.20 0.28 0.22 0.21 0.12 NAr
6 11.19 Dimethylcyclopentane 0.13 0.14 0.16 0.09 NAr
7 11.98 Trimethylpentane 0.21 0.19 0.24 0.12 NAr
8 12.63 Methylpentanone 0.48 0.21 0.18 0.16 0.10 NArO
9 13.34 Dimethylhexane 0.61 0.50 0.44 0.22 0.28 NAr
10 13.45 Ethylcyclopentane 0.10 0.10 0.06 NAr
11 13.95 Methylbencene (toluene) 1.67 2.63 4.40 2.81 2.09 Ar
12 14.11 Methylcyclohexene 0.32 0.43 0.40 0.30 0.22 NAr
13 14.45 Dimethylcyclohexane 0.12 0.10 0.13 0.05 NAr
14 15.00 Octene 0.06 0.09 0.06 0.04 NAr
15 15.48 Dimethylhexadiene 0.12 0.10 0.20 NAr
16 15.64 Dimethylcyclohexene 0.11 0.14 NAr
17 15.82 Dimethylcyclohexene 0.18 0.14 0.17 0.08 NAr
18 16.41 Dimethylcyclohexene 4.43 3.83 4.89 3.95 2.99 NAr
19 16.81 Ethylcyclohexane 1.02 0.60 0.41 0.38 0.26 NAr
20 16.93 Methylheptyne 0.12 0.16 0.12 0.17 0.08 NAr
21 17.13 Ethylcyclohexane 0.33 NAr
22 17.37 Trimethylcyclohexane 0.18 NAr
23 17.82 Ethylbenzene 2.49 2.55 2.79 1.88 1.43 Ar
24 18.09 Dimethylbenzene (xylene) 2.45 2.16 2.71 1.83 1.49 Ar
25 18.73 Nonene 0.23 0.20 0.22 0.12 NAr
26 18.82 Ethenylbenzene (styrene) 1.54 1.77 2.45 1.94 1.44 Ar
27 18.90 Dimethylbenzene (xylene) 0.44 0.57 0.77 0.22 0.41 Ar
28 19.25 Trimethylcyclohexene 0.12 0.09 0.11 NAr
29 19.55 Methyloctene 1.68 1.64 2.20 0.94 0.96 NAr
30 19.62 Trimethylcyclohexene 0.26 0.18 NAr
31 19.88 Isopropylbenzene (cumene) 1.17 0.76 0.61 0.35 0.33 Ar
32 20.45 Trimethylheptatriene 0.83 0.45 0.25 0.49 0.15 NAr
33 20.51 Ethenylmethylbenzene 0.27 0.37 0.31 0.20 0.18 Ar
34 20.73 Propylbenzene 0.97 0.89 0.61 0.44 0.36 Ar
35 20.85 Pinene 1.40 1.00 0.58 0.45 0.38 NAr
36 20.94 Ethylmethylbenzene 0.95 0.94 0.88 0.49 Ar
37 20.99 Ethylmethylbenzene 1.69 1.36 1.17 1.26 0.64 Ar
38 21.13 Trimethylbenzene 0.20 0.23 0.27 0.27 0.16 Ar
39 21.26 Phenol 0.32 0.23 0.24 0.17 0.16 ArO
40 21.49 Methylethenylbenzene 1.04 00.91 1.12 0.31 0.71 Ar
41 21.60 Benzonitrile 0.37 0.38 0.32 0.20 ArN
42 21.76 Propenylbenzene 0.30 0.23 0.23 0.67 0.19 Ar
43 21.82 C3 -benzene 0.83 0.87 1.05 1.49 0.66 Ar
44 21.88 Methylethenylbenzene 0.77 0.29 0.24 0.56 0.16 Ar
45 21.93 Methylethenylbenzene 0.36 0.20 0.20 0.13 0.13 Ar
46 22.54 Isopropylmethylcyclohexene 1.85 0.75 0.51 0.30 NAr
47 22.59 Isopropyltoluene 6.63 2.66 2.01 1.72 1.32 Ar
48 22.64 C3 -benzene 0.33 0.34 0.24 Ar
 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 71 (2004) 917–934 927

Table 5 (Continued )
Peak tR (min) Tentative assignment Tyre pyrolysis temperature (◦ C) Type of
number compound
300 400 500 600 700

49 22.71 Limonene 21.07 8.22 5.12 3.19 3.29 NAr

50 22.84 Isolimonene 0.23 0.14 NAr
51 22.97 Dihydro-1H-indene 0.50 0.44 0.58 0.58 0.36 Ar
52 23.19 1H-indene 0.77 0.43 0.90 0.64 0.60 Ar
53 23.35 Butylbenzene 0.86 0.86 0.67 0.54 0.46 Ar
54 23.84 Ethyldimethylbenzene 0.17 0.15 0.17 0.45 0.12 Ar
55 23.89 Isopropylmethylbenzene 0.32 0.32 0.29 1.06 0.20 Ar
56 23.96 n-C11 0.20 0.21 0.23 0.22 0.14 NAr
57 24.03 Ethyldimethylbenzene 0.24 0.25 0.31 0.19 0.19 Ar
58 24.11 Isopropylmethylbenzene 0.75 0.50 0.54 0.45 Ar
59 24.15 Dihydromethyl-1H-indene 0.40 0.42 0.30 0.14 0.20 Ar
60 24.57 Tetramethylbenzene 0.41 0.28 0.20 0.28 0.13 Ar
61 24.84 Tetramethylbenzene 0.25 0.30 0.28 0.18 0.24 Ar
62 25.12 Ethylisopropylbenzene 0.31 0.24 0.18 0.12 Ar
63 25.22 Dimethylphenol 0.19 0.21 0.19 0.16 0.16 ArO
64 25.31 Dihydromethyl-1H-indene 0.34 0.48 0.45 0.44 0.32 Ar
65 25.43 Benzoic acid 0.29 0.32 0.28 0.48 0.20 ArO
66 25.56 Dihydromethyl-1H-indene 1.20 2.12 2.80 1.03 2.21 Ar
67 25.68 Methyl-1H-indene 0.36 0.57 0.36 Ar
68 25.85 Tetrahydronaphthalene 0.30 0.34 0.28 0.62 0.22 Ar
69 25.92 C4 -benzene 0.12 0.17 0.14 Ar
70 26.04 Cycloundecane 0.18 0.21 0.18 0.16 0.16 NAr
71 26.15 Dihydrodimethyl-1H-indene 0.34 0.28 0.20 0.30 0.15 Ar
72 26.20 Methylphenylethanone 0.51 0.49 0.30 0.26 0.21 ArO
73 26.29 Tetrahydromethylnaphthalene 0.33 0.48 0.31 0.22 0.25 Ar
74 26.37 Naphthalene 0.34 0.45 0.73 0.63 0.59 Ar
75 26.52 Methylbutenylbenzene 0.56 0.84 0.54 0.19 0.37 Ar
76 26.79 Isopropylphenol 0.15 0.10 ArO
77 27.08 Cyclopentylbenzene 0.37 0.36 0.17 0.11 0.18 Ar
78 27.17 Benzothiazole 0.98 1.34 0.93 0.74 0.76 ArNS
79 27.44 Ethyl-1H-indene 0.28 0.32 0.24 Ar
80 27.54 Tetrahydroethylnaphthalene 0.19 0.34 0.34 0.17 0.31 Ar
81 27.57 C6 -benzene 0.35 0.38 0.26 0.28 0.24 Ar
82 27.65 Dimethyl-1H-indene 0.14 0.29 0.33 Ar
83 27.87 Dimethyl-1H-indene 0.35 0.32 Ar
84 28.21 Tetrahydrodimethylnaphthalene 0.25 0.32 0.27 0.25 Ar
85 28.47 Cyclopentenylbenzene 0.41 0.68 0.70 0.44 0.71 Ar
86 28.50 Methylnaphthalene 0.19 0.32 0.84 0.95 0.67 Ar
87 28.84 Methylnaphthalene 0.54 0.68 0.99 0.90 0.82 Ar
88 29.00 Tetrahydrodimethylnaphthalene 0.47 0.44 0.34 0.27 0.40 Ar
89 29.63 Trimethylindene 0.15 0.26 Ar
90 29.81 Trimethylindene 0.43 0.51 0.62 0.54 0.76 Ar
91 29.95 Diphenyl 0.52 0.73 0.91 0.94 0.84 Ar
92 30.25 Ethylnaphthalene 0.34 0.40 0.58 0.86 0.60 Ar
93 30.33 Ethylnaphthalene 0.26 0.34 0.34 Ar
94 30.44 Dimethylnaphthalene 0.25 0.27 0.63 0.66 0.43 Ar
95 30.71 Dimethylnaphthalene 0.31 0.40 0.60 0.45 0.55 Ar
96 30.77 Dimethylnaphthalene 0.43 0.65 0.83 0.68 0.71 Ar
97 31.08 Ethylquinoline 0.58 0.94 1.08 1.10 1.06 ArN
928 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 71 (2004) 917–934

Table 5 (Continued )
Peak tR (min) Tentative assignment Tyre pyrolysis temperature (◦ C) Type of
number compound
300 400 500 600 700

98 31.44 n-C14 0.55 0.98 1.04 0.80 0.56 NAr

99 31.68 Methyldiphenyl 0.21 0.21 0.48 0.73 0.52 Ar
100 31.86 Methyldiphenyl 0.19 0.17 0.28 0.56 0.30 Ar
101 31.89 Acenaphthene 0.21 0.53 0.22 Ar
102 32.06 Trimethylazulene 0.13 0.42 0.21 Ar
103 32.15 Trimethylazulene 0.25 0.27 0.29 0.35 Ar
104 32.36 n-C15 1.15 NAr
105 32.50 Trimethylnaphthalene 0.38 0.53 0.73 0.77 0.80 Ar
106 32.78 Trimethylnaphthalene 0.16 0.28 0.27 0.39 Ar
107 32.82 Trimethylnaphthalene 0.19 0.57 0.23 Ar
108 33.44 Fluorene 0.18 0.36 0.39 0.44 Ar
109 33.91 Dimethyldiphenyl 0.50 0.77 0.31 0.44 0.36 Ar
110 33.96 Dimethyldiphenyl 0.16 0.22 Ar
111 34.33 Pentadecene 0.16 0.19 0.35 NAr
112 34.42 n-C16 0.35 0.56 0.49 0.60 NAr
113 35.09 Methylfluorene 0.15 0.21 0.24 0.34 Ar
114 35.25 Methylfluorene 0.12 0.20 0.33 Ar
115 35.35 Ethyldimethylazulene 0.33 0.21 1.09 0.32 Ar
116 36.40 Phenanthrene 0.21 0.54 0.43 Ar
117 36.54 Anthracene 0.22 0.63 0.44 Ar
118 37.37 Methylphenanthrene 0.22 0.57 0.68 Ar
119 37.85 Pentadecanoic acid 0.59 0.60 0.90 0.43 NArO
120 37.98 Methylphenanthrene 0.31 0.58 0.59 Ar
121 38.28 Methylphenanthrene 0.12 0.44 1.43 Ar
122 38.32 Methylphenanthrene 0.19 0.39 1.52 0.47 Ar
123 39.72 Dimethylphenanthrene 0.19 0.35 0.53 0.71 Ar
124 40.63 Methylheptadecanoate 0.23 0.90 1.11 NArO
125 40.69 n-C19 0.12 0.18 0.29 NAr
126 41.07 Trimethylphenanthrene 0.19 0.48 0.37 Ar
127 41.88 Isopropylmethylphenanthrene 0.24 0.73 0.51 0.81 Ar
128 42.73 n-C20 0.27 0.19 NAr
129 43.32 n-C21 0.27 0.24 0.25 NAr
130 44.95 n-C22 0.16 0.18 0.09 0.20 NAr
131 46.88 n-C23 0.52 0.14 0.24 0.17 NAr
132 49.21 n-C24 0.12 0.15 NAr
Total identified 78.14 68.10 75.03 62.50 57.70

oils are predominantly aromatic, which is in agreement with many other researches
[8,11,13,19,25,37–40]. The aromaticity of tyre oils is due, on the one hand, to the aro-
matic nature of the source polymeric material, styrene–butadiene rubber, and on the other
hand, to ciclation of olefin structures followed by dehydrogenation reactions, which take
place during the pyrolysis process.
Table 6 shows the proportion of aromatic and non-aromatic compounds of the pyrolysis
oils at every temperature; it has been calculated assuming that the non-identified area has
the same aromatic/non-aromatic ratio as the identified one. It can be seen that the proportion
 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 71 (2004) 917–934 929

Table 6
Proportion (percentage area) of aromatics and non-aromatics in tyre pyrolysis oils
Pyrolysis temperature (◦ C)

300 400 500 600 700

Aromatics 53.4 66.6 70.9 74.0 74.8

Non-aromatics 46.6 33.4 29.1 26.0 25.2

of aromatics increases with pyrolysis temperature, which is in agreement with the results
obtained by other researchers [8,11,25,37–39]. The formation of aromatics at the expense
of aliphatics when temperature is raised has been verified by several researchers [41–43] in
studies on pure hydrocarbon compounds. Lucchesi and Maschio [25] found an increase in
oil aromaticity with temperature, by studying the H/C ratio. On the contrary, in this paper
the H/C atomic ratio (Table 4) almost not varies with temperature, while the proportion of
aromatics clearly increases. Therefore it is the opinion of the authors, that as the pyrolysis
temperature is raised, more non-aromatic compounds link to aromatic structures yielding as
a result a greater proportion of aromatic compounds. Williams et al. [44] have also reported
an increase in aromatic compounds having long side chains, when the temperature of the
tyre pyrolysis process is increased.
Table 5 also shows that there is an important proportion of polycyclic aromatic com-
pounds such as alkylated naphthalenes, phenanthrenes, fluorenes, diphenyls, etc., which
is coincident with what has been reported by other researchers [8,11,37,38,45]. It can be
seen that some of the polycyclic aromatic compounds are not present in the lower tem-
perature pyrolysis oils, while at 700 ◦ C are present all of them, and frequently in a higher
proportion than at the lower temperatures. For instance there is neither phenanthrene nor
alkylphenanthrenes in the 300 ◦ C tyre oils, while there is 0.74, 2.63, 4.19 and 5.06% area
of all phenanthrenes in the 400, 500, 600 and 700 ◦ C tyre oils. Therefore assuming that
the proportion of polycyclic aromatics in the non-identified area is equivalent to that of the
identified area, it can be concluded that there is an increase of such compounds with tem-
perature, which has also been observed by other authors [8,11,37,45]; this can be attributed
to reactions between aromatic compounds and olefins, followed by cyclation of the olefinic
branch and then dehydrogenation.
Table 5 shows that there are several oxygenated compounds, such as phenols, acids, etc.,
which amount up to 2–3% of total chromatogram area, whichever the temperature is. The
presence of these compounds may be explained by the thermal degradation of oxygenated
components of the tyre, such as stearic acid, extender oils, etc. Pakdel and Roy [20] detected
also oxygenated compounds in tyre pyrolysis oils.
Nitrogenated compounds are as well present in tyre oils (≈3% area in Table 5). These
compounds are probably derived from the accelerators used in tyre compounding, which
are frequently sulphur and/or nitrogen-based compounds, such as benzothiazoles, thioureas,
thiuram, amines, etc. Some other authors have also detected nitrogenous compounds in tyre
pyrolysis oils [14,20,46]. With respect to sulphurated compounds, benzothiazol is the only
one identified in this study. Its proportion is relatively high, ≈1% area. Benzothiazol is,
as has been mentioned before, an accelerator widely used in tyre formulations. Mirmiram
et al. and Pakdel and Roy [14,20] have also identified benzothiazole in tyre pyrolysis oils.
930 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 71 (2004) 917–934

80
300ºC

70 400ºC

500ºC

60 600ºC

700ºC
Quantified area (%)

50

40

30

20

10

0
10.0-20.0 20.0-30.0 30.0-40.0 40.0-50.0
Retention time interval (minutes)

Fig. 2. Total GC/MS quantified area (identified and non-identified peaks) in each retention time interval.

Finally, in order to finish with the GC/MS discussion, certain attention about the per-
centage of area identified at each temperature must be drawn. Such percentages are in-
cluded at the bottom of Table 5, where it can be seen that except at 500 ◦ C such area
significantly decreases with temperature. In Fig. 2 total quantified area at each temper-
ature, including both identified and non-identified peaks, in each retention time interval
is presented. It can be seen that in the lowest retention time interval (<20 min), there
is not a clear variation of the quantified area with temperature. It is worth mentioning
that at 700 ◦ C such area is clearly lower than at all the other pyrolysis temperatures; ob-
viously at such temperature less light products are obtained. In the 20–30 min retention
time interval there is a decrease of the total quantified area with temperature, while in
the higher retention time intervals (30–50 min), there is an increase of the quantified area
with temperature. It has been verified that, as a general rule, both the identified and the
non-identified areas increase with temperature in these later intervals. This explains why
at high pyrolysis temperatures greater non-identified areas are obtained, since at such tem-
peratures, heavier and more complex products are produced and these are more difficult to
identify.

3.2.2. Distillation
An automatic distillation test at atmospheric pressure was carried out, with a mixture of
the oils obtained in several pyrolysis tests performed at 500 ◦ C. The results are presented
 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 71 (2004) 917–934 931

400

350

300
Temperature (ºC)

250 PYROLYSIS LIQUIDS

70-175 ºC FRACTION
200 Commercial petrol (70-175 ºC)

150

100

50

0
0 10 20 30 40 50 60 70 80 90 100
Distilled (% volume)

Fig. 3. Distillation data of total 500 ◦ C pyrolysis liquids, a commercial petrol and the 70–175 ◦ C tyre oil fraction.

in Fig. 3, where it can be seen that about 20% of such oils distillate under ≈170 ◦ C, which
corresponds to the limit boiling point of light naphtha, about 10% distillate between 160
and 200 ◦ C, which corresponds to heavy naphtha and ≈35% correspond to middle distillate
(200–350 ◦ C). There are several references in the literature [19–21], which report similar
contents of naphtha (≈27%) in tyre pyrolysis oils, while others [14] report only ≈18%
naphtha.
Fig. 3 includes the distillation data of commercial petrol with a 70–175 ◦ C boiling point
range, and the data corresponding to the tyre derived oil fraction with the same boiling
point range, which is about 23% of total oils. At present, the specifications for commercial
petrol concerning distillation are the following: (a) at 100 ◦ C the distillate volume must
be between 46 and 71%; this is more or less fulfilled by the commercial petrol but not by
the tyre oil fraction; (b) at 150 ◦ C at least 75% must have been distilled; this is very well
fulfilled by the commercial petrol, but not by the tyre oil fraction.
In Fig. 4 the distillation data of a commercial automotive diesel oil, together with the data
corresponding to the tyre oil fraction with a boiling range of 150–360 ◦ C (≈53% of total tyre
oils) is presented. Distillation specifications for commercial automotive diesel oil are the fol-
lowing: (a) 65% volume must have been distilled at a temperature ≥250 ◦ C; this is fulfilled
by both the commercial diesel oil and the tyre oil fraction; (b) 85% volume must have been
distilled under 350 ◦ C; this is also attained by both oils; (c) 95% volume must have been dis-
tilled under 360 ◦ C, which is again fulfilled by both oils. Fig. 4 shows that the tyre oil fraction
has more light products than the commercial diesel oil under 300 ◦ C, since for the same tem-
perature a greater distillate volume is obtained with the tyre oil. This is an advantage since the
product can, in this way, be atomized better and so it is possible to initiate the combustion at
a lower temperature. On the contrary over 300 ◦ C the tyre oil has some more heavy products
than the commercial diesel oil; this could be an inconvenient since the tyre oil fraction will
probably contain more polycyclic aromatics, and these are very much restricted in the present
legislations.
932 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 71 (2004) 917–934

400
Temperature (ºC)

350

300

250 150-360 ºC FRACTION

Automotive diesel oil
200

150
0 10 20 30 40 50 60 70 80 90 100
Distilled (% volume)

Fig. 4. Distillation data of a commercial automotive diesel oil and the 150–360 ◦ C tyre oil fraction.

Finally Fig. 5 shows the distillation data of a commercial heating oil, and the tyre oil
fraction with a similar boiling point range (150–390 ◦ C), which is about 79% of total tyre
oils. The specifications for heating diesel oils are the following: (a) 65% volume must have
been distilled at a temperature over 250 ◦ C; this is attained by both oils; (b) 80% volume
must have been distilled under 390 ◦ C; this is also fulfilled by both oils. Fig. 5 shows that
over 225 ◦ C, the tyre oil fraction has more heavy products than the commercial heating
diesel oil. However this fact is less important in heating oils than in automotive diesel oils,
since for the former polycyclic aromatics are not limited in the present legislations.
Therefore considering only distillation data, tyre oil derived fractions could be used
both as automotive diesel oil and as heating diesel oil. Nevertheless it is probable that the
mentioned tyre oil fractions do not fulfil other specifications of the commercial diesel oils,
such as sulphur content, cetane number, etc., especially those of automotive diesel oils.
Consequently tyre oil fractions would require a series of hydrotreatments and/or blending
them with petroleum refinery streams, in order to use them as diesel oils.

Fig. 5. Distillation data of a commercial heating diesel oil and the 150–390 ◦ C tyre oil fraction.
 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 71 (2004) 917–934 933

Acknowledgements

The authors thank the Basque Country University (UPV 112.345-EA122/94 and UPV
112.345-631/98) and the Basque Government (OD 97UN16 and PI-1998-19) for financial
assistance for this work.

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