09575820/98/$10.00+0.

00
Institution of Chemical Engineers
Trans IChemE, Vol 76, Part B, November 1998

COMBUSTION OF TYRE PYROLYSIS OIL

P. T. WILLIAMS, R. P. BOTTRILL and A. M. CUNLIFFE
Department of Fuel and Energy, University of Leeds, Leeds, UK

crap tyres were pyrolysed in a one tonne batch pyrolysis unit to produce an oil, char, gas
and steel product. The derived oil was analysed for fuel properties, including calori c
value, elemental analysis, sulphur, nitrogen, chloride and uoride content. In addition, a
single oil droplet combustion study was carried out and the oil was also analysed in detail for its
content of polycyclic aromatic hydrocarbons (PAH). Comparison of the tyre oil fuel properties
with those of petroleum-derived fuels was made. The oil was combusted in an 18.3 kW
ceramic-lined, oil- red, spray burner furnace, 1.6 m in length 0.5 m internal diameter. The
emissions of NOx , SO2 , particulate and total unburned hydrocarbons were determined in
relation to excess oxygen levels. In addition, the solvent organic fraction of the soot was
extracted and analysed for PAH concentration and compared with the PAH content of the
original fuel. Throughout the combustion tests, comparison of the emissions was made with
the combustion of diesel fuel as a representative of a petroleum-derived fuel with similar
properties. The oils were found to contain 1.4 wt% sulphur and 0.45 wt% nitrogen and have
similar fuel properties to those of diesel fuel/light fuel oil. Total PAH in the tyre oil were
9.2 wt% compared to diesel fuel which contained 3.1 wt%. Combustion of the tyre pyrolysis
oil in the furnace showed that emissions of NOx and SO2 were higher than when diesel fuel
was used, which was attributed to the higher nitrogen and sulphur contents in the tyre oil.
Particulate and total unburned hydrocarbon emissions were negligible and PAH were not
detected in the normal operating mode of the furnace.
Keywords: tyres; pyrolysis; oil; combustion; analysis; emissions.

INTRODUCTION

have been found to have a high calori c value of around

4144 MJ kg 1 , which would encourage their use as
replacements for conventional liquid fuels4 ,6 ,8 . However,
their sulphur contents are in the range 1.01.5 wt% and
consequently this has implications for sulphur oxide
emissions when considering tyre oils as substitutes for
petroleum-derived fuels. In addition, the use of tyre
pyrolysis oils directly as fuels may be restricted since they
have been reported to contain high concentrations of
certain polycyclic aromatic hydrocarbons (PAH) 5 ,8 ,1 3 ,1 6 .
The concern over PAH is centred on the associated health
hazard, since among the environmental chemical groups
PAH comprise the largest group of carcinogens1 8 ,1 9 . Some
of the PAH shown to be present in tyre pyrolysis oils have
been shown to be mutagenic and/or carcinogenic1 9 ,2 0 and
may therefore restrict their handling.
The presence of PAH in the tyre oil as a potential fuel
has further signi cance, in that increased concentrations of
PAH in the fuel may lead to increases in the emissions when
the fuel is combusted. PAH have been found in petroleum
fuels in signi cant concentrations2 1 2 4 . Combustion of such
fuels in certain combustion systems such as diesel engines
and oil- red room heaters have shown soot emissions
containing PAH which have been attributed to the unburned
fuel fraction. Consequently the presence of high concentrations of PAH in tyre pyrolysis oil may lead to high
concentrations of PAH in the combustion emissions and
may limit the use of tyre pyrolysis oil as a directly
combusted fuel. However, there are very few data on the use
of tyre pyrolysis oil as a fuel in any combustion systems.

Current estimates of the annual arisings of scrap tyres in the

European Union are 2.0 million tonnes, in North America
2.5 million tonnes and in Japan 0.5 million tonnes1 3 . The
majority of scrap tyres are disposed of in open or land ll
sites. However, land lling of tyres is declining as a disposal
option, since tyres do not degrade easily in land lls, they are
bulky, take up valuable land ll space and prevent waste
compaction. Open dumping may result in accidental res
with high pollution emissions and tyres can be a breeding
ground for insects and a home for vermin. Alternative waste
management options to land lling and open dumping have
included tyre retreading and crumbing to produce rubber
for applications such as carpets, sports surfaces and
children s playgrounds. Incineration of tyres with energy
recovery is also a growing option since it utilizes the high
calori c value of tyres.
A further alternative waste management option is tyre
pyrolysis which is currently receiving renewed attention.
Pyrolysis has a number of advantages as a waste treatment
option since the derived oils may be used directly as fuels
or added to petroleum re nery feed stocks; they may also
be an important source for re ned chemicals. The derived
gases are also useful as fuel and the solid char may be
used either as smokeless fuel, carbon black or activated
carbon4 1 7 .
In order for tyre pyrolysis oils to compete with
petroleum-derived fuels, the comparative behaviour of the
tyre oil fuel should be determined. Tyre pyrolysis oils
291

292

WILLIAMS et al.

In this paper scrap tyres have been pyrolysed in a

commercial one tonne batch pyrolysis unit. The tyre-derived
oil has been analysed for a wide range of fuel properties
and compared with those of the petroleum-derived
fuels diesel and light fuel oil. The oil was also analysed
for its content of PAH. The oil was then combusted in a
1.6 m long 0.5 m diameter ceramic-lined 18.3 kW furnace,
using a conventional oil-spray burner. The emissions of
SO2 , NOx , particulate and total unburned hydrocarbons
were monitored. The solvent organic fraction of the
particulate was also analysed for PAH. The sources of
PAH in the emissions are discussed.
EXPERIMENTAL
Tyre Samples
The tyres used for the batch reactor were partly shredded
and whole tyres, including the steel cord. The tyres
represented a mixture of UK types and grades. The
proximate and ultimate analyses, on a steel- and fabricfree basis, and the calori c value of the typical raw tyre
tread used, are given in Table 1. Cypres and Bettens1 3
pyrolysed different makes and brands of tyre and found
small but signi cant differences (of the order of 10%) in
the yield of char, oil and gaseous products. Also, the
composition of the gas phase hydrocarbons and oil
composition was dependent on tyre type.
Pyrolysis Unit
The tyre batch pyrolysis unit was manufactured and
operated by Beven Recycling Ltd., Harwell, Oxfordshire,
UK, and consisted of a large capacity pyrolysis reactor into
which partly shredded and whole tyres were loaded. A
schematic diagram of the unit is shown in Figure 1. The
reactor was tted with a gas-tight lid to ensure pyrolysis
conditions were maintained in the unit and the system was

Table 1. Typical composition of the scrap tyre feedstock.

Elemental composition,
%

Proximate analysis,
%

Gross calori c value,

MJ kg 1

C
85.9
H
8.0
N
0.4
S
1.0
O
2.3
(Ash 2.4)

Volatiles
66.5
Fixed carbon 30.3
Ash
2.4
Moisture
0.8

40.0

purged with nitrogen to eliminate any oxygen. The reactor

was loaded into an outer holder which consisted of a
ceramic-lined vessel and was heated initially by oil burners
but as the pyrolysis of the tyres proceeded the oil was
replaced by the pyrolysis gas derived from the scrap tyre
pyrolysis. The maximum temperature of pyrolysis was
950C and the mass of tyres loaded into the reactor
was 1015 kg. The temperature represented a mean maximum temperature in the retort; however, because of the
bulk nature of the tyre load which included partly shredded
and whole tyres, the temperature gradient within each
tyre piece and across the retort would be very variable. The
ring time of the burners heating the retort was 8 hours 40
minutes, with a pyrolysis cycle time of 1214 hours. The
evolved pyrolysis oil vapours and gases were passed
through a heat exchanger to cool the vapours and into an
oil condensing tank; the non-condensed gases were then
passed to a scrubbing unit to clean the gases, before passing
to the burner, or to storage. The oil from the condensing
tank was pumped to storage, or could also be used to
provide auxiliary fuel for the burners. The oil sampled for
analysis was taken from the oil outlet pipe and hence
consisted of a mixture of pre-condenser, shell and tube
condenser and post condenser oils. The batch pyrolysis
system alleviates many of the problems encountered with
continuously fed systems, such as non-maintenance of

Figure 1. Schematic diagram of the Beven Recycling tyre pyrolysis unit.

Trans IChemE, Vol 76, Part B, November 1998

COMBUSTION OF TYRE PYROLYSIS OIL

pyrolysis conditions, feed problems and in-bed fouling by

the metal cord of the tyres.
Tyre Oil Fuel Properties
The tyre pyrolytic oil was analysed for its fuel properties
according to standard Institute of Petroleum (IP) or
American Society for Testing and Materials (ASTM) tests.
The gross calori c value and combustible sulphur content
of the tyre oil was determined by the IP 12 and IP 61
methods equivalent to ASTM 129-64 described in the
standards. The ash point was determined using the PenskyMartens closed cup apparatus, IP 34, ASTM D93-73
method. As preliminary tests showed that the ash point
was in the region 1020C, the sample was cooled in a
freezer prior to testing. The water content of the tyre oil
was determined using the standard IP 74, Dean and Stark
method. The ash content was determined by the IP 4,
ASTM D482-74 method. In view of the high moisture
content of the oil as determined by the Dean and Stark
assay, the IP recommended method of avoiding loss of
material caused by excess frothing upon heating was
followed that is, a 10 ml equi-volume mixture of benzene
and propan-2-ol was stirred into the oil and four strips of
ashless lter paper were placed into the oil such that 23 cm
projected above the oil surface. This procedure was found
to be effective in preventing excessive frothing from
occurring.
A Perkin-Elmer 240C elemental analyser was used to
give the percent composition of the oil by mass of carbon,
hydrogen and nitrogen. The contribution of sulphur and ash
were taken into account when calculating the oxygen
content by difference. The presence of chlorine and uorine
was determined in the washings from the bomb calorimetry
experiments of the determination of calori c value. The
presence and content of uoride and chloride anions in
the washings was determined using a Dionex QIC ion
chromatograph tted with a Dionex Ionpac AS4A 4 mm
column and electrical conductivity detector. The column
was ushed with deionized water between samples to
minimize contamination by sulphate and nitrate ions, which
were present in high concentrations in the washings.
Single Droplet Combustion
The combustion of liquid fuels in many cases involves
spray combustion. The oil is forced under pressure through
a nozzle to produce a spray of ne droplets which then
undergo combustion. A measure of the ease with which
liquid fuels combust is the burning rate coef cient. The
burning rate coef cient (K ) of the pyrolytic oils and the
comparative petroleum-derived fuels was found by employing the suspended, or captive, droplet technique at ambient
temperature, whereby a droplet of fuel is suspended from
a silica bre, then ignited. The assumptions and drawbacks
inherent in such suspended droplet studies are discussed
more fully by Williams2 5 . Most fuels have been found to
obey the `d 2 law , whereby a linear plot is produced of the
initial droplet diameter squared against the burning time.
From this information, K is calculated:
K

d 2 /tb

Trans IChemE, Vol 76, Part B, November 1998

293

where:
K
d
tb

burning rate coef cient, mm 2 s 1 ;

initial fuel droplet diameter, mm;
burning time of the droplet, s.

The droplet is taken to be ellipsoidal, as it is subject to

normal gravitational forces. Hence the equivalent spherical
diameter is calculated from the two greatest dimensions
of the droplet using the following equation:
d

d1 d 22

1/3

where:
d
d1
d2

equivalent diameter, mm;

greatest dimension in the y-axis, mm;
greatest dimension in the x-axis, mm.

In suspended droplet work the equivalent diameter of

the silica support needs to be deducted from the initial
droplet diameter, so:
K

d2

d 2n
tb

where dn equivalent diameter of the needle bulb, mm.

The dimensions of the droplet and residue were measured
by a video camera system. An optical sensor responsive
to the colour of the ame measured tb . After combustion, a
number of dimension measurements were made of the
support. The Bunsen ame was brie y applied to burn off
any residues remaining which were not combusted. The
measurements were repeated over the same orientations,
enabling the thickness of any residues to be determined.
Single droplet combustion may be carried out under
ambient or elevated temperature conditions. Since tyrederived oils have a broad boiling-point range1 5 , both
methods may result in inaccuracies. Using ambient conditions, it is possible that the ame temperature attained
on ignition of the droplet will not be suf cient to burn
the heavier material completely, leaving a carbonaceous
residue. However, the high amount of volatile components,
as evidenced by the low ash-point and high concentrations
of compounds such as benzene, means that some material
may be lost prior to ignition in elevated temperature work.
In the light of this, it was decided to work at ambient
temperature, but to correct the diameter loss to account for
any unburned material by measuring the thickness of such
residues after droplet combustion was complete, giving a
corrected burning rate coef cient K1 . To take account of
the residue, the average residue thickness was added to the x
and y dimensions of the needle bulb as determined earlier
so:
dn

d1

r1 d 2

r2

2 1/3

where:
r1
r2

residue thickness in y-axis, mm;

residue thickness in x-axis, mm.
Oil Analysis

The oil composition was analysed in detail for PAH

by liquid chromatography to separate the oils into chemical
class fractions followed by gas chromatography/mass

294

WILLIAMS et al.

spectrometry and gas chromatography/ ame ionization

detection. The liquid chromatography consisted of 10 cm
1 cm glass columns packed with 5.0 g silica, Bondesil
(sepralyte) sorbent, pre-treated at 105C for 2 h prior to use.
To prevent the formation of a solid phase with the addition
of the pentane mobile phase, and to improve solvent
contacting with the oil, the oil (0.25 g) was intimately mixed
with Chromosorb G/AW/DMCS 60-80 support and packed
in the column above the analytical phase. The column was
then sequentially eluted under vacuum with 10 ml elutions
of pentane, benzene, ethyl acetate and methanol to produce
aliphatic, aromatic, hetero-atom and polar fractions respectively. Analysis using gas chromatography/mass spectrometry and Fourier transform infrared spectrometry
con rmed that these were the compositions of each fraction.
Each fraction was evaporated to dryness, weighed and the
percentage mass in each fraction calculated. The evaporation
of the solvent would inevitably lead to some loss of volatile
material; consequently, this step in the analytical procedure
was carefully carried out to minimize these losses.
The aromatic fractions were analysed by capillary
column gas chromatography/mass spectrometry together
with relative retention times using relative retention
indices2 6 2 8 to determine identi cation of PAH and thereby
verify the separation of the PAH fraction. The mass
spectrometer used was of the bench top ion trap detector
type manufactured by Finnigan-MAT. The ion trap detector had a mass range from 20 to 650 u with scan times
between 0.125 and 2 s and was linked to a computer
with a library containing 38,752 mass spectra. Single
ion monitoring (SIM) was also carried out to con rm
the identi cation of compounds and also to examine the
samples for a series of substituted compounds for
example, phenanthrene and its methyl-, dimethyl-, trimethyl- and tetra-methyl derivatives. The fractions may
contain heterocyclic PAH such as nitrogen-containing PAH
and sulphur-containing PAH, which were not determined
in this study. Quanti cation of the PAH was determined
by capillary column gas chromatography with cold oncolumn injection and a ame ionization detector with
internal PAH standards and data analysis computer package. The capillary columns used in both gas chromatographs were DB5 and the temperature programme was 60C
for 2 minutes followed by a 5C min 1 heating rate to 270C.
A series of sequential dilutions of standard solutions of

PAH for instance, uorene and methylated naphthalenes were analysed to produce straight line plots of
response against concentration, which were then used to
quantify the PAH species identi ed. Accuracy of the
analytical system was 10 ppm. The results represent the
average of two separate quanti cations for each oil.
The analyses were repeated several times and analytical
method developments included full statistical error analysis
and have been reported previously4 ,1 5 1 7 .
Furnace Combustion Tests
The tyre oil and diesel fuel were combusted in a 1.6 m
long 0.5 m internal diameter ceramic-lined furnace
(Figure 2). The overall length included a tapered section
to reduce the furnace diameter prior to the ue. The ue was
water cooled to reduce the temperature of the ue gases to
between 200 and 250C. Throughout the furnace and ue
were sampling ports for gas and particulate sampling and
thermocouples to monitor the temperature. The burner
used was a Nu-Way Boxer (Droitwich, UK) type of 14.7
18.3 kW capacity. The tyre oil and diesel fuel were metered
and drawn via a pump to the burner through in-line lters.
The pressure spray atomizer of the burner was 0.4 mm in
diameter with a xed angle spray of 80 H. The air intake
to the burner was adjusted using an air strap and combustion conditions in the furnace monitored by the use of an
oxygen meter. The furnace was preconditioned for several
hours to establish steady state conditions before sampling.
Gas and particulate sampling was carried out on the ue
gases. A heated sample probe transferred the gases to
either the gas sampling system or the particulate sampling
system. The ue gases were analysed on-line for SO2
using an Analytical Developments Company (UK) infrared
analyser, NOx was analysed using a Thermoelectron (USA)
chemiluminescent analyser, total hydrocarbons were analysed using a Signal (UK) Total Hydrocarbon Analyser
Model 2000 and oxygen and carbon dioxide analysed using
Servomex (UK) Series 1400 analysers. Sample conditioning included gas cooling, particulate removal and drying
of the gases prior to analysis. Speci c drying agents were
used to give minimal absorbance of the speci c gas being
determined. Particulate sampling was via a heated sample
probe maintained at 50C transferred to a commercial
particulate sampling system a Richard Oliver (UK) lter

Figure 2. Schematic diagram of the ceramic-lined furnace.

Trans IChemE, Vol 76, Part B, November 1998

COMBUSTION OF TYRE PYROLYSIS OIL

paper particulate sampler. This allowed a predetermined
total volume of ue gases to be passed through a glass bre
lter paper at a constant temperature and a xed ow rate.
Cooling the gases to 50C not only ensured that hydrocarbon gases were condensed from the gas phase onto the
particulate but also maintained the water vapour largely in
the gas phase thus preventing condensation and blockage
of the lters. The lter papers used were 5.5 cm diameter
Whatman glass bre GF/F grade lters which had a
speci ed retention of 98% of 0.7 mm diameter particles
and ensured ef cient collection of even smaller particles.
The lter papers were kept in the dark at constant relative
humidity and weighed to 10 mg accuracy before and after
the tests.
Analysis of Polycyclic Aromatic Hydrocarbons in
Furnace Particulate Emissions
The solvent organic fraction of the ue gas particulate
was extracted and the content of PAH determined. Highgrade solvents were employed throughout the extraction and
fractionation procedures. Cellulose Soxhlet thimbles were
used to hold the glass bre lters for the extraction process
and were pre-extracted with solvent to remove impurities.
The particulate lter paper samples were placed in the
pre-extracted cellulose Soxhlet thimbles and extracted for
8 hours using 200 ml of 4:1 by volume benzene:methanol
in a Soxhlet apparatus. The solvent mixture has been found
to extract PAH ef ciently in previous studies2 2 ,2 3 . The
extract was evaporated to near dryness using rotary
evaporation and nitrogen blow-down. The extract was
analysed for PAH using the open column liquid chromatography and coupled gas chromatography/mass spectrometry
plus coupled gas chromatography/ ame ionization detection methodologies as outlined earlier for the tyre oil and
diesel fuel.
The combustion emission tests using the tyre pyrolysis
oil were compared to those obtained using diesel fuel
which had similar fuel properties to the tyre oil. The fuel
was obtained commercially and was of A1 grade, the
properties of the fuel were analysed for comparison
purposes or standard speci cation data obtained. In
addition, the emissions were compared to those obtained
with a pure hydrocarbon fuel, n-hexadecane. This was for
the particular case of PAH emissions where the contribution
from unburned fuel-derived PAH could be eliminated.
The n-hexadecane was obtained from Aldrich Chemicals
(UK) and was 99% grade with no PAH present.
RESULTS AND DISCUSSION
Product Yield from the Pyrolysis of Scrap Tyres
The product yield from the pyrolysis of scrap tyres in the
one tonne batch pyrolysis unit are shown in Table 2, in

295

the form of actual mass yields, percentage mass yields and

mass yields corrected for the content of steel in the tyre. The
targeted product for the Beven Recycling unit was char and
consequently process conditions were chosen to optimize
the production of char. This involved slow heating rates in
an inert atmosphere of nitrogen. The char yield was high at
46.8 wt%, after correction for the steel content of the tyres.
Projected end-uses for the char are as low-grade activated
carbon, carbon black, a solid fuel or upgrading to higher
grades of activated carbon. The yield of recovered steel
was signi cant at 12.9 wt% of the original tyre mass and can
be recycled back into the steel industry. The gases produced
consist mostly of hydrocarbons up to C4 , hydrogen and
lower concentrations of carbon dioxide and carbon monoxide. The gases have suf cient calori c value to support
the energy requirements of the pyrolysis unit and so off-set
the costs of recycling. Oil yield was 20.9 wt% and 24.0 wt%
when corrected for the steel content of the tyre. The oil yield
was similar to that reported from other pyrolysis experiments. For example, Kaminsky and Sinn5 obtained a 40%
oil yield in a uidized bed reactor operated at 640C falling
to 27% at 840C, and Collin1 2 obtained a 23% oil yield
using a rotary kiln reactor operated at 700C. Higher oil
yields have been reported by other workers for example,
Roy and Unsworth2 used a vacuum pyrolysis unit at 415C
and reported a maximum oil yield of 56.6 wt% and
Kawakami et al.6 produced an oil yield of 53 wt%. Williams
et al.4 showed that a xed bed reactor with a continuous
gas purge of nitrogen produced an oil yield of 58.8 wt%.
High heating rates with short hot zone residence times and
rapid quenching of the products are regarded as favouring
the formation of liquid products, since the pyrolysis gases
and vapours are condensed before further reaction breaks
down the higher molecular weight species into gaseous
products. Therefore, the removal of pyrolysis products
from the hot zone reduces the extent of secondary
reactions which are known to increase the yield of char at
the expense of oil formation1 3 . Cypres and Bettens1 3
increased the rate of removal of pyrolysis vapours from
scrap tyres from a secondary hot zone by increasing the ow
of nitrogen carrier gas. They found that this increased the
yield of oil by reducing the secondary reactions. Primary
vapours are rst produced in the pyrolysis process, the
characteristics of which are most in uenced by heating
rate. These primary vapours then degrade to secondary tars
and gases, the proportion and characteristics of which are a
function of temperature and time. At higher temperatures
the major product is gas. The reactor described in this
work produced lower oil yields since the unit was of the
slow pyrolysis type and had no sweep gas and consequently
secondary reactions occurred, increasing the yield of char
and gas. Higher temperatures were used to reduce process
time but at the expense of lower char yields and higher
gas yields. The high oil yields produced by other workers

Table 2. Product yield from the batch pyrolysis of scrap tyres.

Product
Actual mass yield, kg
Percentage yield, wt%
Percentage yield corrected for steel cord, wt%

Trans IChemE, Vol 76, Part B, November 1998

Oil

Char

Gas

Steel

212.4
20.9
24.0

413.8
40.7
46.8

242.8
23.9
27.4

131.1
12.9

296

WILLIAMS et al.

are due to either high heating rates with rapid quenching

of the derived pyrolysis vapours6 , or continuous purging of
the products with nitrogen4 or vacuum pyrolysis2 .
Fuel Properties
Table 3 shows the fuel properties of the tyre-derived
pyrolysis oil compared to the fuel properties of diesel fuel
and light fuel oil. The carbon residue result for the tyre oil
was 2.2%. The carbon residue test is a measure of the
tendency of the oil to form carbon, particularly when the oil
is combusted in the absence of a large excess of air or when
the fuel is subject to evaporation and pyrolysis. For
example, a high carbon residue result may lead to coking
of fuel injector nozzles in a diesel engine or spray
combustion ori ces. The typical diesel fuel shown in
Table 3 has a carbon residue of approximately 0.35%;
however, fuel oils used in very large diesel engines may
have carbon residues up to 12%.
The viscosity of the tyre oil was similar to that of diesel
fuel. The viscosity of a fuel is an important property since
it affects, for example, the ow of the fuel through pipes
and other plant items, the atomization of the fuel and the
performance and wear of diesel pumps.
The relative density and API (American Petroleum
Industry) gravity of the tyre oil was similar to that of the
light fuel oil. The API gravity allows values of relative
density which have been made from hydrometers to be
corrected.
The ash point of a liquid fuel is the temperature at which
the oil begins to evolve vapours in suf cient quantity to
form a ammable mixture with air. The temperature is an
indirect measure of volatility and serves as an indication of
the re hazards associated with storage and application
of the fuel. The ash point of the tyre-derived oil was 20C.
The ash point is low when compared to petroleum re ned
fuels for example, diesel fuel has a required minimum
ash point of 75C and light fuel oil 79C. The low ash

points of the tyre oil were not surprising since the oil
represented an un-re ned oil with a mixture of components
having a wide distillation range.
The carbon and hydrogen contents of the tyre oil were
lower than the petroleum re ned fuels. The sulphur content
of the tyre oil was 1.45%. The sulphur content was similar to
that of a light to medium fuel oil. Similar sulphur contents
for tyre-derived pyrolysis oils have been reported in the
literature2 ,4 ,6 . Nitrogen content was somewhat higher than
that of a light fuel oil but similar to a heavy fuel oil at a
nitrogen content of about 0.4 wt%; the fuel nitrogen will
contribute to the formation of NOx on combustion.
Fluorine and chlorine contents in the tyre oil were
signi cantly high and may have consequences on environmental emissions on combustion of the oils. Moisture
content is low but still signi cant.
The distillation range of the tyre oil re ected the fact
that the oil was unre ned and consequently would have a
wide range of boiling points for the components of the oil.
The petroleum re ned fuels have boiling point ranges
consistent with their derivation that is, from the fractional
distillation of crude petroleum oil.
The calori c value of the tyre oil was 42.1 MJ kg 1 . The
calori c value was high and comparable with that of a
light fuel oil, indicating the potential for the use of tyrederived oils as fuel. Similar high calori c values for
tyre-derived pyrolysis oil have been reported. For example,
Kawakami et al.6 collected light and heavy oil fractions
with calori c values of 43.9 and 42.5 MJ kg 1 respectively,
and Roy and Unsworth2 found a calori c value of
43.0 MJ kg 1 .
The single droplet combustion study of the tyre pyrolysis oil showed a burning rate coef cient of 0.75 mm 2 s 1
which compares with values for diesel fuel and light fuel
oil of 0.88 and 0.82 mm2 s 1 respectively. Figure 3 shows
the linear relationship between the burning time and the
rate of decrease of the square of the droplet diameter in
relation to the burning time, i.e., the d 2 relationship for the

Table 3. Typical fuel properties of the tyre pyrolysis oil, diesel fuel and light fuel oil.
Fuel test

Tyre oil

Carbon residue, %
Mid boiling point, C
Viscosity
60C (cs)
40C (cs)
Density, kg m 3
API gravity
Flash point, C
Hydrogen, %
Nitrogen, %
Carbon, %
Sulphur, %
Oxygen, %
Fluorine, ppm
Chlorine, ppm
Initial boiling point, C
10%, boiling point, C
50%, boiling point, C
90%, boiling point, C
CV, MJ kg 3
Ash, wt%
Moisture content, % vol
Burning rate coef cient, mm2 s

2.2
264

<0.35
300

347

2.38
6.30
0.91
15.51
20
9.4
0.45
88.0
1.45
0.5
110
170
100
140
264
355
42.1
0.002
4.6
0.75

1.3
3.3
0.78
31
75
12.6
0.05
87.1
0.2
0.05

180

300

46.0
0.01
0.05
0.88

4.3
21.0
0.89
26.6
79
12.4
0.15
85.5
1.4
0.5

200

347

44.8
0.02
0.1
0.82

Diesel fuel

Light fuel oil

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COMBUSTION OF TYRE PYROLYSIS OIL

297

Figure 3. Single droplet combustion of tyre pyrolysis oil. The `d 2 relationship between the burning time and the rate of decrease of the square of the droplet
diameter.

tyre oil. The atomization of the fuel to produce a ne droplet

spray involves the formation of a distribution of liquid
droplets of various sizes and also of different velocities. The
rates of evaporation or combustion of the droplets will
be determined by the size of the droplets, the physical
properties of the fuel and the temperature and oxygen
concentrations within the liquid spray before the ame
front2 5 . Light fuels will vaporize completely prior to the
ame front and the resultant vapour will burn as a ame
similar to a diffusion gas ame. However, fuels such as the
tyre oil and heavier petroleum-derived fuels do not vaporize
completely prior to the ame zone and instead burn
heterogeneously as discrete single droplets or arrays of
droplets. If combustion is incomplete a solid residue is
formed which burns similarly to solid carbon particles.
The tyre oil formed such a solid residue representing about
89% of the original volume of the droplet, whereas the
diesel fuel and light fuel oil produced no residue. By
comparison a medium fuel oil gave a residue diameter of
24% of the original droplet diameter. The formation of a
residue indicates a higher propensity of the tyre oil to
produce particulates in combustion systems.

increasing post-cracking temperature. Concentrations of

individual PAH included naphthalene at 3.8% and phenanthrene at 1.6% by weight of tyre. Other PAH detected
were uorene, acenaphthene, anthracene and methylnaphthalenes. Wolfson et al.8 pyrolysed scrap tyres in a
retort heated to 500C and separated a light and heavy oil
fraction. The heavy oil fraction was shown to contain the
PAH, biphenyl, acenaphthene and alkyl naphthalenes.
Williams and Taylor16 reported high concentrations of
PAH in tyre pyrolysis oils subject to secondary aromatization reactions, where phenanthrene, pyrene, chrysene and
benzopyrenes were identi ed in the oils.
Some of the PAH shown in Table 3 have been shown
to be carcinogenic and/or mutagenic. Lee et al.1 9 list the
relative carcinogenicities of certain PAH and show that
chrysene and the benzopyrenes have been shown to give
positive results in carcinogenicity tests. Longwell2 0 has
also shown that uoranthene, phenanthrene and the
Table 4. Polycyclic aromatic hydrocarbons in the fuels used for combustion
(mg g 1 ).
PAH

Polycyclic Aromatic Hydrocarbons (PAH) in Tyre

Pyrolysis Oil and Diesel Fuel
Table 4 shows the concentration of the main PAH in
the tyre pyrolysis oil compared to the diesel fuel and
n-hexadecane used in the furnace combustion tests. The
main constituents of the tyre oil were naphthalene,
uorene and phenanthrene and their alkylated derivatives.
In lower concentrations were acenaphthene, acenaphthylene, uoranthene, pyrene, benzo uorenes, chrysene and
benzopyrenes.
Kaminsky and Sinn5 reported concentrations of 0.85%,
0.16%, 0.29% and 0.21% by weight of tyre for naphthalene,
uorene, phenanthrene and pyrene respectively, in the
oil derived from the pyrolysis of tyre pieces at 750C in a
uidized bed reactor. Cypres and Bettens1 3 pyrolysed scrap
tyres via a two-stage process comprising an initial low
temperature pyrolysis phase followed by continuous postcracking of the volatile material at higher temperatures.
They found that concentrations of PAH increased with
Trans IChemE, Vol 76, Part B, November 1998

Naphthalene
Methylnaphthalenes
Biphenyl
Ethylnaphthalene
Dimethylnaphthalenes
Acenaphthylene
Methylbiphenyl
Acenaphthene
Trimethylnaphthalenes
Fluorene
Methyl uorenes
Phenanthrene
Anthracene
Methylphenanthrenes
Fluoranthene
Pyrene
Benzo uorenes
Chrysene
Benzopyrenes
Total
nd

Tyre oil

Diesel fuel

n-hexadecane

31.39
24.56
4.69
1.34
9.22
3.50
3.18
1.48
5.49
2.78
3.38
9.67
1.85
6.83
2.98
3.07
6.66
2.73
1.41

4.68
10.30
1.19
1.28
7.04

1.09

5.16
0.72
3.42
0.66
0.26
1.08

0.16
<0.1
<0.1
<0.1

nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd

37.34
(3.7%)

nd

126.21
(12.6%)
not detected.

298

WILLIAMS et al.

methylphenanthrenes are mutagenic in both human and

bacterial cell tests. In addition, Barfnecht et al.2 9 have
shown that the methyl uorenes are biologically active in
mutagenicity bioassays. In addition, PAH in fuels have been
associated with increases in soot formation when the fuel
is used in certain combustion systems3 0 . Table 4 shows that
biologically active PAH were present in high concentration in the tyre pyrolysis oil. For example, the tyre
oil contained PAH concentrations of 3380 ppm methyl uorenes, 2980 ppm, 9670 ppm phenanthrene, 6830 ppm
methylphenanthrenes, 2730 ppm chrysene, 1410 ppm
benzopyrenes.
The PAH found in the diesel fuel showed a similar range
of PAH species but at a lower concentration. For example,
the diesel fuel contained PAH concentrations of 3420 ppm
methyl uorenes, 660 ppm phenanthrene, 1080 ppm methylphenanthrenes, <100 ppm chrysene, <100 ppm benzopyrenes. The n-hexadecane fuel used for comparative
purposes in the furnace combustion tests showed, as
expected, negligible concentrations of PAH.
The formation of mono and polyaromatic species via
pyrolysis of alkanes to produce alkenes which are subsequently aromatized by a Diels-Alder type reaction to form
PAH is well known3 1 3 3 . For example, Cypres3 1 pyrolysed
model aliphatic compounds and con rmed the Diels-Alder
route to PAH formation in post pyrolysis cracking reactions. Pyrolysis of n-decane produced alkenes by thermal
degradation, post pyrolysis cracking of the alkenes between
600C and 900C with a 2 s residence time showed a
decrease in light alkenes and the formation of single ring
aromatic compounds, such as benzene, toluene and
alkylaromatics by Diels-Alder reactions. In addition,
naphthalene and alkylnaphthalenes were formed and
condensation reactions may continue to produce higher
PAH. Fairburn et al.3 2 examined the ash pyrolysis of
n-hexadecane in a micro-reactor at temperatures between
576C and 842C. They showed that alkenes and dialkenes
are produced which subsequently cyclise to form simple
aromatic compounds such as benzene, toluene, ethylbenzene and styrene via the Diels-Alder reaction. Higher
molecular weight PAH were formed by further reaction
between aromatic compounds and alkenes. Depeyre et al.3 3
have also suggested the Diels-Alder reaction mechanism
as the formation route for aromatic compounds and PAH
in the pyrolysis of n-hexadecane and n-nonane at temperatures between 600 and 900C.
Cypres and Bettens1 3 have applied the Diels-Alder
mechanism in their investigation of secondary cracking
reactions of tyre oil vapours to form PAH. Their results
showed an increase in phenanthrene and naphthalene as the
tyre pyrolysis vapours produced in a primary reactor were
passed to a secondary reactor maintained at between 600
and 800C. They suggested a general reaction scheme for
the aromatization of alkenes to aromatic compounds, with a
consequent increase in the methane and hydrogen of the gas
phase. They found that benzene, xylene and toluene were
present in high concentration in the tyre oil subject to a
secondary cracking temperature but there was little change
in concentration above a threshold temperature of 600C.
Cypres and Bettens1 3 suggested that the pyrolysis of tyres
led to the production of ethene, propene and 1,3 butadiene,
which react to form cyclic alkenes. Dehydrogenation of
the cyclic alkene compounds with six carbon atoms

occurred to produce single ring aromatic compounds and

as a result of subsequent associative reactions may lead
to the formation of PAH such as naphthalene and
phenanthrene.
Emissions from the Combustion of Tyre Pyrolysis Oil
The tyre pyrolysis oils were successfully combusted in
the 1.6 m long ceramic-lined furnace. The tyre oil contained
some particulate material which in the early commissioning
tests quickly blocked the spray nozzles of the burner.
However, the use of in-line ltering of the oil and regular
replacement of lters overcame this problem. The furnace
was able to operate on the tyre oil for extended periods
of several hours without problem. The tyre oil required
no special handling such as pre-heating as the viscosities
were similar to the diesel fuel also used in the furnace
combustion tests.
Table 5 shows the emission of NOx and SO2 from the
combustion of tyre pyrolysis oil and diesel fuel in relation
to excess oxygen levels. Emission levels of NOx and SO2
in the furnace ue gases were higher for the tyre pyrolysis
oil compared to when diesel fuel was used under identical
combustion conditions of excess air level. The higher SO2
concentrations for tyre pyrolysis oil were directly related
to the respective fuel sulphur contents of tyre 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 tyre pyrolysis oil.
Also shown in Table 5 are the SO2 levels calculated using
standard combustion calculations based on the respective
fuel sulphur contents. The predicted gures assumed all
the fuel sulphur was converted to SO2 ; however, it is clear
that the theoretical levels of SO2 were higher than the
measured results. This may not be altogether unexpected
since it has been shown that the sulphur species in tyre
oils and diesel fuel consist in part of polycyclic aromatic
sulphur species and may survive the combustion process
and be deposited as an unburned fuel fraction on the
particulate22,34 . In addition, the theoretical results may be
due to minor analytical errors in the determination of both
fuel sulphur content and SO2 measurements and also the
formation of SO3 which was not determined in this study.
Table 6 shows the emissions of certain PAH in the ue
gas particulate in relation to ue gas excess oxygen levels.
Table 4 showed that several other lower concentration
PAH were found in the tyre pyrolysis oils, including
benzopyrenes, benzo uorenes and chrysene, additionally
many other PAH species have been identi ed in tyre
Table 5. Emissions of NOx and SO2 from the combustion of tyre pyrolysis
oil compared to diesel fuel (ppm).
Fuel

NOx

SO2

Tyre pyrolysis oil

7.6% excess O2
5.3% excess O2
2.1% excess O2

343
466
374

Measured
440
470
530

Theoretical
475
560
670

Diesel fuel
7.6% excess O2
5.3% excess O2
2.1% excess O2

122
124
131

Measured
40
55
110

Theoretical
87
111
121

Trans IChemE, Vol 76, Part B, November 1998

COMBUSTION OF TYRE PYROLYSIS OIL

299

Table 6. Polycyclic aromatic hydrocarbons, total particulate mass and unburned hydrocarbons in the ue gas from the
combustion of tyre pyrolysis oil.
PAH, mg m

1.3% excess O2

1.1% excess O2

1.0% excess O2

Naphthalene
Methylnaphthalenes
Biphenyl
Ethylnaphthalene
Dimethylnaphthalenes
Trimethylnaphthalenes
Fluorene
Phenanthrene
Pyrene

1
12
2
2
9
8
<1
<1
<1

98
129
19
14
64
44
7
20
4

89
183
33
27
93
70
10
9
<1

Total

34

399

514

Total particulate, g m

0.06

Unburned hydrocarbons, ppm

0.36

<20

1.88

<20

pyrolysis oils1 6 ,3 4 . However, only the main PAH emitted

during the combustion tests were quanti ed and compared
with the main PAH found in the tyre pyrolysis oil and diesel
fuel used. The emissions of PAH represented those species
trapped on the particulate and extracted into the solvent
organic fraction of the particulate as described in the
experimental section. The range of excess oxygen levels
reported in Table 6 were low and much lower than the
normal operating conditions of the burner.
It should be noted that the normal operating range of the
burner was with an excess oxygen level of approximately
6%; at such levels there was no formation of particulate
and consequently PAH. In order to obtain measurable
emissions of particulates, the furnace had to be operated
under non-standard conditions, with a restricted air supply.
Even at values of ue gas excess oxygen levels of between
6.0 and 2.0%, there were no emissions of particulates and
PAH detected in the ue gases.
At the excess oxygen levels of 1.31.0%, measurable
particulate and PAH were produced in the ue gases. As the
excess oxygen levels were decreased the concentration
of particulate and PAH increased. In addition, the total
unburned hydrocarbon emissions were increased. In
general, the levels of PAH emitted were quite low and
those emitted in higher concentrations were the nonbiologically active naphthalenes and alkylated naphthalenes. The higher molecular weight PAH found in the tyre
oil and shown in Table 4 such as chrysene and the

44

benzopyrenes which have been shown to be carcinogenic

and/or mutagenic were not detected in the furnace
emissions from the combustion of the tyre oil.
Table 7 shows the emissions of certain PAH in the ue
gas particulate in relation to ue gas excess oxygen levels
when diesel fuel was combusted in the ceramiclined
furnace. Also shown in Table 7 are the emission levels
when a pure hydrocarbon, n-hexadecane, was used as the
fuel. No PAH emissions could be detected when diesel
fuel was combusted at an excess oxygen level of 1.3%;
this compared with a low but measurable emission
of 0.06 mg m 3 particulates and total PAH emission of
34 mg m 3 when tyre oil was combusted in the furnace at
the same excess oxygen level. Lower, non-standard burner
conditions of excess oxygen level had to be obtained
before any particulates or PAH could be detected. Table 7
shows that at excess oxygen levels of 0.8 and 0.5%, PAH
increased as the excess oxygen level fell. As was the case for
tyre oil, the main PAH emitted were the non-biologically
active naphthalene and alkylated naphthalenes. When
n-hexadecane was combusted at 1.0% excess oxygen level,
very low concentrations of PAH were detected producing
only a total PAH of 9 mg m 3 .
The possible sources of the PAH in the emissions from
the furnace combustion of tyre oil and diesel fuel were
either by the chemical reactions of the combustion process
or from unburned fuel2 3 . There have been many studies
of the formation of PAH from combustion, particularly

Table 7. Polycyclic aromatic hydrocarbons in the ue gas from the combustion of diesel fuel and n-hexadecane (mg m 3 ).
Diesel fuel
PAH

n-hexadecane

1.3% excess O2

0.8% excess O2

0.5% excess O2

1.0% excess O2

Naphthalene
Methylnaphthalenes
Biphenyl
Ethylnaphthalene
Dimethylnaphthalenes
Trimethylnaphthalenes
Fluorene
Phenanthrene
Pyrene

nd
nd
nd
nd
nd
nd
nd
nd
nd

7
12
2
2
7
5
<1
2
<1

11
41
10
10
39
29
1
2
23

<1
<1
<1
<1
7
<1
<1
2
<1

Total

nd

37

166

nd

not detected.

Trans IChemE, Vol 76, Part B, November 1998

300

WILLIAMS et al.

their link to soot formation. Combustion-formed PAH are

via either the chemical kinetics of the combustion process
taking place in fuel-air mixtures inside the ammability
limit or by pyrolysis of fuel vapour taking place either
in rich mixtures outside the rich ammability limit or
in low-temperature zones below the fuel ignition temperature23,35,36 . Such studies of PAH formation involved
pre-mixed ames of pure hydrocarbon fuels which upon
combustion decompose to low molecular weight compounds and radicals. Addition reactions of these compounds
and radicals result in PAH formation. Chemical kinetics
routes to the formation of soot often involve PAH precursors2 3 ,2 5 . Combustion-formed PAH tend to give very low
concentrations of PAH, lower than those found with the
unburned fuel route2 3 .
The unburned fuel route to the formation of PAH has
been identi ed by other workers for oil spray combustion
systems. Herlan2 4 investigated the combustion of a light
fuel oil in a room heater. The light fuel oil was analysed
in detail to determine the concentration of PAH and a wide
range of species were identi ed. There was a similar range
of PAH species in the exhaust particulate and it was
concluded that the source of the PAH in the exhaust
particulate was largely derived from unburned fuel.
Kozinski3 7 combusted a heavy fuel oil in a 200 kW burner
coupled to a 2.7 m long 0.6 m square furnace chamber.
A wide range of PAH from two ring naphthalene to
seven ring coronene were identi ed in the fuel. Combustion of the fuel resulted in a particulate containing a
similar range of PAH. Kozinski3 7 concluded that the PAH
in the near ame zone were largely derived from unburned
fuel. As the PAH passed along the furnace there was
oxidation of the PAH; at the same time soot concentrations correspondingly increased suggesting that the PAH
were precursors for the formation of soot. There was also
some evidence for PAH formation during the combustion
process as axial concentrations of PAH were measured
down the furnace chamber. However, the PAH that
survived the combustion process and passed through the
furnace would therefore be largely derived from unburned
fuel, but also with a contribution from combustionformed PAH.
To evaluate further the possible source of PAH in the
furnace emissions, a pure hydrocarbon fuel, n-hexadecane,
was combusted and the concentration of PAH in the exhaust
particulate determined. Table 7 shows the concentration of
PAH emitted. Whilst a range of PAH could be identi ed,
including naphthalene, alkylated naphthalenes, uorene,
phenanthrene and pyrene, they were in very low concentration compared to the results found with either diesel fuel
or tyre oil. Direct comparison of PAH emissions using the
n-hexadecane with tyre oil can be made for the 1.0% excess
oxygen condition. The total PAH were 9 mg m 3 using
n-hexadecane whereas for tyre oil the total PAH were
514 mg m 3 . Since the n-hexadecane fuel contained no PAH
the only possible source of PAH is from the combustionformed route. Comparison of the PAH emissions from
n-hexadecane with tyre oil fuel in terms of their PAHforming capability may not be legitimate since the high
concentration of aromatic compounds in the tyre oil may
result in a higher number of aromatic chemical radicals
available for combustion-generated PAH. However, Table 7
shows that approximately 2% of the PAH found from

the combustion of tyre pyrolysis oil is formed when

n-hexadecane is combusted.
CONCLUSIONS
Tyre pyrolysis oil has been successfully combusted in
a 1.6 m long ceramic-lined furnace for several hours at a
time without problem.
The tyre oil contained high concentrations of PAH
consisting of mainly naphthalene, uorene and phenanthrene and their alkylated derivatives. There were also lower
but signi cant concentrations of biologically-active PAH
including uoranthene, benzo uorenes, chrysene and benzopyrenes. Comparison with the PAH content of petroleumderived diesel fuel showed that the diesel fuel contained
a similar range of PAH but at much lower concentrations.
Combustion of tyre pyrolysis oil produced SO2 concentrations of 530 ppm at 2.1% excess oxygen and 440 ppm
at 7.6% excess oxygen, a factor of between ve and ten
times higher than found for the combustion of diesel fuel.
NOx emissions were 374 ppm at 2.1% excess oxygen and
343 ppm at 7.6% excess oxygen approximately three times
higher than were found for the combustion of diesel fuel.
The results for SO2 and NOx emissions were consistent
with higher fuel sulphur and nitrogen contents in the tyre oil.
Under normal excess oxygen operating conditions of
6% the furnace produced no particulate and no PAH
emissions when the tyre pyrolysis oil or indeed the diesel
fuel were used as the fuels.
At excess oxygen levels of approximately 1.3% and
lower, particulate was formed with the tyre pyrolysis oil
and the particulate contained PAH, which were mainly
naphthalene and alkylated naphthalenes.
Combustion of n-hexadecane produced a low but
signi cant concentration of PAH. The large majority of
PAH found in the emissions from the combustion
of tyre pyrolysis oil were attributed to unburned fuel, with
only approximately 2% of the PAH derived from the
combustion-formed route.
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ACKNOWLEDGEMENTS
We would like to thank the UK Science and Engineering Research
Council for support for this work via research grants (GR/F/06074 and GR/
H/83355). We would also like to thank Beven Recycling, Harwell,
Oxfordshire, UK for the oil samples and pyrolysis data. The award of the
John Henry Garner University of Leeds Scholarship for AMC is gratefully
acknowledged.

ADDRESS
Correspondence concerning this paper should be addressed to
Dr P. T. Williams, Department of Fuel and Energy, University of Leeds,
Leeds LS2 9JT, UK.
The manuscript was received 30 October 1997 and accepted for
publication after revision 20 May 1998.