Fuel 82 (2003) 1023–1031

www.fuelfirst.com

Temperature selective condensation of tyre pyrolysis oils to

maximise the recovery of single ring aromatic compoundsq
Paul T. Williams*, Alexander J. Brindle
Department of Fuel and Energy, The University of Leeds, Leeds LS2 9JT, UK
Received 22 November 2002; accepted 23 November 2002; available online 30 January 2003

Abstract
Scrap tyres were pyrolysed in a fixed bed reactor and the evolved pyrolysis gases were passed through a condenser system maintained at
separately controlled temperature to determine the yield and composition of the condensed oil. The main objective was to maximise the
selective condensation of single ring aromatic compounds which are of known higher commercial value. In addition, the molecular weight
range of the condensed oils was also determined. The influence of condenser packing material was also examined. The results showed that
the type of packing material within each condenser was also examined and found to be important in determining the yield and composition of
the condensed oil. Similarly, condenser temperatures determined the yield and also composition of the oils. Maximum concentrations of
single ring aromatic compounds in relation to the selective condensation process showed significant increases in the concentration of certain
compounds could be achieved in the condensed oils collected in each condenser.
q 2003 Elsevier Science Ltd. All rights reserved.
Keywords: Pyrolysis; Tyres; Recycling; Chemicals

1. Introduction addition to the steel cord, all of which have the potential to
be recycled [2,3]. Process conditions can be altered to
The annual production of scrap tyres throughout the maximise the yield of char, oil or gas, for example, higher
world is estimated at 1000 million, representing a significant pyrolysis temperatures cause the higher molecular weight
treatment and disposal problem. The tyre also represents a oil species to thermally degrade to gas. Rapid removal of the
potentially valuable source of energy, raw materials and pyrolysis gases from the hot zone of the reactor such as with
chemicals. However, in most countries, the preferred option fluidised bed reactors, gas purged fixed bed reactors or
vacuum pyrolysis systems tend to maximise the production
for disposal is landfill or stockpiling. Other treatment
of oil [2 –5].
options for tyres have included the retreading of scrap tyres
There is much interest in the production of hydrocarbon
and the use of crumbed tyres in sports fields, playgrounds,
liquids from waste materials, particularly tyres, since the
pavements and roads. Energy recovery schemes have
production of a liquid product increases the ease of
included for example, tyre incinerators with energy
handling, storage and transport and hence the oil product
recovery and the use of tyres in cement kilns. With
does not have to be used at or near the pyrolysis plant. The
increasing emphasis on recycling of waste, alternative
yield of oil from tyres can be up to 58 wt% of the tyre rubber
process routes for tyres have been examined with the aim of
and the oil has broad fuel properties similar to commercial
recovering some of the value in the tyre [1]. One process
grade light fuel oil/diesel fuel. For example, the energy
which has received considerable recent attention is
value of the oil is 42 MJ kg21 and sulphur content between
pyrolysis of the tyre to produce an oil, gas and char in
0.5 and 1.5 wt% depending on process conditions, and
therefore the pyrolysis oils may be combusted directly [6].
* Corresponding author. Tel.: þ44-1132-33-2504; fax: þ 44-1132-46-
7310.
The oils are chemically very complex, consisting of a range
E-mail address: p.t.williams@leeds.ac.uk (P.T. Williams). of alkanes, alkenes and aromatic species with a molecular
q
Published first on the web via Fuelfirst.com—http://www.fuelfirst.com weight range from , 50 to . 1000 Da [2]. However, of most
0016-2361/03/$ - see front matter q 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0016-2361(03)00016-4
1024 P.T. Williams, A.J. Brindle / Fuel 82 (2003) 1023–1031
interest, the oils have been shown to contain valuable
chemicals such as, benzene, toluene, xylenes and limonene
in significant concentrations which are used in the chemical
industry [3,6 – 8]. The economic importance of such single
ring aromatic chemicals suggests that identification of
processes which maximise the concentrations of such
chemicals would generate a product oil which has potential
as a chemical feedstock rather than a liquid fuel.
In this paper, scrap tyres have been pyrolysed in a fixed
bed reactor and the pyrolysis gases have been passed
directly to a condenser system designed to selectively
condense the pyrolysis gases at different temperatures. The
aim of the work was to obtain condensed fractions of oil
containing increased concentrations of single ring aromatic
compounds. The selective condensation process is mainly
dependant on the dew point of the components of the oil,
which is closely linked to the boiling point of that
compound so it becomes apparent that selective conden-
sation would prove useful for the fractionation of pyrolysis
oil into different temperature indicative cuts. The tempera-
ture selective condensation is analogous to the separation of
the components of oils via distillation. However, tempera-
ture selective condensation differs from distillation in that
fractionation is achieved by cooling gaseous products to
liquids rather than in the case of distillation where oil is
transformed from its liquid state to a vaporous state to afford
separation. The parameters examined were the type of
Fig. 1. Schematic diagram of the pyrolysis reactor and temperature selective condensation system.
packing material used in the condenser and the condenser
temperature.
2. Materials and methods
2.1. Tyres
The tyre rubber used for pyrolysis was obtained from
shredded and crumbed passenger car tyres. The crumbed tyre
rubber was sieved to produce a size range of 1.0 –1.4 mm. A
typical analysis of the tyre, on a steel- and fabric-free basis
was, carbon 86.4 wt%, hydrogen 8.0 wt%, nitrogen 0.5 wt%,
and sulphur 1.7 wt%. The proximate analysis of the tyre
crumb was, volatiles, 62.2 wt%, fixed carbon 29.4 wt%, ash
content 7.1 wt% and moisture content 1.3 wt%. The tyre
rubber had a calorific value of 40.0 MJ kg21.
2.2. Pyrolysis reactor and temperature selective
condensation system
Fig. 1 shows a schematic diagram of the fixed bed
pyrolysis reactor and temperature selective condensation
system. The reactor was constructed of stainless steel and
was 10 cm diameter £ 15 cm high. Each experiment con-
sisted of the pyrolysis of 150 g of tyre crumb. Heating was
via an external electrical heater and temperatures were
 P.T. Williams, A.J. Brindle / Fuel 82 (2003) 1023–1031
controlled to give the sample a ramped heating rate of
5 8C min21 to the final tyre pyrolysis temperature of 570 8C
and held at that temperature for 1 h or until pyrolysis was
complete. The pyrolysis temperature of 570 8C was selected
to ensure complete pyrolysis of the tyre. Temperatures were
monitored throughout the reactor. A continuous purge of
inert nitrogen was introduced to the reactor via a perforated
ring located at the base of the reactor. The nitrogen flow rate
gave a maximum gas residence time of approximately 30 s
within the reactor. The tyre was contained in a sample cage
which fitted into the reactor, flush with the reactor walls. The
sample cage was removable allowing the sample to be
introduced and post-reaction solid product to be removed
easily. Gases exited the reactor downwards via an exit tube
located above the sample cage.
The pyrolysis gases were passed directly to the temperature
controlled condensation system. The first three condensers
were constructed of stainless steel followed by a set of four
glass condensers (impingers). The stainless steel condensers
were located inside separate furnaces and could be tempera-
ture controlled at selected temperatures, monitored by a
thermocouple placed inside the condenser. Condensers were
tested with no packing, a mesh packing (rather like packed
wire wool) and pall rings (similar to perforated steel tubes).
The steel gauze mesh and pall ring packings were stainless
steel and were designed to provide a high surface area and
impingement surface for the pyrolysis gases to condense onto.
These packing materials were compared to experiments where
the condensers had no packing material. Condenser tempera-
ture was tested for temperatures of 100, 150, 200 and 250 8C to
ascertain its effect on separating the oil into separate
condensed oil fractions. For each set of experiments, all
three stainless steel condensers were held constant at one
particular temperature, being either 100, 150, 200 or 250 8C.
The glass condensers were all maintained at about 270 8C
using solid carbon dioxide/acetone. The oil was removable
from each condenser at the end of the experiment. Throughout
each experiment gas samples were taken using PTFE gas
sample syringes and the gases were analysed off-line using
packed column gas chromatography. The gas samples were
taken after the oil condensation system.
Oil yield data for inclusion in the determination of mass
closure was obtained by weighing each condenser, includ-
ing packing material, connecting pipes and condensed oil
before and after pyrolysis. Additionally the mass of tyre
before pyrolysis and mass of char after reaction were
determined by weighing. The mass of each gas produced
was obtained from the gas composition analysis using gas
chromatography, the gas yield profile of each gas through-
out the duration of the experiment together with the
molecular mass data for each gas.
2.3. Gas analysis
Gas composition throughout each experiment was
determined from the analysis of the gases sampled using
1025
the gas syringes. The gases were analysed for hydro-
carbon and non-hydrocarbon gases. Hydrocarbons from C1
to C4 were analysed using a Pye-Unicam gas chromato-
graph with flame ionisation detector, glass column
2.2 m £ 6 mm packed with n-octane Porasil C of 80–
100 mesh size and nitrogen carrier gas. Nitrogen,
hydrogen, oxygen and carbon monoxide were analysed
with a Pye Unicam series 204 gas chromatograph with a
thermal conductivity detector. The column used was made
of stainless steel being 1.8 m £ 6 mm dimensions with
argon as the carrier gas. The silica packing was 5 Å sized
molecular sieve. Carbon dioxide was analysed using a
Gow – Mac Spectra gas chromatograph with a
1.8 m £ 6 mm stainless steel column packed with 100–
120 mesh silica gel, helium carrier gas and thermal
conductivity detector.
2.4. Oil analysis
The oils collected in each of the three stainless steel
condensers was analysed separately. The oils from the four
glass condensers were bulked and analysed together. The
weight average molecular weight of the oils was determined
using size exclusion chromatography. The analytical system
consisted of a 30 £ 0.78 cm column packed with silica
beads of an average pore size of 50 Å, giving the column a
molecular weight exclusion limit of 3000 Da. Samples were
injected with a Rheodyne injection valve with a 20 ml
sample loop. The eluant used was tetrahydrofuran with dual
ultra-violet and refractive index detection. The ultra-violet
data only is presented here since it gave better detection
levels, superior signal to noise ratios and inherent stability.
Calibration of the size exclusion chromatography system
was with a range of standards, including polystyrene
standards with molecular weights of 480, 1050, 1350,
1770 and 2550. Additionally, aromatic and polycyclic
aromatic hydrocarbon standards of lower molecular weights
were used for calibration including benzene (MW of 78),
naphthalene (MW of 128), anthracene (MW of 178),
chrysene (MW of 228) and benzanthracene (MW of 228).
The oils were analysed for their composition of single
ring aromatic compounds, in particular, toluene, xylenes
and limonene, using capillary column gas chromatography.
The chemical complexity of tyre pyrolysis oils usually
involves complex analytical methodologies [3], however,
for this work, as only certain single ring aromatic
compounds were to be analysed, a simple analytical scheme
was adopted. The pyrolysis oils collected from the
condensers were diluted with a suitable solvent to a
known concentration and analysed directly using gas
chromatography with flame ionisation detection. The gas
chromatograph used was a Fisons 8000 with on-column
injection. The column used was a non-polar polydimethyl-
siloxane HT-5 capillary column 30 m in length by 0.32 mm
diameter giving 70,000 theoretical plates/meter and the
carrier gas was helium at a flow rate of 2 ml min21 at 40 8C.
1026 P.T. Williams, A.J. Brindle / Fuel 82 (2003) 1023–1031

The temperature programme of the oven was 40 8C for
2 min followed by a ramp rate of 5 8C min21 to 380 8C, at
which point the oven was held isothermally for 20 min to
ensure elution of all low volatility material.
Toluene, m-, p-, and o-xylene and limonene standard
compounds were used for identification and quantification
via calibration curves in the range 50 –1000 ppm. Identifi-
cation of the single ring aromatic species was also aided by
coupled gas chromatography/mass spectrometry.
3. Results and discussion
3.1. Product yield and gas composition
The pyrolysis of scrap tyres was undertaken at the same
conditions of pyrolysis, but with alterations to the
condensation system, in terms of the type of packing
material used in the condenser and the condenser tempera-
ture. Therefore, as expected, all of the pyrolysis experiments
yielded the same mass balance, since pyrolysis conditions
were identical. The pyrolysis conditions were, a heating rate
of 5 8C min21 to a final pyrolysis temperature of 570 8C,
with a nitrogen gas flow rate of 1.5 l min21. The mean
product yield was a total gas yield of 4.3 wt%, oil yield of
57.1 wt% and char yield of 38.7 wt%. The analysis of the
repeatability of the experiments showed excellent precision
giving standard deviations of 0.19, 0.17 and 0.05 wt% for
the gas, oil and char yields, respectively. Similarly, the gas
composition was the same for each experiment.
Table 1 shows the average gas composition. The gas
composition was mainly composed of alkane and alkene
gases, carbon monoxide, carbon dioxide and hydrogen. The
rubber types used in tyre manufacture include, styrene –
butadiene – rubber, natural rubber (polyisoprene), nitrile
rubber, chloroprene rubber and polybutadiene rubber. The
thermal degradation process will produce highly reactive
free radicals which are often sub-units of the original rubber
Table 1
Gas composition from the pyrolysis of scrap tyres
Gas Yield (wt%)
Hydrogen 0.25
Carbon monoxide 0.22
Carbon dioxide 0.60
Methane 0.96
Ethane 0.51
Ethene 0.40
Propane 0.43
Propene 0.60
Isobutane 0.16
Butane 0.12
But-2-ene 0.02
But-1-ene 0.07
Butadiene 2.13
Total 4.27
molecule [9]. Consequently, the high concentration of
alkenes and dienes and butadiene in particular, are probably
derived as primary degradation products from the thermal
degradation of the tyre rubber. Secondary reactions of
the pyrolysis gases in the hot zone of the reactor will also
lead to the formation of butadiene, methane and hydrogen.
3.2. Influence of condenser packing material
The influence of the packing material placed in the three
stainless steel condensers was examined, using no packing,
a mesh packing, and large and small pall rings. For this
section of the experimental work, all of the steel condensers
were kept at the same temperature of 100 8C. A set of four
glass condensers (impingers), were placed after the three
stainless steel condensers to trap all of the oil. It has
been shown that the presence of a packing material within
the condensers would be beneficial to the efficiency of the
column [10]. The distribution of oil throughout the
condensation system in relation to the packing material
compared to no packing material being present in the
condensers is shown in Fig. 2. It should be noted that the oil
yield was the same for each experiment at 57.1 wt%, only
the distribution of the oil in each condenser changing with
experimental conditions.
For each experiment, all of the three stainless steel
condensers contained either no packing material, mesh,
small pall rings or large pall rings. It was apparent that the
use of pall rings made a significant difference to the
efficiency of the condensation units in condensing oil from
the vapour stream compared to no packing material or mesh.
Both types of pall rings were found to give similar oil
distributions between the three condensation units and the
cooled glass impingers. The improvement in the collection
efficiency of the stainless steel condensation system with the
pall rings was significant. The pall ring packed first column
collected nearly 45% of the pyrolysis oil whereas an
unpacked column condensed only 32% from the vapour
phase. The three packed condensation units removed nearly
70% of the oil from the vapour stream as opposed to the
unpacked condenser train which removed just under 60%.
Pall rings greatly increase the contact surface area within the
condenser. The condenser works by encouraging mass
transfer from the gaseous phase by providing a surface of
condensable temperature. Increasing this surface allows
more of the vapour stream to come into contact with the
surface and allow condensation of condensable vapours at
that given temperature. This reduced the amount of
potentially condensable vapour that bypassed the conden-
sation unit. The improved efficiency of the pall rings was
also attributed to their ability to make the flow of vapour
tortuous and fragmented without reducing the volume of the
condensation unit by a significant amount. Pall rings are
designed to have an extremely high surface area and a high
void volume. Once introduced into the condensation reactor
shell they impart maximum surface area (leading to
 P.T. Williams, A.J. Brindle / Fuel 82 (2003) 1023–1031 1027

Fig. 2. Influence of the presence and type of packing material in the condensation system on the fraction of oil collected in each condenser.

increased mass transfer) whilst reducing the volume of the
condenser by only a small amount.
The use of the mesh packing was found to give
efficiencies of condensation which were only slightly better
than those of the unpacked columns. This indicated that the
mesh was not as effective as pall rings in promoting mass
transfer processes. However, this may have been due to flow
channelling since the mesh was rolled up and placed in the
condenser leading to open channelling within the mesh.
The oil condensed in each of the three stainless steel
condensers and a bulked sample of oil collected from all of
the set of glass condensers was analysed for their weight
average molecular weight using size exclusion chromatog-
raphy. This gave four sets of oils for each experiment. This
data was used to examine the effectiveness of the
condensation system in condensing the tyre pyrolysis oil
into condensed fractions of different molecular weights.
Fig. 3 shows the influence of the type of packing material
on the average molecular weight of the oils collected from the
various condensed fractions of the online condensation
system. Using no packing at all gave the smallest range of
molecular weights between condensed fractions. The
difference in average molecular weight between the oil
collected in the first condenser and that collected in the
cooled impingers was only 40 Da. In comparison, the use of
mesh packing produced condensed oils with a significantly
wider range of average molecular weights from 305 Da in the
first condenser to 240 Da in the cooled glass impingers,
a range of 65 Da. The presence of the pall ring type packing
material further increased this range of average molecular
weights to over a 100 Da. Increasing the range of average
molecular weights of the oils collected across the first,
second, third steel condensers and the set of glass impingers
indicated that the condensation system was working more
efficiently, fractionating the condensable oils into more
distinct molecular weight streams. The small range of
molecular weights between the first condenser and the
glass impingers of the condenser system without packing
material, suggested that a significant amount of higher
molecular weight material had been carried through the
condenser system to be collected in the final glass impingers.
This was undesirable since the aim of the experiments was to
try and fractionate the heavier weight molecular weight
material separately from the lower molecular weight oils.
The use of pall rings greatly improved this molecular
weight difference between the fractions of condensed oils

Fig. 3. Molecular weight range of the condensed tyre pyrolysis oils in relation to the presence and type of packing material in the condensation system.
1028 P.T. Williams, A.J. Brindle / Fuel 82 (2003) 1023–1031
indicating better separation of higher molecular weight
material from lower molecular weight material.
The selective condensation system was examined for its
effectiveness at increasing the higher value chemicals,
toluene, m/p-xylene, o-xylene and limonene in the various
oil fractions condensed in each condenser. In relation to the
type of packing material, the yields of these chemicals
derived from tyre pyrolysis under the fixed conditions of
pyrolysis were constant since the pyrolysis parameters
remained the same, only the type of condensation system
examined changed between experiments. The concentration
of these chemicals in the total tyre pyrolysis oil was
determined by collecting the oil in a single oil fraction and
analysing as a whole. The concentrations determined were,
o-xylene, 0.2 wt%, m/p-xylene 1.1 wt%, toluene, 1.1 wt%
and limonene 3.6 wt%.
Fig. 4 shows the influence of the condenser packing
material on the yields of xylenes, toluene and limonene in
the oils collected in each condenser. The effect of the
packing material was to aid in the selectivity of the
condensation system by increasing the yields of high
value chemicals found in the final glass impinger conden-
sation fraction with a consequent reduction in concentration
in high value chemicals in the condenser fractions 1 – 3. The
presence of the mesh packing in the stainless steel
condensers was found to be marginally beneficial to the
selectivity of the system compared to the presence of no
packing material, increasing the concentrations of the high
value chemicals in the final glass impinger condenser set.
The biggest increase in selectivity was demonstrated by the
use of the pall ring packing material which increased the
Fig. 4. Concentration of xylenes, toluene and limonene in the condensed tyre pyrolysis oils in relation to the presence and type of packing material in the
condensation system.
concentration of limonene condensed in the final glass
impinger fraction from 4.8 to 6.8 wt%. Similar relative
increases in the final condensation set were seen for toluene
which increased in the oil fraction collected in the glass
impingers from 1.9 to 3.2 wt% and for m/p-xylene which
increased from 1.8 to 2.8 wt%. As a consequence of these
increases in concentration of chemicals in the impinger
stream there was a corresponding decrease in the concen-
tration of these chemicals in the preceding stainless steel
condensers, particularly condenser 1. The improved selec-
tivity towards higher concentrations of single ring aromatic
compounds in the condensed oils collected in the final glass
impinger condenser was reflected in the oil molecular
weight data shown in Fig. 3. That data showed that the final
glass impinger condenser collected oil with a lower
molecular weight distribution when pall rings were added
compared to no packing material being present in the
stainless steel condensers.
3.3. Influence of condenser temperature
Fig. 5 shows distribution of condensed oil in the stainless
steel condensers and glass condensers when the stainless
steel condensers were all maintained at either 100, 150, 200
or 250 8C. For this set of experiments, the three stainless
steel condensers were packed with the small pall ring
packing material, since these produced the highest con-
denser efficiency. It should be noted that for each
experiment, all three stainless steel condensers were held
at the same temperature and the glass condensers were
maintained at 2 70 8C and collected all of the remaining oil
 P.T. Williams, A.J. Brindle / Fuel 82 (2003) 1023–1031 1029

Fig. 5. Influence of the temperature of the three stainless steel condensers on the fraction of oil collected in each condenser.

which passed through the first three condensers. Fig. 5
shows that increasing the condenser temperature reduced
the mass balance of oils distributed to the steel condensation
units, a higher mass percentage of oil exited the steel
condensers and was trapped in the final glass impingers.
When the three steel condensers were maintained at 100 8C,
67% of the oil was condensed in the steel condensers, at a
condenser temperature of 250 8C, 50% was collected in the
first three steel condensers. This was reflected in the
collected oil fraction for condenser 1 which collected 42%
at 100 8C and at 250 8C it contained just 25%.
Increasing the condenser temperature above the tem-
perature at which a compound condenses will keep it in the
vapour phase. Hence, compounds that condensed in the
condenser system at 100 8C were eluted to the final glass
impinger condenser system at 250 8C. In addition, by
increasing the temperature of the condensers, the gas flow
velocity would also increase and therefore a reduction in the
gas residence time would occur. The gas residence time at a
condenser temperature of 250 8C was calculated to be 30%
less than at a 100 8C condenser temperature. This would
have an effect on the efficiency of the condensation units
since residence time is an important factor in obtaining good
equilibration and better mass transfer.
Fig. 6 shows the influence of the stainless steel condenser
temperature on the weight average molecular weight
throughout condensation system, where the packing
material was small pall rings. Increasing the temperature
of the heated stainless steel condensation system was, as a
whole, found to give increased molecular weights for oils
collected in the steel condensers. A higher condenser
temperature resulting in fewer compounds of lower
molecular weight condensing until they reach the glass
condenser system which was cooled to 2 70 8C. This effect
was particularly noticeable in steel condenser 1 where the
weight average molecular weight increased from 306 to
368 Da. The two further condensers also showed similar,
but smaller, increases in the molecular weight of the
collected oil. Reference to Fig. 5 for the oil distribution data,
showed that although less oil was collected at the highest
condenser temperature for the three steel condensers and
condenser 1 in particular, it was of a higher molecular

Fig. 6. Molecular weight range of the condensed tyre pyrolysis oils in relation to the temperature of the three stainless steel condensers.
1030 P.T. Williams, A.J. Brindle / Fuel 82 (2003) 1023–1031
weight. One of the effects of increasing the condenser
temperature could have been the exit of more higher
molecular weight material to the glass impinger, condenser
system because of their inability to condense out of the
vapour phase. However, this was not the case, and
increasing stainless steel condenser temperature appeared
to have improved the selectivity of the system. Fig. 6 shows
that increasing condenser temperature actually decreased
the molecular weight of the oil found in the glass impingers.
Hence, the effect of increasing condenser temperature was
to improve the efficiency and selectivity in relation to the
average molecular weight of the oils collected in each
condenser.
The influence of the temperature of the stainless steel
condensers on the concentration of xylenes, toluene and
limonene in the condensed oils was examined and the
results are shown in Fig. 7. Fig. 7 shows that as the
temperature of the steel condensation system was
increased, so too did the difference in concentrations of
the toluene, xylenes and limonene in the glass impingers
compared to the steel condensers. For example, the
concentration of limonene in the oil fraction collected in
condenser 1 at a condensation system operating tem-
perature of 100 8C was 1.5 wt%, whilst in the glass
impingers it was 6.8 wt%. At a steel condenser
temperature of 250 8C the concentration of limonene in
Fig. 7. Influence of the temperature of the three stainless steel condensers on the concentration of xylenes, toluene and limonene in the condensed tyre pyrolysis
oils.
the oil in condenser 1 was reduced to 0.5 wt% a factor of
three reduction. In addition, the concentration of
limonene in the glass impingers was also reduced, but
to a lesser extent, at 5.6%. Similarly, at a condensation
system operating temperature of 100 8C both toluene and
m/p-xylene were present throughout the condensation
system at low levels (< 0.3%) whilst at 250 8C these
chemicals were only found in the glass impinger
condensed oil. It should be noted that the overall yields
of high value chemicals remained similar because
pyrolysis conditions had not changed; the differing
concentrations were the effect of condensation par-
ameters. Totalling the concentration of high value
chemicals of a particular stream with the amount of oil
collected in that stream gave yields similar to those
where all the oil was condensed and bulked to give one
oil sample at o-xylene, 0.2 wt%, m/p-xylene 1.1 wt%,
toluene, 1.1 wt% and limonene 3.6 wt%. It has been
suggested that limonene degrades readily to benzene,
xylene, toluene, trimethylbenzene, styrene and methyl-
styrene [7]. However, this degradation occurs above
temperatures of about 450 8C rather than the maximum
condenser temperature used in this work of 250 8C.
At the higher steel condensation temperatures in
condensers 1– 3, reduced concentrations of toluene, xylene
and limonene were found. This was due to in part, the
 P.T. Williams, A.J. Brindle / Fuel 82 (2003) 1023–1031
reduced gas residence time at the higher temperature of
about 30% as the condensation system was increased from
100 to 250 8C. This would allow less time for compounds to
equilibrate with the surroundings, especially important
if their dew point was just below the condensation
temperature. In addition, as the condensation temperature
was increased, compounds which condense at 100 8C are
less likely to do so at 250 8C therefore greatly reducing their
condensation. It should be noted that the condensation
system design was not optimal with respect to equilibrium
and kinetic conditions.
Fig. 7 also shows that there was a steady decrease in
toluene, xylenes and limonene condensed in the glass
impinger condenser system as the temperature of the steel
condensers 1 – 3, was increased. For example, the concen-
tration of limonene in the oil collected in the glass impinger
condensation fraction was reduced from 6.8 to 5.6 wt% and
the concentration of m/p-xylene was reduced from 2.8 to
2 wt%. This data should be compared to Fig. 5 which shows
that the lower concentration of toluene, xylenes and
limonene in relation to increased condenser temperature
was linked to the higher oil yield carried through to the final
glass impinger. That is, the concentration of these chemicals
in the oil had decreased, but the amount had increased.
Since the same amount of toluene, xylenes and limonene
were obtained overall, irrespective of the condensation
system temperature, it is apparent that the enhanced overall
amount of these chemicals in the oil collected in the final
glass impingers aids the selective concentration by selective
temperature condensation of these chemicals.
4. Conclusions
The pyrolysis of scrap tyres was investigated with a
condensation system which could be controlled to different
temperatures. The influence of the condenser temperature
on the distribution of oil and the composition of the oil in
each fraction was examined. However, initial experiments
were carried out to determine the most suitable type of
condenser packing material which would aid the conden-
sation process. The distribution of oil in the condenser
system was found to be optimal in terms of the amount of oil
condensed, the range of molecular weights of the oil and
1031
the concentrations of toluene, xylene and limonene when
pall rings were used as the condenser packing material.
When the temperature of the first three steel condensers was
increased, it was found that more oil was carried through to
the final glass impinger condensers. It was also found that
the condensed oils in the initial condensers contained higher
molecular weight material. The oils condensed in the final
glass impingers at the higher condensation temperatures had
lower concentrations of toluene, xylenes and limonene
compared to the lower condenser temperatures. However,
whilst the concentration of each species was lower, the total
mass in each oil fraction increased, since the yield of oil in
the final glass condenser had increased.
Acknowledgements
The authors gratefully acknowledge the support of the
UK Engineering and Physical Science for support for this
work (Grant No. GR/L35331/01).
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