Pyrolysis of Waste Tyres A Review

Waste Management 33 (2013) 1714–1728
Contents lists available at SciVerse ScienceDirect
Waste Management
journal homepage: www.elsevier.com/locate/wasman
Review
Pyrolysis of waste tyres: A review

Paul T. Williams ⇑
Energy Research Institute, The University of Leeds, Leeds LS2 9JT, UK
a r t i c l e i n f o a b s t r a c t
Article history: Approximately 1.5 billion tyres are produced each year which will eventually enter the waste stream rep-
Received 19 March 2013 resenting a major potential waste and environmental problem. However, there is growing interest in
Accepted 2 May 2013 pyrolysis as a technology to treat tyres to produce valuable oil, char and gas products. The most common
Available online 2 June 2013
reactors used are fixed-bed (batch), screw kiln, rotary kiln, vacuum and fluidised-bed. The key influence
on the product yield, and gas and oil composition, is the type of reactor used which in turn determines
Keywords: the temperature and heating rate. Tyre pyrolysis oil is chemically very complex containing aliphatic, aro-
Review
matic, hetero-atom and polar fractions. The fuel characteristics of the tyre oil shows that it is similar to a
Tyres
Pyrolysis
gas oil or light fuel oil and has been successfully combusted in test furnaces and engines. The main gases
Oil produced from the pyrolysis of waste tyres are H2, C1–C4 hydrocarbons, CO2, CO and H2S. Upgrading tyre
Char pyrolysis products to high value products has concentrated on char upgrading to higher quality carbon
Gas black and to activated carbon. The use of catalysts to upgrade the oil to a aromatic-rich chemical feed-
stock or the production of hydrogen from waste tyres has also been reported. Examples of commercial
and semi-commercial scale tyre pyrolysis systems show that small scale batch reactors and continuous
rotary kiln reactors have been developed to commercial scale.
Ó 2013 Elsevier Ltd. All rights reserved.
1. Introduction are used in material recovery options through the production of

rubberised flooring in sports fields and playgrounds, paving blocks,
It is estimated that 1,500,000,000 tyres are produced worldwide roofing materials, etc. A significant proportion of the waste tyres
each year which will eventually end-up as waste tyres (ETRMA, are used in civil engineering applications such as road and rail
2011). In terms of tonnages, waste tyres represent a significant foundations and embankments (0.24 million tonnes) re-treaded
proportion of the total solid waste stream. For example, approxi- (0.26 million tonnes) or exported (0.33 million tonnes) each year
mately 3.3 million tonnes of waste tyres were generated annually (ETRMA, 2011). Sienkiewicz et al. (2012) have extensively re-
within Europe (EU-27) in 2010 and an estimated stockpile of 5.7 viewed the waste treatment routes for waste tyres in the European
million tonnes of waste tyres throughout Europe (ETRMA, 2011). Union and its Member States and the possible uses of waste tyres
The management of waste tyres in the European Union has been as a source of raw materials or alternative fuels.
regulated under the End of Life Vehicle Directive which stipulates Typical compositions of passenger and truck tyres are shown in
the separate collection of tyres from vehicle dismantlers and Table 1 (Evans and Evans, 2006). The rubbers and elastomers
encourages the recycling of tyres (EC, 2000). In addition, the EU which make up the rubber component of the tyre are a mixture
Waste Landfill Directive has banned the landfilling of tyres (EC, of several rubbers strengthened with carbon black filler material.
1999). These Directives have dramatically changed the tyre waste The construction of the tyre involves a composite of several layers
treatment routes in the EU over the last 15 years. For example in of the rubber, textile material and steel belt and cord.
1996 approximately 50% of waste tyres were sent to landfill, how- There has been great interest in alternative treatment processes
ever, currently the figure is only 4% (0.13 million tonnes/year) for waste tyres, amongst which is the use of pyrolysis technology
(ETRMA). The main options used for treating waste tyres are (Sienkiewicz et al., 2012). Pyrolysis is the thermal degradation of
through the use of tyres as fuel in cement kilns which accounts the organic components of the tyres, at typical pyrolysis tempera-
for more than 1.15 million tonnes of the total 3.3 million tonnes tures of 500 °C to produce an oil, gas and char product in addition
of waste tyres generated each year in the EU (ETRMA, 2011). Other to the recovery of the steel. The oil may be used directly as a fuel,
energy recovery options for tyres include use in power plants and added to petroleum refinery stocks, upgraded using catalysts to a
co-incineration with other wastes which use approximately 0.1 premium grade fuel or used as a chemical feedstock. The gases
million tonnes per year of tyres. About 1.1 million tonnes of tyres from tyre pyrolysis are typically composed of C1–C4 hydrocarbons
and hydrogen with a high calorific value, of sufficient energy
⇑ Tel.: +44 1133432504. content to act as fuel to provide the heat for the pyrolysis process.
E-mail address: [email protected] The solid char consists of the carbon black filler and also char
0956-053X/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.wasman.2013.05.003
P.T. Williams / Waste Management 33 (2013) 1714–1728 1715
Table 1
Typical composition of passenger and truck tyres (Evans and Evans, 2006).
Component Passenger tyre Truck tyre Comments

(wt.%) (wt.%)
Rubber 47 45 Many different synthetic and natural rubbers are used, e.g. styrene–butadiene rubber, natural rubber (polyisoprene),
nitrile rubber, chloroprene rubber, polybutadiene rubber
Carbon 21.5 22 Used to strengthen the rubber and aid abrasion resistance
black
Metal 16.5 21.5 Steel belts and cord for strength
Textile 5.5 – Used for reinforcement
Zinc oxide 1 2 Used (with stearic acid) to control the vulcanisation process and to enhance the physical properties of the rubber
Sulphur 1 1 Used to cross link the polymer chains within the rubber and also to harden and prevent excessive deformation at
elevated temperatures
Additives 7.5 5 e.g. Clay or silica used to partial replacement carbon black
produced during the pyrolysis of the rubber. It may be used as a so- maximise oil yields of between 54 and 58.8 wt.%, pyrolysis
lid fuel, as carbon black or upgraded to produce an activated temperatures of 600–720 °C were required. It should be noted that
carbon. raising the temperature in a fixed bed reactor system beyond
In this paper, the pyrolysis of tyres is reviewed in terms of the where the rubber has been thermally degraded only marginally in-
range of pyrolysis reactors used. The influence of process parame- creases the yield of oil and gases. These oils and gases are most
ters, on the yield and composition of the products from the pyroly- probably produced from the volatilisation of some of the solid, very
sis of tyres are discussed. The fuel properties of the oils and their higher molecular hydrocarbon content of the char (Dodds et al.,
detailed chemical composition are discussed, the characteristics 1983).
of the chars and gas composition is presented in detail. The re- Using a larger fixed bed reactor with a feedstock loading of
search related to producing higher value products from the tyre 1.5 kg and a pyrolysis temperature of 475 °C and heating rate of
pyrolysis process is also reviewed. The range of pyrolysis reactors 5 °C min 1 Cunliffe and Williams (1998a) obtained yields of oil,
at the commercial and semi-commercial scale are also discussed. char and gas at 58.2 wt.% oil, 37.3 wt.% char and 4.5 wt.% gas. Islam
et al. (2011) using a fixed bed reactor pyrolysed 750 g batches of
waste tyre and also found a high oil yield of 55 wt.% at 475 °C pyro-
2. Pyrolysis reactors and product yield
lysis temperature with a corresponding char and gas yield of
36 wt.% and 9 wt.% respectively. Kar (2011) pyrolysed 10 g batches
A range of different reactors, such as fixed-bed (batch), screw
of waste tyres in a fixed bed, nitrogen purged reactor at
kiln, rotary kiln, vacuum and fluidised-bed have been used for
10 °C min 1 heating rate. The influence of pyrolysis temperature
pyrolysis of waste tyres. Table 2 shows the range of pyrolysis reac-
from 375 to 500 °C was investigated and it was reported that the
tors used to research the pyrolysis of waste tyres and the yields of
maximum oil yield of 60.0 wt.% oil was obtained at 425 °C. At the
oil, char and gas from the process. In some cases, the data include
higher temperature of pyrolysis, of 500 °C, the oil yield decreased
the recovery of the steel belt and cord which typically ranges from
to 54.12 wt.%. The gas yield increased from 2.99 to 20.22 wt.%
10 to 15 wt.% of the waste tyre. Fixed bed, batch reactors have been
and char yield decreased from 50.67 to 26.41 wt.% as the temper-
widely used to investigate pyrolysis of waste tyres. The reactor is
ature of pyrolysis was increased from 375 to 500 °C. However,
typically heated externally by an electric furnace and nitrogen or
for similar pyrolysis conditions, Banar et al. (2012) reported that
another inert gas is used as a carrier gas. The thermally degrada-
for pyrolysis of tyre derived fuel (steel removed) the maximum
tion of the tyre starts at around 350 °C and therefore pyrolysis
oil yield was only 38.8 wt.%, with char yield at 34 wt.% and a high
experiments are usually in the range of 450–700 °C. The derived
gas yield of 27.2 wt.% for a heating rate of 5 °C min 1 at a pyrolysis
gas products are carried by the carrier gas and condensed down-
temperature of 400 °C. A similar oil yield of 38.0 wt.% at the pyro-
stream and the non-condensable gases are collected and analysed.
lysis temperature of 500 °C and 15 °C min 1 heating rate was ob-
The residual char and any steel are collected after experimentation.
tained by Laresgoiti et al. (2004) and de Marco et al. (2001). Rada
Although there are some commercial fixed bed batch reactors for
et al. (2012) also obtained an oil yield of 40 wt.% and gas yield of
processing tyres (see Section 7), the desire for a continuous process
20 wt.% and char yield of 40 wt.% for the fixed bed batch pyrolysis
has led to investigations of rotary kilns, moving bed screw reactors
of tyres. Differences in heating rates and in particular pyrolysis gas
and fluidised beds. In such systems the waste tyre is fed directly to
residence times can significantly impact the relative yields of oil
the hot reactor.
and gas, where higher temperatures of pyrolysis and long gas res-
idence times in the hot zone of the reactor can crack the oil to gas.
2.1. Fixed bed reactors Williams et al. (1990) reported that increasing the heating rate
showed an increase in gas yield, being 6.6 wt.% at 5 °C min 1 heat-
Aydın and Ilkılıc (2012) investigated the pyrolysis of waste ing rate which increased to 14.8 wt.% gas at 80 °C min 1 heating
tyres, with steel and fabric removed, in a 1.15 l capacity fixed rate, where both experiments were undertaken at 720 °C pyrolysis
bed reactor in nitrogen over the temperature range of 400– temperature. Banar et al. (2012) reported a significant influence of
700 °C. They found that the oil yield increased from 31 wt.% at heating rate, where oil yield decreased to 35.1 wt.% and gas yield
400 °C, increasing to 40 wt.% at 500 °C, with little change in yield increased to 33.8 wt.% as the heating rate was increased from 5
at higher temperatures. There was a consequent increase in gas to 35 °C min 1 at the pyrolysis temperature of 400 °C. The influ-
yield. They also investigated the influence of nitrogen flow rate ence of very fast heating rates of 1200 °C min 1 have been investi-
on product yield and found only negligible differences in yield. gated over a temperature range of 500–1000 °C (Leung et al.,
Williams et al. (1990) used a small scale, fixed bed, batch reactor 2002). It was shown that under such high heating rate conditions,
to investigate the influence of pyrolysis temperature from 300 to the gas yield increased from 5.0 wt.% at 500 °C to 23 wt.% at 900 °C.
720 °C and heating rate from 5 to 80 °C min 1 on product yield Large batch reactor systems processing around 1 tonne of whole
from the pyrolysis of 50 g of tyre. At the low temperature of and shredded waste tyres have reported lower yields of oil for
300 °C there was little thermal degradation of the tyres. To example, 20.9 wt.% oil (24.0 wt.% oil, corrected for steel) and
1716 P.T. Williams / Waste Management 33 (2013) 1714–1728
Table 2
Range of pyrolysis reactors and product yield from the pyrolysis of waste tyres.
Reactor Experimental conditions Maximum oil yield References

Temperature Oil Char Gas
(°C) (wt.%) (wt.%) (wt.%)
Fixed bed, batch 400–700 °C Temperature 500 40.26 47.88 11.86 (Aydın and Ilkılıc, 2012)
Fixed bed, batch 500–1000 °C Temperature; 1200 min 1 heating rate 500 58.0 37.0 5.0 (Leung et al., 2002)
Closed batch reactor 350–450 °C; Temperature; 30 min 1 heating rate; 450 63 30 7 (Miranda et al., 2013)
20 g tyre
Fixed bed, batch 300–720 °C Temperature; 5–80 °C min 1 heating 720 58.8 26.4 14.8 (Williams et al., 1990)
rate; 50 g tyre
Fixed bed, batch 450–600 °C Temperature; 5 °C min 1 heating rate; 475 58.2 37.3 4.5 (Cunliffe and Williams,
3 kg, tyre 1998a)
Fixed bed, batch 950 °C Temperature (max.); 2 °C min 1 heating 950 a
20.9 40.7 23.9 (Williams et al., 1998)
rate; 1 tonne tyre
Fixed bed, batch 350–600 °C Temperature; 5 °C min 1 and 35 min 1 400 38.8 34.0 27.2 (Banar et al., 2012)
heating rate
Fixed bed, batch 300–700 °C Temperature; 15 °C min 1 heating rate; 700 38.5 43.7 17.8 (Laresgoiti et al., 2004)
175 g tyre
Fixed bed, batch 375–500 °C Temperature; 10 °C min 1 heating rate; 425 60.0 30 10 (Kar, 2011)
10 g tyre
Fixed bed, batch, internal fire 375–575 °C Temperature; 750 g tyre 475 55 36 9 (Islam et al., 2011)
tubes
Moving screw bed 600–800 °C Temperature; 3.5–8.0 kg h 1 mass flow 600b 48.4 39.9 11.7 (Aylón et al., 2011)
rate
Rotary kiln 550–680 °C Temperature; 4.8 kg h 1 throughput 550 38.12 49.09 2.39 (Galvagno et al., 2002)
Vacuum, conical spouted 425 °C & 500 °C Temperature; 25 and 50 kPa Vacuum 500 60 34 4 (Lopez et al., 2010)
bed
Rotary kiln 450–650 °C Temperature; 12–15 kg h 1 throughput 500 45.1 41.3 13.6 (Li et al., 2004)
Fluidised bed 740 °C Temperature; 1 kg h 1 throughput; tyre 740 30.2 48.5 20.9 (Kaminsky et al., 2009)
powder
Fluidised bed 750–780 °C Temperature; 30 kg h 1 throughput; tyre 750 31.9 38.0 28.5 (Kaminsky et al., 2009)
pieces
Fluidised bed 700 °C Temperature; 200 kg h 1 throughput; whole 700 c
26.8 35.8 19 (Kaminsky et al., 2009)
tyres
Fluidised bed 450–600 °C Temperature; 220 g h 1 throughput; 450 55.0 42.5 2.5 (Williams and Brindle,
tyre granules 2003a)
Circulating fluidised bed 360–810 °C Temperature; 5 kg h 1 throughput; 450 52 28 15 (Dai et al., 2001)
Conical spouted bed 425 and 500 °C Temperature 500 62 35 3 (Olazar et al., 2008)
Vacuum 485–550 °C Temperature; batch (80–180 kg) and 520d 45 36 6 (Roy et al., 1999)
continuous
Vacuum 500 °C Temperature: Pilot scale semi continuous 500 56.5 33.4 10.1 (Pakdel et al., 2001)
Vacuum 450–600 °C Temperature; batch (100 g) 550 47.1 36.9 16 (Zhang et al., 2008)
Drop tube reactor 450–1000 °C Temperature; 30 g h 1 throughput 450e 37.8 35.3 26.9 (Conesa et al., 2004)
Fixed, wire mesh, fast 390–890 °C Temperature; 70–90 °C s 1 heating rate; 860 5 22 73 (Zabaniotou and
reactor 0.2 g Stavropoulos, 2003)
a
12.9 wt.% Steel also produced; 950 °C was the maximum pyrolysis temperature.
b
Tyre mass flow rate of 8.0 kg h 1.
c
13.3 wt.% steel and 5.1 wt.% water also produced.
d
Operated in batch mode; 10 wt.% steel and 3 wt.% water also produced.
e
Product yields average of two experiments.
23.9 wt.% gas for a pyrolysis temperature of 950 °C (Williams et al., 2.2. Screw kiln and rotary kiln reactors
1998). For such large batch reactors, there is a major drawback re-
lated to the transfer of heat to the large volume of tyres contained Continuous operating reactors have been developed for the
within the reactor. For example, the reported 950 °C pyrolysis tem- pyrolysis if waste tyres. For example, Aylón et al. (2008, 2010) used
perature represented the maximum attained temperature over an a moving bed reactor and investigated the influence of various
8 h 40 min heating period. The reactor design would produce pyro- parameters, including pyrolysis temperature, between 600 and
lysis at the outer edge of the reactor and for tyres located in the in- 800 °C and mass flow rate of tyres through the reactor on product
ner part of the reactor and pyrolysed later in the heating cycle, the yield and composition. The reactor was a continuous screw kiln
evolved gases would be subject to significant secondary cracking reactor, externally heated by electrical furnaces. The reactor was
reactions resulting in oil decomposition and cracking to produce fed by a screw feeder from the hopper containing shredded tyres
increased gas For example, Williams and Taylor (1993) examined with throughputs from 3.5 to 8.0 kg h 1. Pyrolysis oils were con-
the influence of tyre pyrolysis gas residence time at high tempera- densed in a shell-and-tube condenser and non-condensable gases
ture by passing pyrolysis gases produced at 450 °C through a sec- were combusted. The solid char was recovered at the end of the
ondary reactor at temperatures from 500 to 720 °C and a gas screw kiln reactor outlet. The reported maximum oil yield of
residence time of 30. The gas and oil yields showed a marked 48.4 wt.% was obtained at a pyrolysis temperature of 600 °C and
change with secondary reactor temperature; the gas yield in- a tyre mass flow rate of 8 kg h 1. The research group report that
creased from 10 to 20 wt.% and the oil yield decreases from 51.5 experiments on a small scale fixed bed reactor produced oil yields
to 41.5 wt.% as the secondary reactor temperature was increased of 56.4 wt.%, the difference compared to the moving bed screw
from 500 to 720 °C. reactor were attributed to the differences in heating rate and gas
residence times between the two reactors (Aylón et al., 2008). Diez size (0.32 mm and 0.8 mm), temperature of pyrolysis (360–810 °C)
et al. (2005) also used a screw kiln reactor, externally heated by an and gas residence time (1–5 s) on product yield and composition.
electrical furnace to investigate the pyrolysis of shredded tyre at a The circulating fluidised bed was 10 cm diameter and 290 cm high.
pyrolysis temperature of 500/600 °C. The plant was designed to The tyre was fed to the bed via a screw feeder and quartz sand is
produce gas and very little oil, so had a long gas residence time circulated at high fluidising velocity through the reactor. Sand
and fast heating rate. The reported product yields were and char escaping the bed are trapped in two cyclones and recircu-
33.5 wt.% char and 66.5 wt.% gas. lated back to the reactor bed. Oils are condensed in a water cooled
Galvagno et al. (2002) (reactor details in, Fortuna et al. (1997)) condenser and product pyrolysis gases are preheated and used as
used a pilot scale rotary kiln reactor to investigate the influence of the fluidising gas. Dai et al. (2001) report a maximum oil yield of
temperature on the product yield from pyrolysis of waste tyres. 52 wt.% at 450 °C which decreased markedly to 30 wt.% at
The rotary reactor was 0.4 m diameter and rotated at 3 r.p.m. 810 °C with a consequent increase in gas yield from 15 to
and externally heated by electrical furnaces with a throughput of 40 wt.%. The influence of particle size was reported as higher
4.8 kg h 1. A condensation system allowed condensed fractions of yields of oil (50 wt.%) for the smaller (0.32 mm) particles com-
heavy and light pyrolysis oil and the non-condensable gases were pared to the larger particles of tyre (0.8 mm) which produced an
scrubbed to remove acid gases and then combusted in a flare. The oil yield of 41 wt.% at the same pyrolysis temperature of 500 °C.
solid residue of pyrolysis (char) was continuously discharged in a Longer residence times of the pyrolysis gases in the hot zone of
water cooled tank. A maximum yield of product oil of 38.12 wt.% the circulating fluidised bed reduced the oil yield from 51 wt.%
was obtained at 550 °C and maximum gas yield of 10.75 wt.% at at 1 s residence time to 48 wt.% at 5 s residence time for a pyro-
680 °C. Li et al. (2004) also used a rotary kiln reactor to investigate lysis temperature of 500 °C.
tyre pyrolysis at different pyrolysis temperatures. The rotary kiln
consisted of a 0.3 m diameter, 3 m long reactor rotating at between
0.45 and 0.9 r.p.m., externally heated by electrical furnaces corre- 2.4. Other types of reactor
sponding to an effective heated length of 1.8 m. The highest oil
yield of 45.1 wt.% was obtained at 500 °C pyrolysis temperature Other novel designs of pyrolysis reactors have been investigated
with a gas yield of 13.6 wt.%. Maximum gas yield was 18.3 wt.% for pyrolysis of tyres, including, spouted beds (Olazar et al., 2008;
at 650 °C due to the secondary cracking reactions of the oil vapour Lopez et al., 2010), vacuum pyrolysis (Roy et al., 1999), drop tube
at higher temperatures and the long residence time of gases in the (Zabaniotou and Stavropoulos, 2003) and wire mesh and other
hot zone of the rotary kiln reactor. rapid heating reactors (Leung et al., 2002; Huang and Tang,
2009). Olazar and co-workers (2004, 2008; Lopez et al., 2010) used
2.3. Fluidised bed reactors a conical spouted bed reactor to study the pyrolysis of tyres. The
spouted bed is a type of fluidised bed reactor with the advantages
Fluidised bed pyrolysis of tyres has been extensively researched of isothermal operation, high heat transfer rate, reduced gas resi-
by Kaminsky and co-workers (Kaminsky and Sinn, 1980; Kamin- dence time which minimises secondary reactions and better inter-
sky, 1985; Kaminsky and Mennerich, 2001; Kaminsky et al., action of sand and solid. There is vigorous bed movement which
2004, 2009). Fluidised bed reactors have been investigated at lab- minimises agglomeration. Olazar et al. (2008) reported an oil yield
oratory scale with 1 kg h 1 throughput, technical scale with of 62 wt.%, char yield of 35 wt.% and gas yield of 3 wt.% for the
30 kg h 1 throughput to pilot scale with 200 kg h 1 throughput. pyrolysis of waste tyre particles. In the same work they investi-
Large scale pilot plant studies were able to process whole tyres. gated the use of catalysts to determine the influence on gas and
The fluidised bed is heated indirectly to typical temperatures of be- oil composition. They also used the spouted bed reactor under vac-
tween 500 and 780 °C via radiant heat tubes within the bed of uum pyrolysis conditions (Lopez et al., 2010). The influence of the
quartz sand, in which the product pyrolysis gas is combusted to vacuum producing oils with a higher diesel fraction and increased
provide heat. The fluidising gas is also the product gas and is pre- yield of isoprene.
heated to 400 °C. Any ash build up in the fluidised bed is removed Vacuum pyrolysis of waste tyres has been extensively investi-
by a screw extractor. The product gases pass through a cyclone to gated by Roy and co-workers (Roy et al., 1990, 1999; Benallal
remove particulate material and the oils condensed and distilled to et al., 1995; Pakdel et al., 2001. Oil yields of up to 56.5 wt.% (Pakdel
produce two oil fractions, heavy and light oils. The gases undergo et al., 2001) from waste tyre granules have been obtained using
further removal of oil droplets in an electrostatic precipitator be- their continuous or semi-continuous pilot scale vacuum pyrolysis
fore storage. Kaminsky et al. (2009) reported that for the laboratory system. Vacuum pyrolysis is reported to be characterised by short
scale 1 kg h 1 fluidised bed reactor oil yields at 740 °C pyrolysis residence times of the pyrolysis gases as the vacuum conditions
temperature were 30.2 wt.% and for the 200 kg h 1 pilot scale reac- quickly remove the gases from the hot zone of the reactor, thereby
tor processing whole tyres at 700 °C, oil yield was 26.8 wt.%, but on minimising secondary char forming and cracking reactions (Roy
a steel free basis was similar to the laboratory reactor oil yield at et al., 1999). In addition, the influence of vacuum conditions en-
30.9 wt.%. hances diffusion of the volatile products formed within the tyre
A laboratory scale fluidised bed reactor was used by Williams due to the pressure gradient inside and outside the particle; the
and Brindle (2003a) to pyrolyse tyre crumb (size 1.0–1.4 mm) over faster diffusion of the volatile gases reduces the time for secondary
the temperature range of 450–600 °C. The reactor was 7.5 cm reactions (Lopez et al., 2010). Kinetic analysis of waste tyres using
diameter and 100 cm high with quartz sand as the reactor bed a thermogravimetric analyser showed that the thermal degrada-
and a throughput of 220 g h 1 of tyre. The incoming fluidising tion of tyre occurred at lower temperature and was faster under
air was nitrogen and was pre-heated to 400 °C by an external elec- vacuum conditions compared to atmospheric pressure (Lopez
trical furnace. Condensation was via a series of water cooled and et al., 2009). Zhang et al. (2008) used a batch vacuum pyrolysis
dry ice/acetone cooled condensers. The maximum oil yield of reactor to pyrolyse tyre granules and reported that pyrolysis oil
55 wt.% was found at 450 °C pyrolysis temperature which was re- yield increased gradually to a maximum of 48.8 wt.% at 600 °C as
duced to 43.5 wt.% at 600 °C, with a consequent increase in gas the pyrolysis temperature was raised from 450 to 600 °C. The oil
yield from 2.5 to 14.0 wt.%. yield is lower than that obtained by other vacuum pyrolysis reac-
A laboratory scale circulating fluidised bed reactor was devel- tors (Roy et al., 1999; Pakdel et al., 2001) but with higher gas yield
oped by Dai et al. (2001) to investigate the influence of tyre particle at 16.3 wt.% gas at 600 °C.
A drop tube pyrolysis reactor was investigated by Conesa et al. higher temperature but also showed initial decomposition at lower
(2004) to study the pyrolysis of waste tyre particles (4 mm size). temperature. Analysis of the tyre rubbers with known rubber com-
The tyre particles were fed in 5 g batches into a hot (450, 750 or position could be related to the composition of the component rub-
1000 °C reactor temperature) reactor of 65.4 cm height. A solid bers. The char yields from the three rubbers showed 4 wt.% of
CO2 cooled condenser trapped the oils. Increasing pyrolysis tem- char, suggesting that the char from the pyrolysis of tyres is mainly
perature showed a marked reduction in oil yield from 37.8 wt.% originated from the carbon black filler. Seidelt et al. (2006) also
at 450 °C, decreasing to 10.9 wt.% at 750 °C and to less than examined the thermal decomposition of styrene–butadiene-rub-
0.01 wt.% at 1000 °C. The solid char residue yield was similar at ber, natural rubber and polybutadiene rubber using coupled ther-
each temperature (37 wt.%) resulting in a high conversion of mogravimetric analysis–mass spectrometry. They confirmed the
the tyre to gas of about 63 wt.% at 1000 °C. relationship between tyre rubber composition and the tempera-
High heating rate tyre pyrolysis using a electrically heated wire tures of the thermal degradation of the three component rubbers.
mesh microreactor system was investigated by Zabaniotou and They also reported that the main degradation product from natural
Stavropoulos (2003). The wire mesh process involved placing rubber was xylene and isoprene dimer and from styrene–butadi-
about 200 mg of the tyre rubber (0.18–1.0 mm particle size) on a ene-rubber the main components were ethylbenzene, styrene
wire mesh. An electric current is passed through the mesh which and cumene.
rapidly raised the temperature (70–90 °C s 1) of the mesh to tem- However, of more significance in determining the product yield
peratures of between 390 and 890 °C. With such rapid heating of and composition of the oils and gases in particular is largely deter-
small particles, there was a low oil yield of less than about mined by the type of reactor used and the consequent heating rate
5 wt.% and a high gas yield which increased from 22 wt.% at and pyrolysis temperature, rather than differences in individual
450 °C to 73 wt.% at 860 °C. tyre compositions.
Huang and Tang (2009) investigated high heating rates and very
high temperatures to determine the conversion of tyre to gas using
3. Tyre pyrolysis oil composition
a plasma reactor. Maximum temperatures investigated were
1500 °C with tyre particles of 200–600 lm. The tyre particles are
Tyre pyrolysis oil is a dark brown/black coloured, medium vis-
passed through the plasma reactor at feed rate of 0.2–0.5 g min 1
cosity oil with a sulphurous/aromatic odour. It is chemically very
via a nitrogen gas flow. The reported highest conversion of the tyre
complex containing more than 100 identified compounds. Table 3
to gas was 78.4 wt.% at 1500 °C, the gas consisting of mainly H2 and
lists some of the reported compounds identified in tyre pyrolysis
CO.
oils (Williams and Bottrill, 1995; Cunliffe and Williams, 1998a;
Dai et al., 2001; Li et al., 2004; Conesa et al., 2004; Laresgoiti et al.,
2.5. Influence of tyre type and composition
2004; Olazar et al., 2008; Kaminsky et al., 2009; Banar et al., 2012).
The oils have been fractionated into broad chemical class frac-
The large majority of the research undertaken on waste tyres
tions and shown to be composed of aliphatic, aromatic, hetero-
has used tyres from reprocessing plants where the tyres will be a
atom and polar fractions. Dai et al. (2001) reported a tyre oil com-
mixture of different brands and types. It has also been reported
position from the pyrolysis of tyres in a circulating fluidised bed of
(Evans and Evans, 2006) that a typical tyre could contain up to
26.77 wt.% of alkanes, 42.09 wt.% aromatics, 26.64 wt.% of non-
30 different types of synthetic rubber, 8 different natural rubbers,
hydrocarbons and 4.05 wt.% as asphalt. Conesa et al. (1996) re-
in addition to a range of different carbon black fillers and up to 40
ported a 39.5 wt.% aliphatic fraction, 19.1 wt.% aromatic fraction,
different additive chemicals. Kyari et al. (2005) investigated the
21.3 wt.% hetero-atom fraction and 20.1 wt.% polar fraction for oils
pyrolysis of seven different types and brands of waste tyres from
produced from a laboratory scale fluidised bed reactor at 700 °C.
different source countries. They reported that the yields of oil,
Aylón et al. (2008) using a screw kiln reactor to pyrolyse tyres at
gas, and char were not significantly influenced by the type and ori-
600 °C reported an alkane fraction of 6.7 wt.%, aromatic fraction
gin of the tyre. However, there were noticeable differences in the
of 65.6 wt.% and polar fraction of 27.8 wt.%. Laresgoiti et al.
composition of the derived gases and oils. Detailed analysis of
(2004) reported an increase in aromatic content of tyre pyrolysis
the pyrolysis oils showed variations in the concentration of certain
oils from a fixed bed reactor from 53.4 to 74.8 wt.% as the temper-
aromatic compounds depending on the tyre type and origin. In
ature was raised from 300 to 700 °C.
addition, they carried out pyrolysis of a mixture of the seven tyres,
and the results of both yield and composition showed that the
resultant products was an average of the individual tyre yields 3.1. Aromatic and aliphatic compounds
and compositions. Cypres and Bettens (1989) also pyrolysed differ-
ent types of waste tyre in a two-stage reactor, with pyrolysis in the The main aromatic compounds found in the oil are benzene, tol-
first stage and post-pyrolysis cracking of the gases in a second uene, xylenes (dimethylbenzenes), styrene, limonene and indene
reactor at higher temperatures. They showed small but significant and their alkylated homologues. In addition, the oils contain poly-
differences in product yield depending on the six types of tyre cyclic aromatic hydrocarbons from 2-ring naphthalene to 5 ring
used. benzopyrenes. The main aliphatic compounds are alkanes, with
Although tyres may be composed of many different types of straight chain hydrocarbons from C6–C37 and lower concentrations
synthetic and natural rubber, the main rubber types used are, typ- of alkenes.
ically, styrene–butadiene-rubber, natural rubber (polyisoprene) Cunliffe and Williams (1998a) reported chemical class fractions
and polybutadiene rubber (Williams and Besler, 1995; Seidelt of tyre oils produced from a fixed bed reactor at temperatures be-
et al., 2006). Williams and Besler (1995) used thermogravimetric tween 450 and 600 °C and showed a clear increase in the aromatic
analysis to investigate the thermal decomposition of three samples fraction and decrease in the aliphatic fraction of the oils as the
of tyre of known rubber composition and the three major rubber temperature of pyrolysis was increased. For example, the oil pro-
components of the tyres, styrene–butadiene-rubber, natural rub- duced at 450 °C consisted of the chemical fractions 51.3 wt.% ali-
ber and polybutadiene rubber. The thermograms showed two dis- phatic, 36.7 wt.% aromatic, 6.6 wt.% hetero-atom and 8.6 wt.%
tinct areas of weight loss, with styrene–butadiene rubber polar. However, at 600 °C pyrolysis temperature, the oil composi-
decomposing at higher temperature and natural rubber at lower tion was 36.1 wt.% aliphatic, 45.6 wt.% aromatic, 11.6 wt.% het-
temperature, the polybutadiene rubber decomposed mainly at ero-atom and 6.6 wt.% polar fractions. Secondary reactions of the
Table 3
Oil composition from the pyrolysis of waste tyres (Williams and Bottrill, 1995; Cunliffe and Williams, 1998a; Dai et al., 2001; Li et al., 2004; Conesa et al., 2004; Laresgoiti et al.,
2004; Olazar et al., 2008; Kaminsky et al., 2009; Banar et al., 2012).
Aliphatic compounds Single ring aromatic compounds Polyaromatic hydrocarbons (PAH) Others
Alkanes Toluene Naphthalene Hydrocarbons
Decane (C10) Ethylbenzene Methylnaphthalene Limonene
Undecane (C11) Styrene Biphenyl Pinene
Dodecane (C12) Xylene (1,2-dimethylbenzene) Ethylnaphthalene Cyclopentene, pentyl-
Tridecane (C13) Xylene (1,3-dimethylbenzene) Dimethylbiphenyl Cyclohexene
Tetradecane (C14) Xylene (1,4-dimethylbenzene) Dimethylnaphthalene Cyclohexene, propenyl-
Pentadecane (C15) Toluene, ethyl Acenaphthene Cyclohexane, ethenyl–methyl-
Hexadecane (C16) Benzene, propyl- Trimethylnaphthalene Cyclopentane, ethylidene-
Heptadecane (C17) Benzene, ethyl–methyl- Dihydromethylnaphthalene Phenol
Octadecane (C18) Methylstyrene Tetrahydronaphthalene Methylphenol
Nonadecane (C19) Indene Fluorene Dimethylphenol
Eicosane (C20) Benzene, butyl- Methylfluorene Isopropylphenol
Heneicosane (C21) Benzene, dimethylpropyl- Phenanthrene Methylbenzaldehyde
Docosane (C22) Benzene, dimethyl- Anthracene Tetradecanoic acid
Tricosane (C23) Benzene, butenyl- Dimethylfluorene Pentadecanoic acid
Tetracosane (C24) Benzene, pentyl- Methylphenanthrene Hexadecanoic acid
Pentacosane (C25) Benzene, cyclopentyl- Methylanthracene Heptadecanoic acid
(C26)–(C35) Benzene, cyclohexyl- Dimethlyphenanthrene Octadecanoic acid
Alkenes Benzene, hexyl- Fluoranthene Sulphur compounds
Hexene Benzene, hexenyl- Pyrene Thiophene
Heptene Methylindene Trimethylphenanthrene Benzothiophene
Octene Dimethylindene Tetramethylphenanthrene Methylbenzothiophene
Nonene Benzene, methyl–butenyl- Chrysene Dimethylbenzothiophene
Terphenyl Benzo[a]pyrene Trimethyldihydrobenzothiophene
Dimethylindene Benzo[e]pyrene Tetramethyldihydrobenzothiophene
Trimethylindene Benz[a]anthracene Dibenzothiophene
Ethylindene Naphthothiophene
Methylnaphthothiophene
Methyldibenzothiophene
Dimethyldibenzothiophene
Trimethyldibenzothiophene
Benzonaphthothiophene
Nitrogen compounds
Aniline
Benzothiazole
Benzonitrile
Quinoline
Diphenylamine
Heptadecanenitrile
Dimethylquinoline
PCDD/PCDF
Hexachlorodibenzofuran
Heptachlorodibenzofuran
Octachlorodibenzodioxin
pyrolysis gases at extended residence time in the hot zone of the similarly toluene increased from 2.27 to 7.06 wt.% over the same
pyrolysis reactor will also result in increased aromatic content of temperature range. There was a corresponding decrease in
the tyre oil (Cypres and Bettens, 1989; Williams and Taylor, limonene concentration with increasing temperature. It has been
1993). Differences in the relative concentrations of the different suggested that limonene decomposes to a range of products
fractions reported by different authors could be related to the ana- including benzene, xylene, toluene, trimethylbenzene, styrene
lytical fractionation method in addition to differences in reactor and methylstyrene which occurs at pyrolysis temperatures above
characteristics, heating rate of the tyre, pyrolysis temperature, ex- 500 °C and/or with long hot zone residence times (Pakdel et al.,
tent of secondary reactions, etc. 1992; Williams and Besler, 1995; Li et al., 2004).
Kaminsky et al. (2009) have reported detailed analyses of tyre
pyrolysis oils obtained from pyrolysis of tyres in fluidised beds 3.2. Polycyclic aromatic hydrocarbons
ranging in throughputs from laboratory scale at 1 kg 1 to pilot
scale at 200 kg h 1. They report benzene and toluene concentra- Tyre pyrolysis oils contain a wide range of polycyclic aromatic
tions of 4.2 wt.% and 3.8 wt.% respectively for a laboratory scale hydrocarbons (PAHs), but the highest concentration of PAH identi-
reactor at 740 °C. Cunliffe and Williams (1998a) reported maxi- fied consist largely of alkylated naphthalenes, fluorenes and phe-
mum concentrations of volatile aromatic compounds of toluene nanthrenes. Table 3 shows some of the PAH identified in tyre
at 1.77 wt.%, total xylenes at 1.68 wt.%, styrene at 0.36 wt.%, limo- pyrolysis oil (Williams and Bottrill, 1995; Cunliffe and Williams,
nene at 3.13 wt.% and indene at 0.32 wt.%. Using a rotary kiln reac- 1998a; Dai et al., 2001; Li et al., 2004; Conesa et al., 2004; Laresgo-
tor, Li et al. (2004) reported concentrations of benzene, xylene, iti et al., 2004; Olazar et al., 2008; Kaminsky et al., 2009; Banar
toluene, styrene and limonene at 550 °C pyrolysis temperature of et al., 2012). Concentrations of total PAH in tyre pyrolysis oils are
1.49 wt.%, 2.05 wt.%, 5.16 wt.%, 1.42 wt.% and 0.42 wt.% respec- reported at 1.72 wt.% for a fixed bed reactor at 500 °C (Cunliffe
tively. It was reported that there was a marked influence of and Williams, 1998a), however, higher concentrations of PAH
temperature on volatile aromatic concentrations, for example, ben- totalling over 16 wt.% have been reported for the rotary kiln pyro-
zene increasing from 0.40 wt.% at 450 °C to 2.09 wt.% at 650 °C, lysis of waste tyres at the same temperature (Li et al., 2004). A wide
range of PAH have been reported by Laresgoiti et al. (2004), con- The presence of sulphur containing PAH (PASH) and nitrogen
sisting of mainly naphthalene, fluorene and phenathrene and their containing PAH (PANH) have been reported. For example,
alkylated homologues. Kaminsky et al. (2009) reported the presence of PASH in the form
It has been shown that higher temperatures of pyrolysis and of thiophene, methylthiophene, dimethylthiophene and
long residence times produce increased concentrations of PAH dimethylbenzothiophene at concentration levels of about 0.1–
(Williams and Taylor, 1993; Cunliffe and Williams, 1998a). For 0.3 wt.% for the fluidised bed pyrolysis of tyres. They also reported
example, for fixed bed pyrolysis of waste tyres, total PAH content the presence of PANH in the form of aniline, and benzothiazol and
of the derived oils increased from 1.53 wt.% at 450 °C to dimethylquinoline at concentrations of 0.1 wt.%. Williams and
3.43 wt.% at 600 °C, with alkylated compounds of naphthalene, flu- Bottrill (1995) undertook detailed analysis of the sulphur polycy-
orene and phenanthrene increased with pyrolysis temperature clic aromatic compounds found in tyre pyrolysis oils. The PASH
(Cunliffe and Williams, 1998a). For example, total alkylated naph- were mainly benzothiophene and dibenzothiophene and their
thalenes increased from 0.54 to 1.43 wt.%, alkylated fluorenes in- alkylated derivatives, and naphthothiophenes and their methyl
creased from 0.08 to 0.26 wt.% and the alkylated phenanthrenes derivatives. The PASH in oils derived from the fluidised bed pyro-
increased in concentration from 0.54 to 0.81 wt.% as the pyrolysis lysis of tyres showed an increase in concentration as the tempera-
temperature was increased. Li et al. (2004) reported a similar influ- ture of pyrolysis was increased.
ence of temperature but at higher concentrations of PAH, with There has been very limited work in relation to determination
naphthalene homologues increasing from 8.6 to 10.1 wt.%, fluorene of the concentration of dioxins (polychlorinated dibenzodioxins,
homologues increasing from 1.17 to 2.57 wt.% and phenanthrene PCDD) and furans (polychlorinated dibenzofurans, PCDF) in tyre
homologues increasing from 2.15 to 6.51 wt.% with increased pyro- pyrolysis oil. However, Banar et al. (2012) analysed tyre pyrolysis
lysis temperature from 450 to 650 °C. Laresgoiti et al. (2004) also oil produced from a fixed bed reactor and reported concentrations
reported increased PAH with increased pyrolysis temperature. of 1234678-HpCDF at 0.021 pg g 1, 1234789-HpCDF at
Secondary cracking of tyre pyrolysis gases to produce PAH has 0.015 pg g 1, 123478-HxCDD at 0.008 pg g 1 and OCDD at
been confirmed by experiments using secondary reactors at high 0.021 pg g 1. They also reported very low concentrations of metals
temperature and long residence times. For example, Williams in the tyre pyrolysis oil, with levels of arsenic, cadmium, chromium
and Taylor (1993) for the pyrolysis of tyres in a batch reactor with and lead at the parts per billion level and also chloride at the parts
post-pyrolysis heating of the tyre vapours. They found that the to- per million level.
tal PAH content of tyre derived oils increased from 1.4 wt.% at
500 °C post-pyrolysis temperature to over 10 wt.% total oil at
720 °C post-pyrolysis temperature. Cypres and Bettens (1989), also 3.3. Fuel properties of tyre pyrolysis oils
using a post-pyrolysis secondary reactor, found a similar trend of
increasing PAH in derived tyre pyrolysis oils with secondary reac- Table 4 shows the fuel properties of tyre pyrolysis oil from sev-
tions of the gases. A Diels–Alder reaction mechanism has been sug- eral reported reports and Table 5 shows the properties of petro-
gested as being responsible for the increase in aromatic content leum derived fuel oils for comparison. Aydın and Ilkılıc (2012)
with temperature (Cypres and Bettens, 1989; Williams and Taylor, investigated the sulphur content of tyre pyrolysis oil in relation
1993). Banar et al. (2012) used a fixed bed reactor and reported to temperature and found that differences of about 0.3 wt.% lower
that PAH concentrations in the product oil were increased with sulphur content could be found for an oil produced at 550 °C com-
increasing reactor heating rate. Kyari et al. (2005) analysed the tyre pared to a tyre pyrolysis oil produced at 400 °C. They also found
pyrolysis oil from different types and brands of waste tyre using a that increasing the pyrolysis temperature increased the sulphur
fixed bed reactor and reported different tyres produced different content of the derived pyrolysis oil. Cunliffe and Williams
concentrations of single ring and PAH in the product oils. (1998a) also found that lower pyrolysis temperatures of 450 °C
Table 4
Fuel properties of waste tyre pyrolysis oil.
Property Reference (Williams et al., 1998) Reference (Li et al., 2004)a Reference (Banar et al., 2012)b Reference (Murugan et al., 2008a)
Flash point (°C) 20 17.0 65 43
Carbon residue (%) 2.2 1.78 – –
Density (kg l 1) 0.91 0.962 0.833 0.924
Viscosity cSt (at 40 °C) 6.30 – – 3.77
Viscosity cSt (at 50 °C) – 2.44 1.01 0.924
Viscosity cSt (at 60 °C) 2.38 – – –
Carbon (wt.%) 88.0 84.26 79.61 –
Hydrogen (wt.%) 9.4 10.39 10.04 –
Nitrogen (wt.%) 0.45 0.42 0.94 –
Sulphur (wt.%) 1.5 1.54 0.11 0.72
Oxygen (wt.%) 0.5 3.39 9.3d –
Initial B.Pt. (°C) 100 – 38.5 70
10% B.Pt. (°C) 140 – 58.2 114.5
50% B.Pt. (°C) 264 – 174.8 296.1
90% B.Pt. (°C) 355 – – 386.4
Calorific value (MJ kg 1) 42.0 41.7 42.66 38
Ash (wt.%) 0.002 Tr – 0.31
Moisture (vol.%) 4.6 0.88c – –
Tr = Trace.
a
Tyre oil produced at 500 °C.
b 1
Tyre oil produced at 35 °C min heating rate.
c
Wt.%.
d
By difference.
Table 5 similar to conventional petroleum fuels in terms of H/C ratio, den-

Fuel properties of petroleum derived fuel oils (Harker and Backhurst, 1981). sity, viscosity, calorific value and elemental composition. The
Property Kerosene Gas oil Light fuel oil author suggesting that the product pyrolysis–catalysis oil could
Flash point (°C) 40 75 79 be successfully blended with various conventional fuels.
Carbon residue (%) – <0.35 – A further test related to the fuel properties of an oil is the burn-
Density (kg m 3) 0.84 0.78 0.89 ing rate coefficient determined using a single droplet combustion
Viscosity cSt (at 40 °C) 1.2 3.3 21 test. Since combustion in diesel engines and furnace and boiler
Carbon (wt.%) – 87.1 85.5
Hydrogen (wt.%) 13.6 12.8 12.4
burners involves spraying the liquid fuel under pressure through
Nitrogen (wt.%) – 0.05 0.15 a nozzle to form fine droplets which are then combusted. The test
Sulphur (wt.%) 0.1 0.9 1.4 involves combustion of single droplets of fuel of different diame-
Initial B.Pt. (°C) 140 180 200 ters and the rate reflects the reduction in the diameter of the drop-
50% B.Pt. (°C) 200 300 347
let as it combusts. Williams et al. (1998) reported a burning rate
90% B.Pt. (°C) 315 – –
Calorific value (MJ kg 1) 46.6 46 44.8 coefficient for tyre pyrolysis oils of 0.75 mm s 1 which compares
Ash (wt.%) – 0.01 0.02 with the coefficients for gas oil of 0.88 mm s 1 and for light fuel
Moisture (vol.%) – 0.05 0.1 oil of 0.82 mm s 1.
3.4. Combustion of tyre pyrolysis oils
and 475 °C produced a higher sulphur content (1.4 wt.%) compared Murugan et al. (2008a, 2008b, 2008c, 2008d) have extensively
to oils produced at higher temperatures. investigated the use of tyre pyrolysis oil blended with petroleum
The fuel properties of a liquid fuel define the characteristics of diesel fuel in a direct injection diesel engine. For blended tyre pyro-
the fuel in terms of its potential performance in a combustion sys- lysis oil-diesel fuel blends, Murugan et al. (2008a) reported that the
tem, storage and transport issues, likely emissions, distillation brake thermal efficiency (overall efficiency) of the engine was only
range, etc. The flash point of a liquid fuel represents the tempera- marginally influenced by the use of the tyre pyrolysis oil-diesel
ture that flammable gases are produced and will ignite and indi- fuel blends compared to using diesel fuel alone at blends of 10%,
cates the fire hazards associated with storage, transport and use 30% and 50% of tyre pyrolysis oil. In some cases, there was a mar-
of the fuel. The flash point of the tyre-derived oils is generally ginal increase in brake thermal efficiency with the blended fuel.
low when compared to petroleum refined fuels due to the tyre They also reported that there was no seizing of the engine or injec-
oil being an unrefined oil with a range of boiling point fractions, tor nozzle blocking with the use of the blended tyre oil and diesel
including volatile hydrocarbons. The carbon residue test is a mea- fuel. In terms of emissions, it was reported that hydrocarbon emis-
sure of the tendency of the oil to form carbon under poor combus- sions were significantly increased by 15% and 21% when tyre oil-
tion conditions which may lead to carbon coking of diesel engine diesel fuel blends of 30% and 50% respectively were used under
fuel injector nozzles or spray combustion burners. The tyre oil car- peak load conditions compared to diesel fuel. This was attributed
bon residues are quite high at between 1.78% and 2.2% compared to the higher concentration of PAH in tyre oil compared to diesel
to gas oil at <3.5%, suggesting that nozzle or spray burner blockage fuel. In addition, nitrogen oxides (NOx) emissions were found to
with extensive time of use may be an issue. The viscosity of a fuel be 4.5% and 10% higher for the 30% and 50% tyre oil blends respec-
influences the flow of the fuel through pipework, valves and pumps tively compared to diesel fuel under peak load conditions. The
and also fuel atomization in engines and spray burners. The viscos- emission of smoke (particulate material) was increased by 7% com-
ity of the tyre oils was similar to that of gas oil. The sulphur content pared to diesel fuel when the 50% blend of tyre oil and diesel was
of the tyre pyrolysis oils are between 0.11 and 1.54 wt.%. The sul- used at peak load.
phur content is similar to that of a light fuel oil. Higher ratios of tyre pyrolysis oil-diesel fuel with up to 90%
Aydın and Ilkılıc (2012) investigated the reduction of sulphur in addition to diesel fuel were also investigated by Murugan et al.
tyre pyrolysis oils. They determined a range of fuel properties of (2008b, 2008d). At higher blend ratios the tyre oil was modified
the oil derived from the pyrolysis of waste tyres using a calcium by sulphur reduction, moisture removal and distillation prior to
hydroxide additive, used to reduce the sulphur of the tyre pyrolysis blending. It was reported that the direct injection diesel engine
oil. They found that the product pyrolysis oil had fuel properties could not operate satisfactorily on 100% modified tyre pyrolysis
similar to petroleum derived diesel fuel. Blended mixtures of the oil, but could at 90% tyre oil with 10% diesel fuel. A small (2%)
modified tyre pyrolysis oil and diesel fuel showed fuel properties reduction in engine efficiency and an 11% increase in hydrocarbon
which were very similar to diesel. The boiling point/distillation emissions was observed but an 18% decrease in NOx was reported
range of the tyre pyrolysis oils reflected the fact that the oil was at peak load using the 90% tyre oil blend. There was however a
unrefined and consequently would have a wide range of boiling marked increase in the emission of smoke.
points for the components of the oil. The caloric value of the tyre Williams et al. (1998) investigated the combustion of raw tyre
oils ranged between 38 and 42.66 MJ kg 1 and was comparable pyrolysis oil compared to petroleum derived gas oil in a 1.6 m long
with that of the petroleum fuels shown in Table 5. Others have re- by 0.5 m diameter ceramically lined furnace. The liquid fuel spray
ported the calorific value of the tyre pyrolysis oil to be between 38 burner used a pressurised spray atomiser of 0.4 mm diameter with
and 49.5 MJ 1 (Williams et al., 1998; Li et al., 2004; Murugan et al., an in-line particulate filter upstream of the burner. The authors re-
2008a; Banar et al., 2012; Rada et al., 2012). Kar (2011) used exported that the furnace was able to operate successfully for several
panded perlite as a catalyst mixed with waste tyre in an attempt hours without problem, producing no particulate or PAH emissions
to improve the fuel properties of the product pyrolysis oil. Perlite at the normal operating conditions of the furnace at 6% excess oxy-
is a natural glassy volcanic rock composed mainly of silica and alu- gen combustion conditions. Combustion of tyre pyrolysis oil pro-
mina which is heated to between 850 and 1000 °C to produce a duced flue gas SO2 concentrations of 530 ppm at 2.1% excess
porous catalyst support. The support was used with added metals oxygen and 440 ppm at 7.6% excess oxygen, compared to 40 ppm
to produce the catalytic activity. Without the catalyst the oil yield and 55 ppm respectively for the gas oil fuel. NOx emissions were
was 60.0 wt.% and with the catalytic pyrolysis, oil yield was im- 374 ppm at 2.1% excess oxygen and 343 ppm at 7.6% excess oxygen
proved to 65.1 wt.% with a perlite:waste tyre ratio of 0.10. The fuel approximately three times higher than were found for the
properties of the product oil were reported and were shown to be combustion of gas oil. The results for SO2 and NOx emissions were
consistent with higher fuel sulphur (1.45 wt.%) and nitrogen of the product chars decreased with increasing temperature, from
(0.45 wt.%) contents in the tyre oil compared to the gas oil (0.2 16.61 to 6.27 wt.%, with typical surface area 89 m2 g 1. Galvagno
and 0.45 wt.% respectively). et al. (2002) also used a rotary kiln reactor and reported a decrease
in volatile content from 12.78 to 5.24 wt.% with increasing pyroly-
sis temperature from 550 to 680 °C. The metals content of the
4. Char characteristics chars was also reported, but there appeared to be no particular
trend in relation to increased temperature of pyrolysis. Kaminsky
Table 2 showed that the char produced from the pyrolysis of and Mennerich (2001) showed that increasing the pyrolysis tem-
tyres ranges from 22 to 49 wt.%, with a typical values around perature for the fluidised bed pyrolysis of a synthetic tyre rubber
38–40 wt.%. For example Kyari et al. (2005) reported that the char produced chars which increased from 76 m2 g 1 to 85 m2 g 1 as
yield from the fixed bed pyrolysis of seven different types and the pyrolysis temperature was increased from 500 to 600 °C. Con-
brands of tyre obtained from a range of locations were between esa et al. (2004) investigated the influence of temperature but over
37.1 and 41.7 wt.%. They also reported that the surface area of a much higher temperature range of pyrolysis of between 450 and
the chars ranged from 64.5 m2 g 1 to 83.8 m2 g 1 depending on 1000 °C. Volatile content of chars decreased from 7.78 wt.% at
the tyre and brand of tyre, and consequently the rubber formula- 450 °C to 1.06 wt.% at 1000 °C, hydrogen also decreased (from
tion of the tyres. Table 6 shows a range of reported properties of 0.60 to 0.17 wt.%) with a corresponding increase in surface area
chars derived from the pyrolysis of tyres. The chars have high car- from 93 to 139 m2 g 1. Metal contents in the chars were reported
bon contents of up to 90 wt.% and high sulphur contents reported to be similar for the 450 and 750 °C chars, but at the higher tem-
to be between 1.9 and 2.7 wt.%. However, most notably the chars perature of 1000 °C there was significant vaporisation of the zinc
have a high ash content reported at between 8.27 and 15.33 wt.% out of the char into the gas phase. The zinc concentration de-
related to the additive metals, mostly zinc, added in the formula- creased in the char from 6.68 to 0.935 wt.% as the temperature
tion of the tyre and dirt material found with the waste tyres. was increased from 450 to 1000 °C.
The influence of process conditions on the characteristics of There have been many studies investigating the properties of
product chars have been investigated by several researchers. For the char as a substitute carbon black (Darmstadt et al., 1995; Saho-
example, Cunliffe and Williams (1998b) reported char characteris- uli et al., 1996; Roy et al., 1999; Kaminsky and Mennerich, 2001;
tics in relation to pyrolysis temperature over the range of Pantea et al., 2003; Tang and Huang, 2005; Mikulova et al.,
450–600 °C for 1.5 kg batches of tyre using a fixed bed reactor. 2013). The carbon black/char produced from pyrolysis of tyres dif-
They reported that the volatile content and hydrogen content of fers from commercial carbon black in that the char consists of the
the product chars was reduced with a small increase in surface recovered carbon black and also pyrolytic char. Williams and Bes-
area and mesopore volume as the temperature of pyrolysis was in- ler (1995) have shown that the main source of the carbonaceous
creased. This was attributed to the loss of high molecular weight char is the original carbon black filler, since the main rubber com-
solid hydrocarbons with increasing temperature which resulted ponents of the tyre such as styrene–butadiene rubber, natural rub-
in pore widening and consequent increase in surface area. There ber and polybutadiene rubber only produce about 4 wt.% of char.
was little influence of pyrolysis temperature on the trace metal Darmstadt et al. (1995) reported that carbon blacks obtained
or sulphur content of the chars over the temperature range inves- from the pyrolysis of tyres in a vacuum pyrolysis reactor at
tigated. Li et al. (2004) also investigated the characteristics of chars 500 °C contained less pyrolyitic carbon compared to pyrolysis
produced from a rotary kiln reactor over a similar temperature under atmospheric pressure conditions. The pyrolytic carbon
range of 450–650 °C. They also reported that the volatile content deposits on the original carbon black deactivating the carbon black
Table 6
Properties of tyre pyrolysis chars.
Property Reference (Cunliffe and Reference (Conesa et al., Reference (Li et al., Reference (Galvagno et al., Reference (Olazar et al.,
Williams, 1998b) 2004) 2004) 2002) 2008)
Reactor Fixed bed Drop tube Rotary kiln Rotary kiln Conical Spouted bed
Pyrolysis temperature 500 °C 450 °C 500 °C 550 °C 500 °C
Tyre 3 kg batch 30 g h 1 throughput 12–15 kg h 1
4.8 kg h 1 throughput –
throughput
Proximate analysis
(wt.%)
Moisture 0.4 0.37 2.35 3.57 –
Volatiles 2.8 7.78 16.14 12.78 –
Ash 11.6 8.27 12.32 15.33 –
Ultimate analysis
(wt.%, dafa)
Carbon 90.6 88.19 82.17 85.31 80.3
Hydrogen 0.9 0.6 2.28 1.77 1.3
Nitrogen 0.7 0.1 0.61 0.34 0.3
Sulphur 2.3 1.9 2.32 2.13 2.7
Chlorine 0.08 – – – –
Calorific value 30.5 30.8 31.5 30.7 29.3
(MJ kg 1)
Surface area (m2 g 1) 64 93 – – 83
Metals (wt.%)
Zn 4.1 6.68 – 4.06 3.8
Ca 1.2 0.13 – – –
Fe 0.2 0.04 – 0.54 –
Al 0.15 – – 1.09 –
Si 0.42 1.69 – – –
Pb – 0.01 – Tr –
a
daf = Dry ash-free.
activated sites making the carbon less effective in relation to the 5. Gas composition from the pyrolysis of waste tyres
original carbon black added to the tyre. In addition, Darmstadt
et al. (1995) and Sahouli et al. (1996) show that the surface chem- Table 7 shows the analysis of the gases produced from the pyro-
istry of the recovered carbon black is similar to low grade commer- lysis of waste tyres. The main gas components are hydrogen (H2),
cial carbons. The surface roughness of the carbon black is an methane (CH4), ethane (C2H6), ethene (C2H4), propane (C3H8), pro-
important property in that it influences the interaction of the ac- pene (C3H6), butane (C4H10), butene (C4H8), butadiene (C4H6), car-
tive sites of the carbon black with the elastomer. The authors re- bon dioxide (CO2), carbon monoxide (CO) and hydrogen sulphide
port that increasing pyrolysis pressure and to some extent (H2S). The gas composition arising from the tyres is dependent
temperature in vacuum pyrolysis reduces the surface roughness. on the composition of the various rubbers used in tyre manufac-
Kaminsky and Mennerich (2001) also noted the presence of pyro- ture, such as styrene–butadiene-rubber, natural rubber (polyiso-
lytic carbon on the recovered carbon black (char) from the fluidised prene), nitrile rubber, chloroprene rubber, polybutadiene rubber.
bed pyrolysis of synthetic tyre rubber at 600 °C and showed that The thermal degradation process will produce highly reactive free
the surface area of the recovered char was 85 m2 g 1 compared radicals which are often sub-units of the original rubber molecule
to the carbon black used in the tyre rubber formulation of (Dodds et al., 1983). As the tyre rubbers are thermally degraded
115 m2 g 1. They also noted that the high ash content of the char during the pyrolysis process, the main primary degradation prod-
(10 wt.%) would represent a problem for the use of the char as ucts produce high concentrations of alkenes and dienes and buta-
a commercial carbon black. A typical carbon black used in tyre diene in particular. Secondary reactions of the product pyrolysis
manufacture must be below 0.5 wt.%. (Tang and Huang, 2005). gases in the hot zone of the reactor will also lead to the formation
Cunliffe and Williams (1998b) also highlighted the high ash con- of light hydrocarbons from the oil vapours produced during pyro-
tent of the recovered char as a drawback to its use as a substitute lysis. The gas has a significant calorific value and has been reported
carbon black, with ash contents reported at around 12 wt.%. They to be between 20 MJ m 3 and more than 65 MJ m 3 depending on
used an acid wash process on the chars that could reduce the ash the gas composition which in turn would depend on the tempera-
content by up to 90%. A typical carbon black used in tyre manufacture of pyrolysis, heating rate, type of reactor, etc. (Williams et al.,
ture must have an ash content below 0.5 wt.%. (Tang and Huang, 1990; Leung et al., 2002; Kyari et al., 2005; Rada et al., 2012). It is
2005). Tang and Huang (2005) used rapid heating, plasma pyroly- suggested that the gas has sufficient energy value to provide
sis of tyre particles to produce a char product and comparison was the process fuel to heat the tyres to the required pyrolysis
made with commercial carbon blacks. The surface area of the chars temperature.
was 64.8 m2 g 1 compared to a commercial carbon black (N330) at Kyari et al. (2005) analysed the gases produced from the pyro-
80 m2 g 1. In addition, the ash content was 15.14 wt.% compared to lysis of different types and brands of tyre in a fixed bed batch reac-
the commercial carbon black at 0.4 wt.%. tor at 500 °C. The gas compositions for each type of tyre produced
Table 7
Gas composition from the pyrolysis of waste tyres (wt.% of tyre mass).
Reactor Temperature Gas composition References

(°C)
H2 CH4 C2H6 C2H4 C3H8 C3H6 C4H10 C4H8 C4H6 CO2 CO H2S
(wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%)
Fluidised bed 450 0.06 0.29 0.17 0.24 0.16 0.04 Tr 0.08 1.26 Tr Tr – (Williams and
0.2 kg h 1 Brindle, 2003a)
throughput
Fluidised bed 600 0.24 2.39 0.74 3.84 0.40 1.92 Tr 0.26 2.60 Tr Tr – (Williams and
0.2 kg h 1 Brindle, 2003a)
throughput
Fluidised bed 598 0.59 2.9 1.2 1.6 0.76 2.2 0.41a 5.75b 0.74 1.8 1.6 0.38 (Kaminsky et al.,
1.4 kg h 1 2009)
throughput
1.4 kg h 1 2009)
throughput
1.4 kg h 1 2009)
throughput
Fixed bed, batch 500 0.2 0.8 0.3 1.2 0.3 0.5 0.2a 0.3b 1.9 0.3 0.1 – (Williams and
Brindle, 2003b)
Drop tube reactorc 450 0.05 0.65 0.24 0.59 0.09 0.22 0.01a 0.02b 0.01 3.37 – – (Conesa et al.,
2004)
Drop tube reactorc 750 0.35 4.62 1.11 2.42 0.14 1.11 0.03 0.01 0.18 4.11 0.60 – (Conesa et al.,
2004)
c
Drop tube reactor 1000 1.00 7.89 0.10 0.71 Tr 0.03 – – 0.01 1.81 1.32 – (Conesa et al.,
2004)
Rotary kiln 600 1.4 1.11 0.67 0.67 – – – – – 0.70 0.31 0.21 (Galvagano
et al., 2002)
Moving screw bed 600 0.7 3.6 – – – – – – – – – 1.4 (Aylón et al.,
2010)
Moving screw bed 800 1.8 13.8 – – – – – – – – – 0.8 (Aylón et al.,
2010)
Tr = Trace.
a
Iso-butane and n-butane gases.
b
Trans-2-butene, 1-butene, iso-butene, cis-2-butene gases.
c
Data are the average of two experiments.
significantly different gas compositions, for example hydrogen and cumene which are used for the production of plastics, resins,
yield ranging from 13.8 to 27.6 vol.% and methane ranging from fibres, surfactants, dyestuffs and pharmaceuticals (Franck and Sta-
14.1 to 27.9 vol% depending on tyre type. The calorific value of delhofer, 1988). Toluene is used in the production of pesticides,
the total gases was also influenced by tyre type, ranging from dyestuffs, surfactants and solvents. Xylenes have applications in
29.9 to 42.1 MJ m 3. Cypres and Bettens (1989) also reported the plastics industry to produce plasticisers, polyester resins and fi-
significant differences in gas composition from the pyrolysis of bres and for use in the dyes and pigments industries. Styrene is
different brands of tyre. For example, for the six different tyres they used in the production of plastic materials and is also used to make
investigated, there were variations of more than 100% in the synthetic rubber and other polymers. Limonene is used for exam-
reported concentrations of hydrogen, ethane and ethene. ple, in the formulation of industrial solvents, resins and adhesives
The influence of pyrolysis temperature on product gas composi- and for the production of fragrances and flavourings (Pakdel et al.,
tion has been investigated by several researchers. Overall gas yield 1992; Franck and Stadelhofer, 1988).
is known to increase with increasing pyrolysis temperature as, the Tyre pyrolysis oils may contain high concentrations of such
higher temperature results in thermal cracking of the pyrolysis oil chemicals, depending on process conditions and type of reactor.
vapours producing higher gas yields and lower oil yields as dis- For example, Kaminsky et al. (2009) reported a benzene yield in
cussed in Section 2. Increasing pyrolysis temperature produces relation to the mass of feedstock tyre of 9.2 wt.% and toluene yield
an increase in hydrogen, methane and C1–C4 hydrocarbons. For of 6.0 wt.% for the fluidised bed pyrolysis of tyre pieces in a
example, Kaminsky et al. (2009) pyrolysed tyres in a 1.4 kg h 1 30 kg h 1 throughput reactor at 780 °C. Dai et al. (2001) used a cir-
throughput fluidised bed and showed total gas yield increasing culating fluidised bed reactor and reported high concentrations of
from 20 wt.% at 598 °C to 24 wt.% at 600 °C and to 33 wt.% at limonene and indene in the product oil. Kyari et al. (2005) have
700 °C pyrolysis temperatures. They also reported hydrogen yields shown that limonene concentration varied between 2.82 and
increasing from 0.59 to 1.1 wt.%, methane from 2.9 to 6.9 wt.%, C2 4.76 wt.% and ethylbenzene varied from 0.74 to 1.51 wt.% depend-
hydrocarbons from 2.8 to 5.8 wt.% and C3 hydrocarbons increasing ing on the type or brand of tyre pyrolysed.
from 2.96 to 5.03 wt.% as the pyrolysis temperature was increased Laresgoiti et al. (2004) pyrolysed tyres in a fixed bed autoclave
from 598 to 700 °C. Carbon dioxide, carbon monoxide and hydro- reactor continuously purged with nitrogen. The composition of the
gen sulphide also showed an increase with increasing fluidised derived oil was shown to be very complex, with 132 different com-
bed pyrolysis temperature. Williams and Brindle (2003a) also for pounds identified. The main compounds with concentrations
a fluidised bed reactor, but at 0.2 kg h 1 throughput and a temper- greater than 1% were toluene, dimethylcyclohexenes, ethylben-
ature range of 450–600 °C, reported lower total gas yields ranging zene, xylenes, styrene, methyloctene, ethylmethylbenzenes, meth-
from 2.5 wt.% at 450 °C, 6.0 wt.% at 525 °C and 14 wt.% at 600 °C. ylethenylbenzenes and limonene. Concentration of toluene was
However, increasing pyrolysis temperature showed that hydrogen 4.4%, 3.48% xylene, and 5.12% limonene at 500 °C pyrolysis temper-
and the hydrocarbons increased in yield, the main gas yields were ature, the data being reported as chromatogram peak area percent-
for methane, ethene, propene and butadiene. age, with total percentage peak area of all the compounds
Galvagno et al. (2002) used a rotary kiln reactor between 550 identified being 75.0%. They also investigated the influence of tem-
and 680 °C and reported an increase in gas percentage composition perature from 300 to 700 °C on oil composition and showed that
for hydrogen, carbon monoxide, methane, ethane, ethene and C3+ limonene concentration (reported as chromatogram peak area) de-
hydrocarbons. They also reported an increase in hydrogen sulphide creased from 21.07% at 300 °C to 3.29% at 700 °C. Benzene, ethyl-
with increased pyrolysis temperature. Leung et al. (2002) used a benzene and xylenes also showed a decrease in concentration at
fixed bed reactor, but at temperatures from 500 °C up to 1000 °C high temperature. Olazar et al. (2008) reported a limonene concen-
and reported that the main gases produced were hydrogen, meth- tration of 26.8 wt.% in the oil from the pyrolysis of tyres in a conical
ane and ethene. Between 800 °C and 1000 °C, hydrogen continued spouted bed reactor. The high concentration was reported to be
to increase in yield, but methane and ethene showed a small de- due to the short residence time of the primary pyrolysis products
crease. Conesa et al. (2004) also investigated high temperature in their reactor which minimised the cracking of the limonene to
pyrolysis of tyres at 450, 750 and 1000 °C in a drop tube reactor. aromatic and polyaromatic hydrocarbons.
Methane yield showed a marked increase with increasing pyrolysis However, Li et al. (2004) also investigated the influence of tem-
temperature, whereas carbon dioxide and ethene decreased be- perature between 450 and 650 °C on the concentration of various
tween 750 and 1000 °C pyrolysis temperature. volatile aromatic hydrocarbons. They reported an increase in ben-
zene from 0.40 to 2.09 wt.%, toluene from 2.26 to 7.05 wt.%, xylene
from 1.53 to 2.01 wt.% and styrene from 1.20 to 2.64 wt.%. The in-
6. Higher value products from waste tyre pyrolysis
creases in benzene, toluene, xylene and styrene were attributed to
the thermal degradation of limonene, which decreased from 5.44
Attempts have been made to increase the value of tyre pyrolysis
to 0.07 wt.% as the temperature of pyrolysis was increased from
products, through for example, selective pyrolysis temperature,
450 to 650 °C (Pakdel et al., 1992; Cunliffe and Williams, 1998a).
post pyrolysis selective condensation, distillation of the product
Vacuum pyrolysis of tyres has shown a yield of limonene of
oil and the use of catalysts to influence the oil or gas composition
3.6 wt.% of feedstock tyre, but on distillation yields of 15 wt.% of
or through upgrading of the char to produce activated carbon or
limonene were found in the naphtha fraction which constituted
higher value carbon black.
26.8% of the total pyrolysis oil (Pakdel et al., 1992, 2001) Stanciule-
scu and Ikura (2006) also distilled tyre pyrolysis oil produced from
6.1. Chemicals from tyre pyrolysis oils an ablative reactor system and reported that vacuum distillation of
the oil produced a naphtha yield of 25.5 wt.% containing 16.3 wt.%
Table 3 showed that the tyre pyrolysis oils contain a wide range limonene. They also reported a toluene concentration of 11 wt.%,
of chemicals. However, of great interest the oils have been shown xylene at 23.8 wt.%, styrene at 8 wt.% and benzene at less than
to contain significant concentrations of valuable chemicals such as, 3 wt.%. Redistillation of the fraction increased the limonene con-
benzene, toluene, xylenes, styrene and limonene which are used in centration to approximately 32–37 wt.% (Stanciulescu and Ikura,
the chemical industry (Pakdel et al., 1992; Cunliffe and Williams, 2006).
1998a; Li et al., 2004; Kaminsky et al., 2009). For example, benzene Williams and Brindle (2003c) examined the use of post-pyroly-
is used to produce derivatives such as ethylbenzene, cyclohexane sis selective temperature condensation of tyre pyrolysis oils to
concentrate higher value aromatic compounds. Three separate benzene, xylene and toluene. They also reported that polyaromatic
condensers were used fixed at 100, 150, 200 or 250 °C were inves- hydrocarbons were markedly increased with the HY catalyst but
tigated together with a final condenser held at 70 °C to trap the less so with the ZSM-5 catalyst. For example, naphthalene in-
final condensable gases. The influence of the type of packing mate- creased from 0.24 to 4.95 wt.% and the methyl-, dimethyl- and tri-
rial within the condenser system was also examined. The results methyl naphthalenes increased from 0.22 to 11.9 wt.% for the HY
showed that the concentration of limonene in the oil fraction col- catalyst. Shen et al. (2007) also investigated the use of zeolite Y
lected in the first condenser at a condensation system operating and ZSM-5 type catalysts using a two-stage (pyrolysis–catalysis)
temperature of 100 °C was 1.5 wt.%, and was 6.8 wt.% in the final fixed bed reactor. They reported a dramatic increase in single ring
condenser. At 250 °C condenser temperature the concentration of aromatic compounds when the catalysts were used. Analysis of the
limonene in the oil in the first condenser was reduced to 0.5 wt.% light fraction (<220 °C) of the oil produced after catalysis showed
and was 5.6% in the final condenser. The type of packing material concentrations of toluene of 11.62 wt.%, benzene 1.6 wt.% and xy-
in the condensers was also shown to influence the concentrations lenes of 16.69 wt.% for the Y catalyst. Zhang et al. (2008) investi-
of the aromatic compounds found in the condensers. gated the pyrolysis of tyres under vacuum conditions between
450 and 600 °C in the presence of Na2CO3 and NaOH in an attempt
6.2. Catalytic pyrolysis of waste tyres to increase the concentration of limonene in the oil and conse-
quently in the distilled naphtha fraction. They obtained concentra-
Catalysts have been used in the tyre pyrolysis system to in- tions of 12.39 wt.% limonene in the naphtha distillation fraction of
crease the yield of aromatic compounds. Williams and Brindle the tyre oil derived from vacuum pyrolysis of tyres with the NaOH
(2003b) investigated the use of two types of Y zeolite catalyst additive. However, no improvement was obtained with the Na2CO3
(CBV-400 and CBV-780) and a zeolite ZSM-5 catalyst for the pro- additive.
duction of higher value aromatic hydrocarbons in relation to the
catalyst:tyre ratio. They used a fixed bed tyre pyrolysis reactor at
6.3. Hydrogen from waste tyre pyrolysis
500 °C and the pyrolysis vapours were passed directly to a heated
secondary catalysis reactor also at 500 °C. They reported a decrease
There is much interest in producing hydrogen from various
in oil yield from 55.8 to 32 wt.% as the amount of catalysts in the
materials, including waste tyres to help in the fulfilment of the pre-
secondary reactor was increased and a consequent increase in gas
dicted hydrogen economy of the future. For example, Mastral et al.
yield, mainly methane, propane and isobutene. However, examina-
(2002) have suggested that pyrolysis of tyres to produce an oil that
tion of the oil showed a dramatic increase in concentration of ben-
is subsequently gasified with oxygen to produce hydrogen. They
zene, xylenes and toluene. For example, for the Y zeolite (CBV-400)
showed that 1 kg of waste tyre could be converted to 0.158 kg of
produced a product oil containing 24 wt.% toluene, 5 wt.% benzene,
hydrogen using oxygen gasification and the presence of steam.
20 wt.% m/p-xylenes and 7 wt.% o-xylene. The Y zeolite (CBV-400)
The hydrogen derived from the tyre hydrogen content and the
with larger pore size and higher surface activity was found to pro-
steam input via the water gas shift reaction conversion of carbon
duce the higher aromatic content in the product oils. They also re-
monoxide. The use of post-pyrolysis catalysis at higher tempera-
ported a marked increase in concentration of naphthalenes and
ture using nickel based catalysts has been investigated to produce
alkylated naphthalenes as the catalyst:tyre ratio was increased.
hydrogen from waste tyres (Elbaba et al., 2010, 2011; Elbaba and
Williams and Brindle (2002) also used the same reactor system
Williams, 2012). Elbaba et al. (2010) used a reactor system which
and the Y zeolite CBV-400 and ZSM-5 catalysts and investigated
consisted of fixed bed pyrolysis of tyres at 500 °C, the tyre pyrolysis
the influence of secondary catalyst temperature from 430 to
gases were then passed directly to a fixed bed of a nickel based Ni–
600 °C. For the Y-zeolite (CBV-400) catalyst, benzene increased
Mg–Al catalyst at 800 °C and reacted with steam. They also re-
from 2.8 to 10.2 wt.% as the catalyst bed temperature was in-
ported hydrogen production from several different rubbers used
creased from 430 to 600 °C. Toluene increased from 16.3 to
in tyre manufacture. The gas yield from pyrolysis–gasification in-
21.7 wt.%. However, m/p-xylene decreased with increasing cata-
creased from 22.2 wt.% in the absence of steam and catalyst to
lysts temperature above 530 °C, falling from 14 to 8.5 wt.%, o-xy-
36.2 wt.% in the presence of steam and catalyst. The gas consisted
lene also decreased from 4.8 to 2.7 wt.%. The authors (Williams
of more than 65 vol% of hydrogen, representing conversion of tyre
and Brindle, 2003a) extended the research to investigate the pyro-
to hydrogen of 5.43 wt.%. It was reported that polybutadiene rub-
lysis–catalysis of tyres in a fluidised bed reactor. The tyre particles
ber produced 15.26 wt.% of hydrogen, styrene–butadiene-rubber
were pyrolysed in a 0.2 kg h 1 fluidised bed with a fixed catalyst
produced 12.00 wt.% hydrogen and natural rubber 8.98 wt.%
bed placed in the freeboard of the reactor. Although benzene, xy-
hydrogen during pyrolysis–catalytic steam gasification. Elbaba
lene and toluene concentrations increased in the product oil in
et al (2011) and Elbaba and Williams (2012) further investigated
the presence of the catalysts, the concentrations were lower com-
the influence of various process conditions on the yield of hydro-
pared to the fixed bed reactor. The reduced concentrations of aro-
gen using the same reactor system. They showed that increased
matic products was attributed to the shorter residence time of the
hydrogen production could be achieved at increased nickel content
product tyre pyrolysis gases passing through the fixed catalyst bed
of the catalyst, high catalyst temperature (900 °C), higher cata-
due to the increased gas velocity in a fluidised bed reactor which is
lyst:tyre ratio (2.0 g g 1) and higher steam flow rate (10.4 g h 1).
required to maintain the fluidisation of the sand bed.
Olazar et al. (2008) also investigated the use of HY and HZSM-5
zeolite catalysts using a conical spouted bed reactor. They reported 6.4. Carbon black and activated carbons from waste tyre pyrolysis
an increase in the concentration of single ring aromatic compounds
in the oil from 20.17 wt.% in the absence of the catalysts to Upgrading the tyre product char has centred on improving the
32.49 wt.% with the HZSM-5 catalyst and to 40.49 wt.% with the characteristics of the char for recovered carbon black or through
HY catalyst. In addition, the presence of the catalyst in the pyroly- post-pyrolysis activation to produce activated carbons. Post-pyroly-
sis reactor system led to increased benzene, toluene and xylene sis heat treatment (between 670 and 860 °C) to minimise pyrolytic
concentrations compared to only thermal pyrolysis; from 0.21 to carbon deposition has been applied to the vacuum pyrolysis of tyres
3.64 wt.% for benzene, 0.78 to 7.39 wt.% for toluene and from (Pantea et al., 2003). The surface chemistry of the resultant carbon
1.23 to 9.00 wt.% for the xylenes in the presence of the ZSM-5 blacks was changed by the secondary heat treatment producing a
catalyst. For the HY catalyst, there were only small increases in more polyaromatic character and the electrical conductivity of the
carbons were improved to values greater than commercial carbon between 850 and 950 °C for 4 h. They reported that as the activa-
blacks. tion temperature was increased from 850 to 950 °C in the presence
The production of activated carbons from carbonaceous chars of the carbon dioxide, the burn-off increased from 21.3% to 51.3%
requires and activating agent such as steam or carbon dioxide. with a consequent increase in surface area of the activated carbons
The activating agent reacts with the carbon of the char to produce from 125 to 306 m2 g 1 (the maximum surface area achieved).
mainly hydrogen, carbon monoxide, carbon dioxide and methane Helleur et al. (2001) used a continuous ablative reactor system to
when steam is used and for carbon dioxide as the activating agent, pyrolyse waste tyres at 550 °C, the ablative system providing high
carbon monoxide is the main gas product. The reaction with the heating rates and rapid removal of products. The product chars
carbon to produce gases opens up the pores of the char to produce were subsequently carbonised under nitrogen at 900 °C for 1 h
higher surface areas, approaching those of activated carbons of prior to activation at 900 °C using steam or carbon dioxide and at
typically between 400 and 1500 m2 g 1 (Cunliffe and Williams, different activation times. The maximum reported surface are of
1999). This results in loss of carbon or ‘burn-off’ of the carbon the product activated carbons was 302 m2 g 1, achieved using
which is increased at increased gasification temperatures and/or steam at 900 °C for 3 h activation time.
extended reaction time. Because tyre pyrolysis chars contain typi-
cally between 8 and 15 wt.% ash (Table 6), the loss of carbon in-
creases the relative wt.% of the ash. With typical burn-off carbon 7. Commercial and semi-commercial tyre pyrolysis systems
losses of between 50 and 70 wt.%, the ash content can increase to
more than 30 wt.% of the product activated carbon. Table 8 shows examples of commercial and semi-commercial
Cunliffe and Williams (1998b, 1999) investigated the upgrading tyre pyrolysis systems from around the world. The table shows
of tyre pyrolysis char produced from the fixed bed pyrolysis of some examples, rather than an exhaustive list of the wide range
tyres at 450 °C using a fixed bed reactor and steam or carbon diox- of companies which have developed tyre pyrolysis technologies.
ide as the activating agent at activation temperatures of 835 °C, Batch tyre pyrolysis reactors have throughputs of typically 1–2
865 °C, 900 °C and 935 °C. The production of the activated carbons tonnes per day and for increased throughputs additional modules
required removal of the ash in the product activated carbon using would be added. For larger throughputs continuous tyre pyrolysis
concentrated hydrochloric acid for 90 min which reduced the ash reactors have been developed, the most common being rotary kiln
content to between 2 and 5 wt.%. The maximum surface area reactors.
obtained for the product activated carbon was obtained using Kouei Industries (2013) have developed a batch reactor which
steam at 935 °C activation temperature and 65 wt.% carbon burn- can process one tonne batches of whole tyres in a pyrolysis cycle
off was 640 m2 g 1. The pore size characteristics of the carbons which with a typical two unit system can process 16 tonnes per
showed that they were mainly mesoporous carbons. The burn-off day of waste tyres. The tyres are placed in an inner cartridge which
reaction sequence involved micropore formation, pore widening is placed into a furnace. The furnace heats the tyres using tyre
and at longer burn-off times, pore wall destruction and loss of sur- pyrolysis oil produced by the pyrolysis process. The heating time
face area. Carbon dioxide activation produced activated carbons is of the order of 3 h. The product pyrolysis gases pass to vertical
with a 20% lower surface area than those produced with steam. condensation columns which condenses the oil into light and hea-
Teng et al. (1995) reported the pyrolysis of waste tyres in a ther- vy oil fractions, while gases exit from the top of the condensers. At
mogravimetric analyser at temperatures up to 900 °C and the sub- the end of the pyrolysis cycle the cartridge containing the char and
sequent activation of the product chars in a carbon dioxide/helium steel is removed from the furnace and another reactor cartridge is
atmosphere, at 900 °C. They reported surface areas of the pyrolysis inserted into the furnace containing a further one tonne batch of
chars of typically less than 100 m2 g 1. However, after activation tyres. The original cartridge is left to cool and the char is removed
and with 50% burn-off, surface areas of up to 813 m2 g1 and separated from the steel using magnetic separation and wash-
(980 m2 g 1 on an ash free basis) were reported. Zabaniotou and ing. No-waste Technology (2013) also produce a batch pyrolysis
Stavropoulos (2003) used a very high heating rate wire mesh reac- system to process whole waste tyres. The system also comprises
tor to produce chars from the pyrolysis of waste tyres. The product an inner reactor which is placed inside a furnace. Each reactor
chars were then activated in a fixed bed reactor system using processes approximately one tonne of tyres over a process cycle
either steam or carbon dioxide as the activating agent and at reac- of 4–6 h, representing 4 tonnes per day throughput. The oils are
tion temperatures of 850–1000 °C and with varying reaction times. condensed to produce a fuel oil and off-gases are scrubbed and
They reported maximum surface areas of 600 m2 g 1 for both stored under pressure. The char is separated from the steel and
steam and carbon dioxide activating agents at the higher temper- processed via milling/grinding for sale as carbon black. From one
atures of reaction and at longer activation times, i.e. higher degrees tonne of tyres, the products are approximately 380 kg of char,
of burn-off. Li et al. (2004) used a pilot scale rotary kiln reactor to 300 kg pyrolysis oil, 170 kg steel and 150 kg of gas, mainly com-
pyrolyse tyres over a range of temperatures from 450 to 650 °C. posed of methane.
The product char produced at 550 °C was subsequently activated Xinxiang Doing Renewable Energy Equipment Co. Ltd., (2013)
in a fixed bed reactor using carbon dioxide and at temperatures produce several sizes of continuous tyre pyrolysis systems ranging
Table 8
Examples of commercial and semi-commercial tyre pyrolysis systems.
1
Company Location Reactor type Capacity (tonnes day ) References
Splainex Ltd Hague, Netherlands Rotary kiln 20 Splainex (2013)
Xinxiang Doing Renewable Energy Equipment Co., Ltd Xinxiang, China Rotary kiln 6–10 Xinxiang Doing (2013)
RESEM Shangqui, China Rotary kiln 8–20 RESEM (2013)
Kouei Industries Vancouver, Canada Fixed bed/Batch 16 Kouei Industries (2013)
DG Engineering Gummersbach, Germany Rotary kiln 10 DG Engineering (2013)
FAB India Amedabad, India Rotary kiln 5–12 FAB India (2013))
Octagon Consolidated Selangor, Malaysia Rotary kiln 2.4–120 Octagon Consolidated (2013)
No-Waste Technology Reinach, Germany Fixed bed/Batch 4 No-Waste Technology (2013)
PYReco Teeside, UK Rotary kiln 200 PYReco (2013)
Pyrocrat Systems Navi Mumbai, India Rotary kiln 2–10 Pyrocrat Systems (2013)
from 6 to 10 tonnes per day throughput of waste tyres. The system Aylón, E., Fernández-Colino, A., Navarro, M.V., Murillo, R., García, T., Mastral, A.M.,
2008. Waste tyre pyrolysis: comparison between fixed bed reactor and moving
is based on a rotary kiln reactor of size ranging from 2.2 m to 2.8 m
bed reactor. Industrial Engineering Chemistry Research 47, 4029–4033.
diameter and length from 5.5 to 8 m depending on throughput. The Aylón, E., Fernández-Colino, A., Murillo, R., Navarro, M.V., García, T., Mastral, A.M.,
rotary kiln rotates at approximately 0.4 r.p.m. The oil is condensed 2011. Valorisation of waste tyre by pyrolysis in a moving bed reactor. Waste
into heavy and light oil fractions and in some cases a catalytic Management 30, 1220–1224.
Banar, M., Akyıldız, V., Ozkan, A., Cokaygil, Z., Onay, O., 2012. Characterization of
chamber is also included prior to oil condensation. Oil yield is pyrolytic oil obtained from pyrolysis of TDF (Tire Derived Fuel). Energy
reported to be between 45 and 52 wt.%, char at 30 wt.% and steel Conversion and Management 62, 22–30.
at between 12 and 15 wt.%. The product gas is cleaned and com- Benallal, B., Roy, C., Pakdel, H., Chabot, S., Poirier, M.A., 1995. Characterization of
pyrolytic light naphtha from Vacuum pyrolysis of used tyres comparison with
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Pyrolysis of Waste Tyres A Review

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Waste Management 33 (2013) 1714–1728

Contents lists available at SciVerse ScienceDirect

Pyrolysis of waste tyres: A review

1. Introduction are used in material recovery options through the production of

Component Passenger tyre Truck tyre Comments

Reactor Experimental conditions Maximum oil yield References

Table 5 similar to conventional petroleum fuels in terms of H/C ratio, den-

3.4. Combustion of tyre pyrolysis oils

Reactor Temperature Gas composition References

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