Journal of Analytical and Applied Pyrolysis 112 (2015) 113

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Journal of Analytical and Applied Pyrolysis

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Review

A review of dipentene (dl-limonene) production from waste tire

pyrolysis
B. Danon , P. van der Gryp, C.E. Schwarz, J.F. Grgens
Process Engineering Department, Stellenbosch University, Private Bag X1, Matieland 7602, South Africa

a r t i c l e

i n f o

Article history:
Received 12 August 2014
Accepted 27 December 2014
Available online 7 January 2015
Keywords:
Dipentene
dl-Limonene
Waste tire
Pyrolysis

a b s t r a c t
The present review concerns the production of dipentene (dl-limonene) from the pyrolysis of waste
tires and is divided into three parts, which discuss (1) the mechanism of dipentene formation from
polyisoprene, (2) the reported dipentene yields from experimental studies and (3) the separation and
purication of dipentene from a tire-derived oil. Dipentene is formed via an intramolecular cyclization
reaction of the allylic radicals formed by random scission of the bonds with respect to the double
bonds in the polyisoprene chains. Dimerization of two isoprene molecules to form dipentene seems
unlikely under pyrolytic conditions. Especially at higher temperatures, the formed dipentene transforms
further into either isoprene or aromatic compounds, the latter possibly via a diallyl diradical. Both the
pyrolysis operating conditions and the tire type and brand have signicant inuence on the dipentene
yield. Among these, the pyrolysis temperature is the most important variable, with temperatures between
400 and 500 C resulting in maximum dipentene yields. Vacuum pyrolysis and basic additives have been
propounded as a means of further improving this yield, but additional results are required to conrm this
conclusively. Based on the presently available information in the literature, at least 2.5 wt% of a steel-free
tire can be converted to dipentene. Finally, the literature has shown that it is not a trivial exercise to obtain
a highly concentrated dipentene fraction of sufcient quality from the tire-derived oil. In particular, the
removal of sulfur-containing compounds and the separation of dipentene from 1,2,3-trimethylbenzene,
m- and p-cymene and indane are challenges that need to be addressed in the future.
2014 Elsevier B.V. All rights reserved.

Contents
1.
2.
3.
4.
5.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Reaction mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Dipentene production from waste tire pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Dipentene separation and purication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1. Introduction
The continually growing global automobile industry unavoidably results in also steadily increasing amounts of end-of-life or
waste tires. It is estimated that about 1.5 billion waste tires are
produced annually worldwide (see Table 1). Until recently, the
majority of these scrap tires were landlled; it is reported that

Corresponding author. Tel.: +27 (0)218089485.

E-mail address: [email protected] (B. Danon).
http://dx.doi.org/10.1016/j.jaap.2014.12.025
0165-2370/ 2014 Elsevier B.V. All rights reserved.

1
2
4
11
11
12
12

about 4 billion waste tires are currently in landlls and stockpiles

world-wide [1]. However, this type of disposal can result in signicant environmental disturbances, such as, uncontrolled res (with
accompanying pollution of the atmosphere, soil and groundwater)
or by supplying breeding grounds for, e.g., rats or mosquitoes [2].
Also, the voluminosity of a tire, in combination with its resistance
to down-sizing, makes that landlling requires very large spaces.
Due to legislation becoming more stringent over the last years,
in combination with the above-mentioned issues, valorization of
waste tires is gaining both academic and industrial attention. For
example, two European Commission Directives (the Waste Landll

B. Danon et al. / Journal of Analytical and Applied Pyrolysis 112 (2015) 113

Table 1
Number of annually generated waste tires in some countries.
Country

Waste tires (millions year1 )

Year

World-wide [1,7]
USA [15]
European Union [15]
Australia [15]
South Korea [46]
South Africa [85]

1500
500
289
53
28
11

2011
2007
2011
2008
2011
2012

Directive, which bans landlling of tires, and the End Life Vehicle Directive, which stipulates the separate collection of tires from
vehicle dismantling and encourages the recycling of tires) have led
to a decrease from 62% of the generated waste tires being landlled
in the European Union in 1994 to 4% in 2010 [3]. Thus, as large
parts of generated waste tires are currently revalorized, the waste
tire problem has become both an environmental and an economic
challenge.
From a technical viewpoint, several approaches have been
employed for the revalorization of waste tires, such as, tire retreading, mechanical grinding, rubber reclaim, direct combustion or
incineration, amongst others [4]. At present, the majority of waste
tires are reused as ground rubber, e.g., as a binder in asphalt or
in articial sporting grounds [5]. Furthermore, large quantities of
waste tires serve as a direct energy source (so-called tire-derivedfuel or TDF), due to their relatively high caloric value (around
32 MJ kg1 ) compared to other fuels, such as coal or wood [3]. Applications of energy utilization include cement kilns, power plants and
co-incineration with other wastes. However, drawbacks of using
waste tires directly for incineration are its relatively high SO2 and
polynuclear aromatic hydrocarbon (PAH) emissions [6]. One way
to overcome these difculties is to pyrolyze the tire before energy
recovery.
Pyrolysis is a thermal degradation process of volatile matter in
the absence of oxygen which generates a three phases product; a
gas, a liquid and a solid. The volatile matter of a tire mainly consists
of rubbers, the most important being natural rubber (NR), synthetic
polyisoprene (PI), butadiene rubber (BR) and styrene-butadiene
rubber (SBR). Apart from these rubbers, a tire additionally includes
a plethora of processing oils, additives, llers, vulcanization accelerators/inhibitors, which are all added during either the rubber or
tire processing. Generally, a waste tire pyrolysis process results in
520 wt% gas, 4060 wt% liquid and 3040 wt% solid, depending
on operating conditions [1,7]. The solid-phase product or pyrolytic
char consists mostly of carbon black and other additives or llers
(zinc, sulfur, clays and silica) [8,9]. The char can be used as a fuel
directly, or, after upgrading, as an activated carbon or carbon black
[8,10,11]. The gas-phase products are typically C1C4 hydrocarbons and hydrogen [12] and can be used on-site as a fuel to provide
the energy requirements for the pyrolysis process [13]. The liquidphase products or tire-derived-oil (TDO) are typically a mixture of
parafns, olens and aromatic compounds [14] and have a very
high caloric value between 4045 MJ kg1 [7,15]. As part of the
sulfur and most of the ash remains in the char, both the gas and
liquid can be used more readily for energy recovery. Several excellent reviews have been published recently regarding waste tire
pyrolysis focusing on energy recovery from the pyrolytic products
[1,7,15].
The drawbacks of tire pyrolysis for the recovery of fuels are
twofold. Firstly, the pyrolysis process is endothermic, thus less
energy can be recovered compared to direct incineration of the
tire. Secondly, there is the lack of industrial acceptance of the TDO,
and to a lesser extent also the char. Companies that are currently
involved in waste tire pyrolysis face signicant challenges nding
a market for their liquid and solid pyrolytic products.

Fig. 1. Chemical structure of cis-1,4-polyisoprene, dipentene (dl-limonene, 1methyl-4-(1-methylethenyl)-cyclohexene) and isoprene (2-methyl-1,3-butadiene).

One possible approach to make the pyrolytic processing of waste

tires more attractive (from an economical point of view) is the
recovery of valuable chemicals. It is known that the TDO contains
many valuable chemicals, such as, dipentene, benzene, toluene,
xylenes, ethyl benzene, amongst others. Also in the gaseous product there are compounds such as isoprene and butadiene, which
are monomers of the rubbers that are found in tires, that have high
market values. As most studies report that the dipentene concentration in the TDO (from pyrolysis processes operated at relatively
low temperatures) is predominant, this compound has attracted
the most attention. The present review will therefore focus on the
production of dipentene from waste tire pyrolysis.
Dipentene comprises of the racemic mixture of the two
enantiomers d- and l-limonene [14,16]. Its systematic name
is 1-methyl-4-(1-methylethenyl)-cyclohexene, an unsaturated
hydrocarbon classied as a monoterpene. It is the dimer of two isoprene units, which originate from the (either natural or synthetic)
polyisoprene content of the tire. In Fig. 1 the chemical structures of
polyisoprene, dipentene and isoprene are presented. At room temperature dipentene is a colorless oily liquid. Its molecular formula
is C10 H16 , molar mass is 136.24 g mol1 , boiling point is 176 C and
melting point is 74 C. The price of dipentene currently ranges
between 1500 and 2500 US$ per metric tonne, depending mostly
on its purity. It is mainly used as an industrial solvent, as a cleaning agent for, e.g., electrical circuit boards, as a dispersing agent for
pigments, or as an active ingredient in different pesticide products
[7,1517]. Furthermore, carvone can be synthesized from dipentene, which can be used as a mosquito repellent. Finally, while
d-limonene smells like oranges, l-limonene has the smell of pine.
Due to these typical smells, it can also be employed for fragrances
and avorants, that is, if the two enantiomers can be sufciently
separated. It has to be noted here that most of the current dipentene demand is satised by citrus-derived pure d-limonene. Since
a tire-derived dipentene is the racemic mixture of the two enantiomers and probably has a lower consumer appeal, it is also less
suitable as a fragrance or avorant. Therefore, the price for a tirederived dipentene will be slightly lower than that of citrus-derived
limonene.
This review aims at supplying an exhaustive overview of the
currently available literature on the production of dipentene from
waste tires and is subdivided threefold. Firstly, in the subsequent section, the mechanism of polyisoprene degradation under
pyrolytic conditions is reviewed. Secondly, reported dipentene
yields, assembled from literature sources of experimental studies on waste tire pyrolysis, are overviewed and discussed. The
extensive analysis of the dipentene yields based on initial tire
sample weight (in contrast to dipentene concentrations in the
tire-derived oil) allows for indications for future research and technical assessment of dipentene production from waste tires. Finally,
the (scarcely) available information on dipentene separation and
purication from a pyrolytic oil is summarized.
2. Reaction mechanism
The degradation or depolymerization of natural rubber (NR) or
(synthetic) cis-1,4-polyisoprene is a radical reaction, initiated by

B. Danon et al. / Journal of Analytical and Applied Pyrolysis 112 (2015) 113

Fig. 2. Radical generating depolymerization initiation by scission of the bond with

respect to the double bonds in cis-1,4-polyisoprene.

Fig. 3. Depropagation (unzip) of allylic radicals 1 and 2 to isoprene monomer.

Fig. 4. Intramolecular cyclization and scission of allylic radical 1 to dipentene.

scission of the bond with respect to the double bonds of the main
polymer chain [1823]. Whereas Bhowmick et al. also considered
radical formation by scission of the bond and methyl scission,
Chien argues, due to differences in bond strengths, that scission of
the bond is energetically the most favorable among these [18,19].
Fig. 2 shows that scission of the bond in cis-1,4-polyisoprene
results in two different allylic radicals, with the radical either two
carbons (radical 1) or one carbon (radical 2) separated from the
methylated carbon. Cataldo shows that these allylic radicals can be
terminated by adventitious agents (such as oxygen) under milder
conditions than pyrolytic conditions (temperatures not exceeding
380 C), resulting in a liquid polyisoprene with a lower average
molecular weight [24]. However, under pyrolytic conditions, both
radicals can depropagate or unzip towards the monomer isoprene
[18,19,22]. In Fig. 3 this depropagation reaction is shown for the
two radicals.
Simultaneously, both radicals 1 and 2 can also undergo an intramolecular cyclization followed by scission [22]. Such a reaction
of radical 1 will yield dipentene, while radical 2 will yield 1,5dimethyl-5-ethenyl-cyclohexene [18,19,22]. Remarkably, the yield
of dipentene is much higher than that of 1,5-dimethyl-5-ethenylcyclohexene, which has been attributed to steric hindrance of the
methyl group in the cyclization reaction of radical 2 and to higher
stability of radical 1 due to hyper-conjugation [18,19]. In Fig. 4 the
intramolecular cyclization of radical 1 yielding dipentene is presented [18,19,22,25].
Accordingly, the presence of structural units other than 1,4
units (such as 3,4 units) in the polyisoprene polymer can be
identied by the presence of appreciable amounts of various
other C10 compounds among the degradation products, such
as 1-methyl-5-(1-methylethenyl)-cyclohexene (diprene) or 3,4dimethyl-4-ethenyl-cyclohexene [18,19]. It is noted by Golub that
2,3-polyisoprene also results in dipentene, next to the dimer
diprene [22].
While in most studies concerning the composition of a TDO
dipentene is mentioned as the most prevalent product, Bhowmick

Fig. 5. C10-diradical from scission of two bonds in polyisoprene (3) [29,30], and
diallyl diradical of dipentene (4) [33,34].

et al. surprisingly recorded isoprene as the most abundant product

[19]. This was explained by the fact that they used Guayule rubber,
which consisted of 100% 1,4 units, allowing for higher unzipping to
isoprene. Kwon et al. explained the abundance of dipentene compared to isoprene to a radical termination reaction between two
radical 2 molecules [23].
Some researchers have propounded that dipentene can also be
formed via dimerization of two isoprene monomers [16,19,20,25].
Groves et al. based this assumption on the fact that the
monomer/dimer ratio increases for higher temperatures and
decreases for larger particle sizes [25]. These observations made
the authors conclude that the dimers are formed by a DielsAlder
type recombination reaction within the melt. Chen and Qian explicitly did not exclude the possibility of isoprene recombination via
DielsAlder addition based on similarities with butadiene recombinations (from polybutadiene rubbers) [20].
However, as already postulated by Chien and Kiang, this mechanism seems unlikely, since it should lead to signicant yields of
other isoprene dimers [18]. Indeed, Kar et al. has modeled the
dimerization of isoprene using predictive force-eld calculations
[26]. It was calculated that between 25 and 1000 C the conformer diprene was the energetically more favorable product of the
dimerization, not dipentene. Moreover, Sauer states that the steric
hindrance for 1,3-disubstituted DielsAlder products from this type
of reaction is of little signicance [27]. Finally, experimental results
of the DielsAlder addition of methyl acrylate (dienophile) to isoprene (diene) show that, at temperatures between 20 and 400 C,
at least signicant amounts of the 1,3-disubstituted isomer should
be formed [27,28]. Thus, it is concluded that, although isoprene
dimerization cannot be conclusively excluded, the lack of diprene
as a pyrolysis product indicates that this reaction seems unlikely.
An alternative mechanism for the direct formation of dipentene from polyisoprene has been proposed [29,30]. After scission
of two bonds with respect to the double bonds in the main chain,
a C10-diradical is formed (see radical 3 in Fig. 5), which subsequently isomerizes to its cyclic form (dipentene), analogously to
the isomerization of propene towards cyclopropane. However, no
experimental data are supplied to substantiate the proposed mechanism. Moreover, it is also not specied how (simultaneously or
subsequently) or why the main chain is scinded specically to form
this C10-diradical. Actually, the scission of the bonds in the main
polyisoprene chain is mostly considered to be random. The fact that
Groves et al. and Hall et al. observed isoprene oligomers (up to hexamers) as the product of the thermal degradation of natural rubber
and latex gloves, respectively, also stipulates that the scission is
random [25,31].
Finally, it is considered that although isoprene and dipentene
were the two predominant products of polyisoprene pyrolysis
below a temperature of around 410430 C [20,32], at higher pyrolysis temperatures their yield decreases. This can be due to further
fragmentation or aromatization of the formed monomers and
dimers [14,19], and/or due to fragmentation of the polymer (competitively with unzipping and internal cyclization reactions) [20].
It has been shown that the pyrolysis of dipentene around 450 C
yields isoprene, other terpenes and aromatics [33,34]. The formation of these products were explained by reactions of dipentene

B. Danon et al. / Journal of Analytical and Applied Pyrolysis 112 (2015) 113

via a diallyl diradical, see radical 4 in Fig. 5. Furthermore, the production of isoprene from the pyrolysis of dipentene has also been
demonstrated by Davis et al. [35]. The fact that maximum isoprene
concentrations have been reported at slightly higher pyrolysis temperatures than those for maximum dipentene yields, could be a
result of this latter reaction [3639]. Thus, as the fragmentation
and aromatization of dipentene under pyrolytic conditions seems
proven, the decrease of the dipentene yields at higher temperatures
is either solely due to these reactions, or due to the combination
of them with competitive fragmentation of the main polyisoprene
polymer.
Tamura et al. have investigated the thermal degradation of
cis-1,4-polyisoprene and its vulcanizates, containing either carbon or sulfur cross linkages [21]. Generally, scission of the main
polymer chain starts at 300 C, but the devolatilization of the polyisoprene with sulfur cross linkages started at lower temperatures
(around 200 C). This was attributed to the breaking of the polysulde cross linkages, which occurs at lower temperatures, due to
their lower bond dissociation energies [40]. The formed polythiyl
radicals abstract allylic hydrogen from the polyisoprene, which is
followed by scission of the main chain and subsequent mono- and
dimer production.
Finally, it has been reported (erroneously) by some authors that
dipentene can also be formed from polybutadiene [14,30]. This
claim was based on a misinterpretation of the papers by Brazier
et al. and Madorsky [41,42]. The pyrograms presented by Miguel
et al. conrm that no dipentene is formed from polybutadiene [43].
Thus, it can be concluded that both isoprene and dipentene
are mainly formed via direct depolymerization of polyisoprene,
initiated by random scission of the bonds with respect to the
double bonds in the main polymer chain. The monomers and
dimers are formed by unzipping and intramolecular cyclization
reactions, respectively. The lack of dipentene conformers among
the pyrolytic products indicates that dimerization of isoprene is
unlikely. However, dipentene itself (especially at higher temperatures) can transform further into either isoprene or aromatic
compounds, the latter possibly via a diallyl diradical.

3. Dipentene production from waste tire pyrolysis

In this section an exhaustive overview is presented of reported
experimental yields of dipentene from waste tire pyrolysis. At
present such an overview is lacking in the literature. While Pakdel
and Zhang made an effort on presenting selections of reported
yields (either in text or tabulated, respectively), both authors report
dipentene concentrations in the pyrolytic oil [17,40]. Since it is
known that the oil yield can vary signicantly between different
pyrolysis operating conditions, this seems unsatisfactory. Therefore, in this work the dipentene yields are based on the initial tire
or crumb sample weight fed to the reactor.
It is, however, noted that the current approach is still accompanied by some difculties, which induce some caution for direct
comparison of the presented results. Firstly, some authors report
that they used tires including the bers, whereas others explicitly separated them from the sample. Secondly, while in some
studies the steel content of the tires was present in the pyrolysis reactor, all reported yields were compensated for the steel
content. Thirdly, and more importantly, the separation, identication, and accordingly the quantication, of specic compounds
is notoriously difcult in TDOs. Due to the plethora of compounds
present, the oil cannot be completely separated using highly optimized 1-dimensional GC methods. This is clearly conrmed by
comprehensive 2-dimensional GC (GCGC) separation of TDOs,
see for example the GCGC chromatograms of Rathsack et al. [44].
To overcome this difculty some authors use a pre-fractionation

Fig. 6. Graphical overview of governing variables in pyrolysis.

step before analysis. This inevitably introduces other inaccuracies,

such as variable recoveries, combined with the fact that many different fractionation methods are used, which further complicates
direct comparison of the results. Finally, the various ways of detecting and quantifying compounds also show major variations. Only
a few studies explicitly mention that analytical standards were
used [14,4552]. The paper of Kyari et al. supplies very insightful results in this respect, as they report for one experiment both
the %-area (13.79%) using a GC/MS instrument and the calibrated
wt% (3.11%) of dipentene [52]. Although the peak area of a Flame
Ionization Detector (FID) can be used to estimate the weight percentage for hydrocarbons, the denition of the total peak area will
have a large inuence on the calculated percentage area. In a typical
GC-FID chromatogram of a TDO, a large hump of unresolved material is often encountered (especially for relatively fast separations)
[52,53]. The inclusion and integration of this hump has a signicant effect on the nal wt% of the individual compounds. In order
to assist the reader with the correct interpretation of the presented
data, it was therefore decided to include in the overviews which
analysis method was used and whether calibration with analytical
standards was performed for determining the dipentene yield.
Taking into account these difculties, the trends in the dipentene yields will be mostly discussed per study. Merely those values
that were (explicitly) calibrated will be compared among each
other.
In the remainder of this section, the results are presented and
discussed based on the main pyrolysis variables that have been
studied in the literature. In Fig. 6 the most important governing
variables in pyrolysis are schematically overviewed, these being the
pyrolysis temperature, heating rate, pressure, sample particle size,
feedstock composition, inert atmosphere ow rate, the residence
time in the reactor and nally the use of catalysts. A distinction
has been made between primary and secondary pyrolytic reactions. The primary reactions include radical initiation reactions and
subsequent depolymerization (and possible fragmentation) of the
polymer chain. Cross linking or condensation reactions of the polymer chains, which are due to reactions of the radicals with the main
chain, are also considered as primary reactions. The secondary reactions then comprise of the thermal fragmentation of the remaining
condensed product, as well as any further reactions of the volatile
products of the primary reactions (e.g., cracking, aromatization and
recombination reactions). Thus, it is noted that the primary and
secondary reactions both include not only devolatilization but also
solid formation reactions.
In the following, results will be subsequently presented for studies focusing on varying the temperature, pressure, type of tire and
catalytic pyrolysis, respectively. It is noted here that the residence
time is also a very important variable, mainly due to secondary
reactions in the gaseous phase of the formed monomers and dimers.
However, since measured or estimated values of the residence time
are scarcely reported, a thorough discussion of this variable would
be highly speculative and was therefore not included in this review.
Finally, the inuence of the type of reactor is discussed.

Table 2
Dipentene yields from studies that have varied the pyrolysis temperature. ACR, autoclave reactor; CSBR, conical spouted bed reactor; FBR, uidized bed reactor; FID, ame ionization detection; FR, feeding rate; HR, heating rate;
GC, gas chromatography; KR, Kiln reactor; MR, microreactor; n.m., not mentioned; p, pressure; PCT, passenger car tire; (Q)MS, (quadrupole) mass spectrometry; RKR, rotary kiln reactor; SS, sample size; T, temperature; TDO,
tire-derived oil; TT, truck tire; XBR, xed bed reactor; XBR-FT, xed bed reactor with re tubes; XBR-MW, xed bed reactor with microwave.
Tire type

Particle size

FR (kg/h)
SS (kg)

Reactor type

T ( C)

HR ( C min1 )

p (kPa)

Carrier gas

Flow (L/min)

TDO (wt%)

Dipentene (wt%)

Analysis method

Calib?

[54]

n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
TT
TT
TT
TT
n.m.
n.m.
PCT-1
PCT-1
PCT-1
PCT-1
PCT-1
PCT-1

1315 mm
1315 mm
1315 mm
1315 mm
1315 mm
4 mm
4 mm
12 mm
12 mm
12 mm
12 mm
10.5 tires
10.5 tires
10.5 tires
10.5 tires
3 1.5 50150 cm
3 1.5 50150 cm
3 1.5 50150 cm
3 1.5 50150 cm
3 1.5 50150 cm
3 1.5 50150 cm
11.4 mm
2030 mm
2030 mm
2030 mm
2030 mm
2030 mm
n.m.
n.m.
< 1 mm
< 1 mm
< 1 mm
< 1 mm
< 1 mm
< 1 mm
< 1 mm
4000 mm3
4000 mm3
4000 mm3
4000 mm3
14 mm
14 mm
20 20 mm
20 20 mm
20 20 mm
20 20 mm
20 20 mm
20 20 mm

1215
1215
1215
1215
1215
0.03
0.03
0.05
0.05
0.05
0.05
310
771
770
1015
3
3
3
3
3
3
0.15
0.175
0.175
0.175
0.175
0.175
1.20E05
1.20E05
0.002
0.002
0.002
0.002
0.18
0.18
0.18
0.75
0.75
0.75
0.75
0.01
0.01
0.21
0.23
0.25
1.5
0.5
0.06

RKR
RKR
RKR
RKR
RKR
ACR
ACR
XBR, 2.2 L
XBR, 2.2 L
XBR, 2.2 L
XBR, 2.2 L
KR, 4300 L
KR, 4300 L
KR, 4300 L
KR, 4300 L
XBR, 16.3 L
XBR, 16.3 L
XBR, 16.3 L
XBR, 16.3 L
XBR, 16.3 L
XBR, 16.3 L
FBR, 1.2 L
ACR, 3.5 L
ACR, 3.5 L
ACR, 3.5 L
ACR, 3.5 L
ACR, 3.5 L
MR
MR
CSBR
CSBR
CSBR
CSBR
CSBR
CSBR
CSBR
XBR-FT, 2.1 L
XBR-FT, 2.1 L
XBR-FT, 2.1 L
XBR-FT, 2.1 L
XBR, 0.24 L
XBR, 0.24 L
XBR-MW, 1 L
XBR-MW, 1 L
XBR-MW, 1 L
XBR-MW, 5 L
XBR-MW, 1 L
XBR-MW, 1 L

450
500
550
600
650
450
750
500
600
700
800
700
850
800
950
450
475
500
525
560
600
570
300
400
500
600
700
450
500
425
500
550
610
425
500
600
425
475
525
575
400
400
599
491
493
514
471
344

Fast
Fast
Fast
Fast
Fast
Fast
Fast
10
10
10
10
n.m.
n.m.
n.m.
n.m.
5
5
5
5
5
5
5
15
15
15
15
15
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
15
15
15
15
5
35
6 kW
3 kW
1.5 kW
3 kW
3 kW
3 kW

85
85
85
85
85
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101

N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
He
He
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2

n.m.
n.m.
n.m.
n.m.
n.m.
1.5
1.5
2
2
2
2
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
1.5
1
1
1
1
1
0.1
0.1
6.5
6.5
6.5
6.5
9.5
9.5
9.5
8
8
8
8

43.0
45.1
44.6
42.7
42.9
37.8
10.9
38.3
30.9
30.5
29.8
27.3
32.5
23.9
24.0
58.1
58.2
56.2
56.9
55.4
53.1
57.1
4.8
24.8
38.0
38.2
38.5
43.2
52.3
65.4
62.0
63.0
62.7
64.3
62.3
54.4
52.0
55.0
51.0
48.0
38.8
31.1
31.5
42.6
20.7
39.3
44.0
30.1

2.34
0.85
0.19
0.05
0.03
0.69
0.02
2.55
1.16
1.27
1.24
0.63
0.42
0.26
0.24
1.82
1.77
1.63
1.65
1.36
1.33
2.06
1.01
2.04
1.95
1.22
1.27
14.00
9.42
23.93
16.94
13.59
6.34
20.40
10.29
0.94
26.42
27.97
12.67
10.20
0.66
0.01
1.17
1.46
0.52
1.86
2.06
2.89

GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC
GC
GC
GC
GC-FID
GC-FID
GC-FID
GC-FID
GC-FID
GC-FID
GC-FID
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC-FID
GC-FID
GC/MS
GC/MS
GC/MS
GC/MS
GC-FID
GC-FID
GC-FID
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS

No
No
No
No
No
No
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
Yes
Yes
No
No
No
No
No
No

[86]
[46]

[47]

[14]

[48]
[53]

[37]
[36]

[39]

[30]

[45]
[56]

B. Danon et al. / Journal of Analytical and Applied Pyrolysis 112 (2015) 113

Ref.

B. Danon et al. / Journal of Analytical and Applied Pyrolysis 112 (2015) 113

Many studies have investigated the inuence of the pyrolysis

temperature on the dipentene yield, see Table 2. The investigated
temperatures range from 300 C up to 950 C. All these studies
report lower dipentene yields at higher temperatures. This trend
is in accordance with the reported temperature range at which
dipentene is formed (between 410 and 430 C) and its propounded
degradation and/or aromatization at higher temperatures (see
previous section). At relatively low temperatures (below around
450 C) the nal dipentene yields are reduced due to low liquid yields (and thus incomplete pyrolysis). For example, the high
dipentene concentration in the oil from an experiment at 300 C,
as reported by Laresgoiti et al., is much lower when considered
on weight basis of the sample. Actually, about double amounts of
dipentene are obtained at 400 and 500 C [53]. There seems to be
a maximum in the dipentene yield within the temperature range
400500 C. This maximum is reported at 400 [53], 425 [36,39],
450 [14,37,54], 475 [30], or 500 C [46] for the different studies.
The variation in this temperature for maximum dipentene yield is
mainly due to the inuences of the other governing variables. The
highest calibrated dipentene yields are 2.06 and 2.55 wt% at 500
and 570 C, respectively [46,48], while above 600 C these yields do
not exceed about 1.5 wt% [14,46,47]. Moreover, it has to be noted
that if the heating rate is low and the (nal) pyrolysis temperature
exceeds the temperature at which the tire is completely pyrolyzed
(i.e. around 550 C), this nal pyrolysis temperature will have no
effect on the product distribution [14,46,47,53].
There is only one study that specically investigated the inuence of heating rate on the nal dipentene yield [45]. Two different
heating rates were compared (5 and 35 C min1 ), with a nal pyrolysis temperature of 400 C, and the highest dipentene yield was
obtained with the lower heating rate. Thus, the supposedly lower
thermal degradation rates allowed for more production of dipentene. Unfortunately, this study did not report dipentene yields at
higher pyrolysis temperatures for the different heating rates. As
can be observed in Fig. 6, the heating rate also has an inuence
on the temperature within the tire particle, mainly in concordance
with the sample particle size, see also [55]. So the trend observed by
Banar et al. could be different for different particle sizes [45]. Unfortunately, no results are available for the inuence of the particle size
on the dipentene yield.
Undri et al. have studied the pyrolysis of waste tires using
microwave heating [56]. As it turned out to be very complicated to
measure (or even estimate) the actual pyrolysis temperature, they
mainly use the microwave power over the sample mass squared
(Pm2 ) instead. However, the values of the Pm2 do not show a
straightforward relation with the temperatures they did measure.
From the results it can be concluded that highest dipentene yields
are obtained at a power of 3 kW and with the smallest investigated
sample size.
Next, studies that either use reduced pressure or vary the
operating pressure are discussed, see Table 3. The group of Laval
University in Canada has investigated waste tire pyrolysis on
different scales for dipentene production at vacuum conditions
[16,17,5759]. From all their papers, Roy reported the highest
dipentene yield of 5.0 wt% for a xed bed reactor at 500 C [59].
The experimental results of vacuum pyrolysis by Zhang et al. conrm this value (they show a dipentene yield of 4.9 wt% at 500 C)
using similar analytical apparatus [40]. Generally, the use of vacuum pyrolysis is considered as promising for dipentene production
since the residence times of the evolved volatiles are shorter compared to atmospheric pyrolysis (avoiding secondary reactions of the
dipentene). However, since all the presented values were obtained
from non-calibrated analyses, it is not yet possible to conclusively
state that vacuum pyrolysis actually results in higher dipentene
yields. Actually, Lopez et al. investigated the decrease of pressure
systematically from atmospheric pressure to 25 kPa in a spouted

bed reactor [60]. They show that the dipentene yield decreases
with decreasing pressure. Simultaneous to this decrease in dipentene, an increase in the isoprene concentration is observed. The
authors explain these trends by assuming that the dimerization
of isoprene in vacuum is inhibited. However, it needs to be noted
here that these experiments are performed at reduced pressure,
rather than in vacuum. An alternative explanation (if dimerization
is assumed to be unlikely, see previous section) is that unzipping
reactions (which yield one isoprene molecule per isoprene unit) are
favored over internal cyclization reactions (which form one dipentene molecule for every two isoprene units) at reduced pressures,
analogously to Le Chateliers principle for chemical equilibria.
In Table 4 the experimental yields of studies varying the type
of tire used are overviewed. There are two studies that compare
dipentene yields from both truck tires (TT) and passenger car tires
(PCT) [38,61]. Lopez et al. report higher dipentene yields (almost
double) for a PCT (with 30 wt% NR) compared to a TT (with 60 wt%
NR) at 425 C in a spouted bed reactor [38]. At higher temperatures (500 and 600 C) the dipentene yields are comparable for the
two tires. Admittedly, the isoprene concentrations are lower for the
PCT, however, the sum of these mono- and dimers are still higher
for PCT than for TT. Actually, at 425 C the reported isoprene and
dipentene concentrations sum to 25 wt%, with an initial NR content in the sample of 30 wt%. Ucar et al. show that dipentene covers
almost 30 %-area in the GC chromatogram for a pyrolytic oil from
TT (with 51 wt% NR) using a xed bed reactor at 650 C [61]. When
PCT is used (with 35 wt% NR) at the same conditions, no peak for
dipentene is observed. The comparative study of Roy et al. of pyrolysis of a TT and poly-isoprene also shows that higher dipentene
yields are to be expected from a tire with a higher NR content [59].
Islam has reported dipentene yields from the pyrolysis of truck
tires (TT), motorcycle tires (MT) and bicycle tires (BT) [62,63]. The
amount of dipentene formed decreases for these tires in the order
TT > MT > BT. Although no exact rubber contents are presented for
the three tires types, it can be estimated from the presented DTG
curves of MT that it has more BR and SBR than natural rubber or
synthetic polyisoprene [62]. Hall shows dipentene yields for the
pyrolysis of latex gloves [31].
Kyari et al. and Undri et al. have both reported the dipentene
yields for different brands of PCT [52,64]. Both use a xed bed reactor, but Undri uses a microwave for heating, which makes direct
comparison more complicated (see above). The main conclusion
that can be drawn from these two studies is that also different
brands of PCT (can) result in signicant differences in the dipentene
yield. For example, Undri observes consistently higher dipentene
yields from PCT-2 (BFGoodrich) compared to PCT-1 (Michelin).
Kyari shows that Michelin tires produce average amounts of dipentene, compared to the other tire brands. These differences can most
probably be explained by the specic rubber compositions of the
different PCTs.
There are many studies that have used different types of catalysts in order to increase the concentrations of targeted valuable
chemicals in the TDO. Most of these studies use acidic catalysts (various types of zeolites), see Table 5 [31,37,4951,6570]. Generally,
the objective (and the result) of the usage of this type of catalyst is
an increase in the yield of single-ring aromatics. This improvement
in the benzenetoluenexylenes content is however at the expense
of the dipentene yield. For all the experiments reported using zeolites a distinct decrease in the dipentene yield is observed, see also
the pyrograms of Miguel et al. [43]. The governing variables for the
catalysis are catalyst pore size, silica/alumina ratio and catalyst to
sample ratio. Generally, it is assumed that the volatile hydrocarbons from pyrolysis (including dipentene) are cracked (secondary
reactions) by the acidic zeolites, followed by reforming reactions
[50,65]. Olazar et al. substantiated this hypothesis by their observation of an increase in the lighter hydrocarbon fraction in the

Ref.

Tire type

Particle size

FR (kg/h)
SS (kg)

Reactor type

T ( C)

HR ( C min1 )

p (kPa)

Carrier gas

Flow (L/min)

TDO (wt%)

Dipentene (wt%)

Analysis method

Calib?

[57]
[16]
[58]
[59]

n.m.
PCT
PCT
TT
TT
PCT
TT
TT
TT
TT
TT
TT
n.m.
n.m.
n.m.
PCT
PCT
PCT
PCT
PCT
PCT

n.m.
613 mm
6 12 mm
2000 mm3
2000 mm3
2700 mm3
< 3800 mm3
< 3800 mm3
< 3800 mm3
< 3800 mm3
< 3800 mm3
< 3800 mm3
2060 mesh
2060 mesh
2060 mesh
< 10 mm
< 10 mm
< 10 mm
< 10 mm
< 10 mm
< 10 mm

<100
3.5
19
1
1
21
42
25
33
0.2
0.2
0.2
0.1
0.1
0.1
0.18
0.18
0.18
0.18
0.18
0.18

SBR
SHF, 770 L
MBR, 850 L
XBR, 15 L
XBR, 15 L
SHF,770 L
MBR, 850 L
MBR, 850 L
MBR, 850 L
XBR, 1L
XBR, 1L
XBR, 1L
ACR, 0.1 L
ACR, 0.1 L
ACR, 0.1 L
CSBR
CSBR
CSBR
CSBR
CSBR
CSBR

525
510
500
500
500
500
500
540
451
480
440
480
450
500
550
425
425
425
500
500
500

Fast
Fast
Fast
15
15
Fast
Fast
Fast
Fast
n.m.
n.m.
n.m.
20
20
20
Fast
Fast
Fast
Fast
Fast
Fast

1.3
1
13
1
6
12
13
10
12
1
1
1
4
4
4
101
50
25
101
50
25

N2
N2
N2
N2
N2
N2

9.5
5.3
3
9.5
5.3
3

n.m.
55.0
50.0
62.2
61.7
57.5
56.5
40.9
53.7
60.0
43.4
n.m.
32.9
42.1
47.1
64.3
62.3
61.4
61.7
61.6
60.2

2.26
2.20
0.69
5.00
4.20
2.60
1.60
0.80
3.60
3.30
3.30
2.80
3.94
4.94
2.22
20.40
10.88
9.80
10.29
9.40
5.07

n.m.
GC-FID
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(IT)MS
GC/(IT)MS
GC/(IT)MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS

No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No

[17]

[40]

[60]

B. Danon et al. / Journal of Analytical and Applied Pyrolysis 112 (2015) 113

Table 3
Dipentene yields from studies that have varied the pyrolysis pressure. ACR, autoclave reactor; CSBR, conical spouted bed reactor; FID, ame ionization detection; FR, feeding rate; GC, gas chromatography; HR, heating rate; (IT)MS,
(ion trap) mass spectrometry; MBR, moving bed reactor; n.m., not mentioned; p, pressure; PCT, passenger car tire; (Q)MS, (quadrupole) mass spectrometry; SBR, sliding blade reactor; SHF, six-hearth furnace; SS, sample size;
T, temperature; TDO, tire-derived oil; TT, truck tire; XBR, xed bed reactor.

8
Table 4
Dipentene yields from studies that have varied the type of tire. BT, bicycle tire; CSBR, conical spouted bed reactor; FID, ame ionization detection; FR, feeding rate; GC, gas chromatography; HR, heating rate; (IT)MS, (ion trap)
mass spectrometry; LG, latex gloves; MT, motorcycle tires; n.d., not detected; n.m., not mentioned; p, pressure; PCT, passenger car tire; (Q)MS, (quadrupole) mass spectrometry; SS, sample size; T, temperature; TDO, tire-derived
oil; TT, truck tire; XBR, xed bed reactor; XBR-FT, xed bed reactor with re tubes; XBR-MW, xed bed reactor with microwave.
Tire type

Particle size

FR (kg/h)
SS (kg)

Reactor type

T ( C)

HR ( C min1 )

p (kPa)

Carrier gas

Flow (L/min)

TDO (wt%)

Dipentene (wt%)

Analysis method

Calib?

[61]

PCT
TT
TT
TT
TT
PCT
PCT
PCT
MT
BT
TT
PCT-1
PCT-2
PCT-3
PCT-4
PCT-5
PCT-6
PCT-7
PCTs
PCT-1
PCT-1
PCT-1
PCT-1
PCT-2
PCT-2
PCT-1
PCT-2
PCT-1
PCT-2
PCT-2
PCT-2
LG
LG

1.52 mm
1.52 mm
< 10 mm
< 10 mm
< 10 mm
< 10 mm
< 10 mm
< 10 mm
4000 mm3
4000 mm3
4000 mm3
25 30 mm2
25 30 mm2
25 30 mm2
25 30 mm2
25 30 mm2
25 30 mm2
25 30 mm2
25 30 mm2
20 20 mm
20 20 mm
20 20 mm
20 20 mm
20 20 mm
20 20 mm
20 20 mm
20 20 mm
20 20 mm
20 20 mm
20 20 mm
20 20 mm
100 mm2
100 mm2

0.13
0.13
0.18
0.18
0.18
0.18
0.18
0.18
0.75
0.75
0.75
0.045
0.045
0.045
0.045
0.045
0.045
0.045
0.045
0.21
0.23
0.5
0.06
0.25
0.25
0.24
0.25
0.24
0.25
0.5
0.5
0.01
0.01

XBR, 0.6 L
XBR, 0.6 L
CSBR
CSBR
CSBR
CSBR
CSBR
CSBR
XBR-FT, 2.1 L
XBR-FT, 2.1 L
XBR-FT, 2.1 L
XBR, 0.2 L
XBR, 0.2 L
XBR, 0.2 L
XBR, 0.2 L
XBR, 0.2 L
XBR, 0.2 L
XBR, 0.2 L
XBR, 0.2 L
XBR-MW, 1 L
XBR-MW, 1 L
XBR-MW, 1 L
XBR-MW, 1 L
XBR-MW, 1 L
XBR-MW, 1 L
XBR-MW, 1 L
XBR-MW, 1 L
XBR-MW, 1 L
XBR-MW, 1 L
XBR-MW, 1 L
XBR-MW, 1 L
XBR, 0.4 L
XBR, 0.4 L

650
650
425
500
600
425
500
600
475
475
475
500
500
500
500
500
500
500
500
599
491
471
344
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
380
480

7
7
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
10
10
10
10
10
10
10
10
6 kW
3 kW
3 kW
3 kW
6 kW
3 kW
6 kW
6 kW
3 kW
3 kW
6 kW
3 kW
10
10

101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101

N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2

0.025
0.025
9.5
9.5
9.5
9.5
9.5
9.5
8
8
8
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0
0
0
0
0
0
0
0
0
0
0
0
0.2
0.2

48.4
56.0
62.8
60.9
54.9
64.3
61.7
55.9
49.0
46.0
55.0
59.8
59.7
56.6
60.1
59.7
57.1
58.7
60.1
31.5
42.6
44.0
30.1
42.8
38.8
27.8
35.7
27.6
26.9
37.0
31.9
57.9
79.8

n.d.
16.12
12.75
11.00
0.93
20.40
10.29
0.94
14.47
5.04
27.97
1.69
1.79
2.22
2.86
2.61
1.84
1.91
1.87
1.17
1.46
2.06
2.89
2.04
1.25
1.04
3.58
1.34
0.94
2.10
3.41
0.11
0.12

GC/MS
GC/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC/MS
GC/MS
GC/MS
GC/(IT)MS
GC/(IT)MS
GC/(IT)MS
GC/(IT)MS
GC/(IT)MS
GC/(IT)MS
GC/(IT)MS
GC/(IT)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC/(Q)MS
GC-FID/MS
GC-FID/MS

No
No
No
No
No
No
No
No
No
No
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
No
No
No
No
No
No
No
Yes
Yes

[38]

[62]
[63]
[52]

[56]

[64]

[31]

B. Danon et al. / Journal of Analytical and Applied Pyrolysis 112 (2015) 113

Ref.

Table 5
Dipentene yields from studies that used catalytic pyrolysis with acidic catalysts. CSBR, conical spouted bed reactor; GC, gas chromatography; HR, heating rate; FBR, uidized bed reactor; FID, ame ionization detection; FR, feeding
rate; MR, microreactor; MS, mass spectrometry; n.m., not mentioned; p, pressure; PCT, passenger car tire; S/C, sample-to-catalyst ratio; SS, sample size; T, temperature; TDO, tire-derived oil; XBR, xed bed reactor; XBR-MW,
xed bed reactor with microwave; ZB, zeolite beta type; ZSM, zeolite ZSM-5 type; ZY, zeolite Y type.
Particle size

FR (kg/h)
SS (kg)

Reactor type

T ( C)

HR ( C min1 )

p (kPa)

Carrier gas

Flow (L/min)

Catalyst

S/C ()

T catalyst ( C)

TDO (wt%)

Dipentene (wt%)

Analysis method

Calib?

[49]

PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT
PCT

11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
11.4 mm
810 mm
810 mm
810 mm
810 mm
810 mm
810 mm
810 mm
810 mm
810 mm
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m
n.m
n.m

0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.220.23
0.2
0.2
0.2
0.2
0.02
0.02
0.02
0.02
0.01
0.01
0.01
0.01
0.01
1.20E05
1.20E05
3.50E06
3.50E06
3.50E06
8.00E06
8.00E06
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002

FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
XBR, 1.2 L
XBR, 1.2 L
XBR, 1.2 L
XBR, 1.2 L
XBR, 0.1 L
XBR, 0.1 L
XBR, 0.1 L
XBR, 0.1 L
XBR, 0.1 L
XBR, 0.1 L
XBR, 0.1 L
XBR, 0.1 L
XBR, 0.1 L
MR
MR
MR
MR
MR
MR
MR
CSBR
CSBR
CSBR
CSBR
CSBR
CSBR
CSBR
CSBR
CSBR

500
500
500
500
500
500
500
500
500
500
500
500
500
500
500
450
500
525
550
600
450
500
525
550
600
450
500
550
600
500
500
500
500
500
500
500
500
500
500
500
500
500
450
500
450
450
450
450
450
425
425
425
500
500
500
500
500
500

Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
10
10
10
10
200250
10
10
10
10
10
10
10
10
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast
Fast

101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101

N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2

He
He
He
He
He
He
He
N2
N2
N2
N2
N2
N2
N2
N2
N2

n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
0
0
0
0
0
0
0
0
0
0.1
0.1
0.1
0.1
0.1
0.1
0.1
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.
n.m.

ZY
ZY
ZY
ZY
ZSM
ZSM
ZSM
ZSM
ZY
ZY
ZY
ZSM
ZSM
ZSM

ZY
ZY
ZY
ZY
ZY
ZSM
ZSM
ZSM
ZSM

ZY-1
ZY-2
ZSM
ZY

ZSM
ZY

ZY
ZY
ZY
ZY

ZSM
ZY
ZB
ZSM
ZSM

ZSM
ZY

ZSM
ZY

ZSM
ZY

0.25
0.5
1
1.5
0.5
1
1.5
2
1
1
1
1
1
1

1
1
1
1
1
1
1
1
1

4
4
2
2

2
1/2

4
2
1.3
1

0.2
0.2
0.2
5.3E05
1.9E08

0.13
0.13

0.13
0.13

0.13
0.13

500
500
500
500
500
500
500
500
500
450
550
600
450
550
600
500
500
500
500
500
500
500
500
500
500
500
500
500
500
500
500
500
500
400
400
400
400
400
400
400
400
400

In-situ
In-situ
In-situ
450
450

In-situ
In-situ

In-situ
In-situ

In-situ
In-situ

53.8
50.0
48.0
46.0
45.6
49.0
48.0
46.0
43.0
48.0
45.0
42.0
49.0
47.5
40.0
55.0
53.5
52.0
51.0
43.5
48.5
46.5
44.0
42.5
39.0
49.5
45.5
43.5
41.0
55.8
48.0
48.0
47.0
32.7
52.0
32.6
40.4
45.9
31.0
24.0
20.0
13.8
43.2
52.3
44.1
51.1
42.2
24.5
25.5
64.7
58.3
62.2
63.2
45.5
61.8
63.2
45.5
61.8

2.31
1.85
1.49
1.29
0.96
1.72
1.25
1.06
0.82
1.92
0.68
0.17
2.25
0.67
0.12
2.75
2.09
1.30
0.41
0.04
1.75
1.40
1.06
0.51
0.08
1.88
1.18
0.65
0.12
2.01
0.24
0.12
0.14
0.55
5.33
2.81
0.36
3.89
1.02
0.22
0.07
0.04
14.00
9.42
0.12
0.93
0.01
0.26
0.21
23.93
5.51
1.99
16.94
3.78
2.37
16.94
3.79
2.39

GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC-FID/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC-FID
GC-FID
GC-FID
GC-FID
GC-FID
GC-FID
GC-FID
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC-FID
GC-FID
GC-FID

Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No

[50]

[51]

[65]
[66]

[67]

[37]

[68]

[69]

Tire type

B. Danon et al. / Journal of Analytical and Applied Pyrolysis 112 (2015) 113

Ref.

No
No
No
No
No
No
No
No
No
No
No
No
No
GC/(IT)MS
GC/(IT)MS
GC/(IT)MS
GC/MS
GC/MS
GC-FID/MS
GC-FID/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
4.94
5.75
5.20
0.87
0.92
1.50
21.25
2.69
2.14
2.53
6.52
1.31
4.61
42.1
48.1
42.0
60.0
65.1
66.5
72.3
33.3
33.5
33.6
48.0
20.0
18.0

In-situ
In-situ

In-situ
In-situ
In-situ

In-situ
In-situ
In-situ

In-situ

33
33

10
1
1

2000
2000
1000

EP
WLO
WLO

LBO

LBO

Lignite

NaOH
Na2 CO3

ZSM-5
ZSM-5

0.1
0.1
0.025
0.025

0.03
0.03

N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
4
4
4
101
101
101
101
101
101
101
101
101
101
20
20
20
10
10
7
7
10
10
10
10
10
10
500
500
500
425
425
550
550
430
430
430
430
700
700
ACR, 0.1 L
ACR, 0.1 L
ACR, 0.1 L
XBR, 0.3 L
XBR, 0.3 L
XBR, 0.6 L
XBR, 0.6 L
XBR, 0.06 L
XBR, 0.06 L
XBR, 0.06 L
XBR, 0.06 L
XBR
XBR
0.1
0.1
0.1
0.01
0.01
0.065
0.065
0.01
0.01
0.01
0.01
0.05
0.05
[73]

[70]

[72]

[71]

n.m.
n.m.
n.m.
PCT
PCT
PCT
TT
PCT
PCT
PCT
PCT
PCT
PCT
[40]

2060 mesh
2060 mesh
2060 mesh
2 mm
2 mm
1.52 mm
1.52 mm
10 30 mm
10 30 mm
10 30 mm
10 30 mm
n.m.
n.m.

Analysis
method
Dipentene
(wt%)
TDO (wt%)
T catalyst ( C)
S/C ()
Co-pyrolysate
Catalyst
Flow
(L/min)
Carrier
gas
p (kPa)
HR
( C min1 )
T ( C)
Reactor
type
FR (kg/h)
SS (kg)
Particle
size
Tire
type
Ref.

TDO of catalytic pyrolysis [69]. Furthermore, this catalytic behavior holds both for studies where a separate catalytic bed was used
[37,4951,6567], and for studies where the catalyst was present
in the pyrolysis reactor itself (in-situ) [37,6870].
Apart from these acidic catalysts, only a few other catalysts have
been investigated, see Table 6. Most promising from a dipentene
point of view is the use of basic additives [40]. Zhang et al. showed
that the dipentene yield can be improved signicantly when using
NaOH as the catalyst at vacuum conditions. Although the dipentene concentration in the TDO is comparable with that of their
uncatalyzed experiment, the fact that more oil is obtained when
using NaOH indicates that more dipentene is formed. Analogously,
Kar showed an increase in the oil yield using expanded perlite as
the catalyst [71]. However, the dipentene concentration in this
oil was slightly lower, resulting in comparable nal dipentene
yields.
Finally, the inuence of the type of reactor is assessed. For
this purpose, the calibrated dipentene yields of experiments at
500 C in different reactors of comparable size, i.e., xed-bed (XBR)
and uidized-bed reactors (FBR), are compared. These values are
2.55 wt% [46], 2.01 wt% [51] and 1.692.86 wt% [52] for XBRs and
2.31 wt% [49] and 2.09 wt% [50] for FBRs. These values do not
indicate any signicant differences for these two reactor types.
It has to be noted that the dipentene yields obtained in a conical
spouted bed reactor (CSBR), where residence times are assumed to
be even shorter than in a FBR, are signicantly higher then abovementioned values [36,39]. However, these latter values have not
been calibrated, so they should be considered with care.
Few other studies need to be mentioned in this section. Three
studies have presented dipentene yields of the co-pyrolysis of
waste tires with (waste) lubricant oil [70,72] and with lignite [73].
Unfortunately, all these studies did not calibrate their analytical apparatus. Since the composition of the obtained co-pyrolytic
oils can differ signicantly from that of pyrolysis of waste tires
alone, in these cases, it seems difcult to compare the results even
among themselves. For general informative purposes, the results
are included in Table 6 nevertheless.
Furthermore, it is just noted here that several papers have
reported dipentene yields for experiments with relatively low oxygen levels in the reactor [7476]. From a comparison between fully
inert and slightly oxidative pyrolysis of latex gloves it is concluded
that lower dipentene yields are obtained when oxygen is present
[31,76]. Because this review focuses on pyrolysis proper, the results
are not included in the overviews. It is noted that Boxiong et al. also
did not use an inert carrier gas or vacuum, but as their reactor is
closed air-tight, only the initially present oxygen is available in the
reactor [6567]. Because this is a relatively small amount and it is
readily removed from the reactor, their reaction conditions are still
considered to be pyrolytic.
Finally, both Dai et al. (waste tires in a uidized bed reactor)
and Pradhan et al. (bicycle tires in a xed bed reactor) reported
dipentene yields in their TDO, however, in both cases the operating conditions, under which these TDOs were produced, were not
specied [77,78].
It can be concluded, based on presently available information
in the literature, that at least 2.5 wt% of the steel-free tire can
be converted to dipentene. The main operating conditions during
pyrolysis inuence this yield signicantly, of which temperature
seems to be the most important (and also the most investigated)
one. Also, the importance of tire type and tire brand is stressed here,
while most probably these two variables are both linked to the
polyisoprene content of the tire. Additionally, some studies have
indicated that the above mentioned yields can be further improved.
The use of vacuum pyrolysis has been propounded as such a possible improvement. Also, the use of basic additives, e.g., NaOH, seems
to improve the nal dipentene yields. However, more conclusive

Calib?

B. Danon et al. / Journal of Analytical and Applied Pyrolysis 112 (2015) 113
Table 6
Dipentene yields from studies that used catalytic pyrolysis using non-acidic catalysts and co-pyrolysis. ACR, autoclave reactor; FID, ame ionization detection; FR, feeding rate; GC, gas chromatography; HR, heating rate; (IT)MS,
(ion trap) mass spectrometry; n.m., not mentioned; p, pressure; PCT, passenger car tire; S/C, sample-to-catalyst or sample-to-copyrolysate ratio; SS, sample size; T, temperature; TT, truck tire; TDO, tire-derived oil; XBR, xed
bed reactor.

10

B. Danon et al. / Journal of Analytical and Applied Pyrolysis 112 (2015) 113

data (such as calibrated dipentene yields for systematic studies of

vacuum or NaOH catalyzed pyrolysis) are required.

4. Dipentene separation and purication

From the previous section it becomes clear that the dipentene yield, and thus also its concentration in the tire-derived oil,
varies considerably with pyrolysis conditions as well as tire type
and brand. Moreover, the dipentene is also present in the TDO
together with a plethora of other components, with studies reporting from an excess of 130 components using one-dimensional GC
[53], to several hundreds of compounds using GCGC [44]. Both the
types of components and their concentrations can vary signicantly
[17,29,52]. Although almost all studies report that dipentene is the
most abundant component present in the TDO, should dipentene
be produced as a value-added chemical from waste tire pyrolysis,
it needs to be separated from the multitude of other components.
While a signicant number of publications have considered the
pyrolysis proper, considerably less work has been performed on
the fractionation of TDO or on the separation and purication of
possible valuable chemicals from TDO.
Typically, the TDO can be characterized, based on its properties,
between a light and medium fuel oil [14]. It consists predominantly
of alkylated benzenes, alkylated naphthalenes, alkanes and alkenes
[52]. Analysis of the distillation curves of various TDOs show that
it has a wide boiling range with up to 50 wt% of the sample distilling before 200 C [52,61,62]. Approximately 10 wt% of the oil has a
normal boiling point between 160 and 200 C, the fraction in which
dipentene would typically be present [53,79].
A number of studies have considered separating the oil into various fractions, by and large for the end use as a fuel or fuel additive
[10,48,80]. This can either be achieved with relative ease through
distillation [10,80], or, as studied by Williams and Brindle [48], by
selective condensation of the reactor outlet. For distillation studies, the majority of the dipentene is present in the so-called light
naphtha fraction (normal boiling point below 200 C) at reported
concentrations between 15 and 25 wt% [1,7,16,17]. Further separation of the light naphtha could yield a fraction with a boiling point
between 160 and 200 C, containing the majority of the dipentene.
In the selective condensation study of Williams and Brindle the
highest concentration of dipentene is present in the lightest fraction, with concentrations up to 7 wt% [48]. This fraction should have
a similar composition to the light naphtha fraction and further separation and purication of this fraction may result in a dipentene
enriched fraction. It should also be noted that the three condensers
used for the selective condensation study of Williams and Brindle
were all operated at the same temperature. Operation using a temperature gradient between the different condensers may improve
the separation efciency signicantly.
While it is relatively easy to obtain a dipentene enriched light
naphtha (or similar) fraction, further purication is not so simple. In a series of publications, Pakdel and co-workers studied the
dipentene production from tire-derived oil extensively [16,17,81].
Initially, they fractionated the oil through distillation at atmospheric pressure and the light naphtha fraction, with a normal
boiling point below 204 C contained approximately 15 wt% dipentene. A small sample (1 g) of this fraction was then puried on
preparative scale and they succeeded in producing a 95 wt% pure
dipentene. However, the methods used are not easily transferable
to larger scale, and, as pointed out in their conclusions, further
research is required. They suggested that at least two consecutive distillation steps, followed by a purication step, would
be required to produce high purity dipentene. In a follow-up
study, a much larger scale of operation was considered [17].
The oil was fractionated rst in a 300 L batch still, where after

11

the dipentene in the naphtha fraction was further concentrated

in a 5 L batch column. Then, solid liquid chromatography on a
dual layer silica and alumina column was used to obtain subfactions for analysis. Importantly, fractions containing between
50 and 92 wt% dipentene were obtained. It was also found that
separation of dipentene from 1,2,3-trimethylbenzene, 1-methyl-3(1-methylethyl)benzene (m-cymene), and indane is very difcult
due to their similar boiling points (all between 175 and 176 C).
Although not specically mentioned, dipentene is probably also
aromatized to p-cymene (1-methyl-4-(1-methylethyl)benzene),
which also has a boiling point very close to dipentene (177 C).
Stanciulescu and Ikura also considered the fractionation of a
tire-derived oil, with the aim of obtaining relatively pure dipentene
for conversion to dipentene esters [82,83]. In their initial study, the
TDO was subjected to a double fractionation, but they found that
the complexity of the TDO and the low concentration made dipentene collection difcult [82]. In their follow-up study, the TDO was
fractionated at 3.33 kPa, using a batch still, with various cuts being
obtained [83]. They found that the normal boiling point cuts of
170180 C and 180190 C both contained approximately 75 wt%
dipentene, with these cuts representing 5.4 and 1.2 wt% of the total
charge, respectively. They noted that further fractionation was very
difcult, again highlighting the challenges in separation.
In addition to obtaining a fraction concentrated in dipentene,
it is also important to consider the other components present,
in particular the sulfur-containing components. Sulfur-containing
components, even in very low concentrations, can result in a foul
odor to the oil, thus reducing the quality and economic value
thereof. Williams et al. found that the TDO contains approximately
1.4 wt% sulfur, which is rather signicant in this respect [84]. Pakdel
et al. demonstrated, using pure dipentene, that the odor threshold for thiophene was 15.4 and 20.6 ppm for dl-limonene and
d-limonene, respectively [17]. While most of the sulfur-containing
compounds were removed during the distillation process, Pakdels
concentrated dipentene samples still had an unpleasant smell and
contained up to two orders of magnitude higher sulfur component concentrations than the odor threshold they measured [17].
Stanciulescu and Ikura observed a similar foul odor [83].
In conclusion, the literature has shown that it is not a trivial exercise to obtain a highly concentrated dipentene fraction of sufcient
quality. Especially, the separation of dipentene from some other
compounds present in the TDO (viz. 1,2,3-trimethylbenzene, mand p-cymene and indane) and the removal of the sulfur-containing
compounds, due to their foul odor, is essential and remain the principle challenges for future research.

5. Conclusions
It is concluded that dipentene is produced by the intramolecular
cyclization of the allylic radicals. The allylic radicals are formed
by random scission of the bonds with respect to the double
bonds in the polyisoprene chains. Dimerization of isoprene (which
is produced by unzipping of these radicals) towards dipentene
seems unlikely, due to the lack of other isoprene dimers among
the pyrolytic products. Next, dipentene is involved in secondary
reactions at pyrolytic conditions, such as aromatization, possibly
via a diallyl diradical, or fragmentation towards isoprene, among
others. The main operating conditions during pyrolysis inuence
the dipentene yield signicantly. Of these, the pyrolysis temperature seems to be most important, with temperatures between
400 and 500 C resulting in maximum dipentene yields. Also, the
importance of tire type and tire brand is stressed here, while most
probably these two variables are both linked to the polyisoprene
content of the tire sample. Both the use of vacuum pyrolysis and
the use of basic additives, e.g., NaOH, have been propounded as

12

B. Danon et al. / Journal of Analytical and Applied Pyrolysis 112 (2015) 113

means to further improve the dipentene yield. However, more

conclusive data (such as calibrated dipentene yields for systematic studies of vacuum or NaOH catalyzed pyrolysis) are required.
Based on the presently available information in the literature, it
can be concluded that at least 2.5 wt% of a steel-free tire can be
converted to dipentene. Thus, hypothetically, if a steel-free tire
weighs 10 kg, it yields 0.25 kg dipentene, which returns (at a mean
dipentene price of 2 US$ kg1 ) about half a US$ per processed
tire. Besides, the remaining hydrocarbons mixtures can still be
used as an energy source. Therefore, the production of dipentene
from end-of-life tires is a very promising route to add value to
the tire pyrolysis process. However, prerequisite for this route
to be viable is the recovery of a highly pure dipentene from the
TDO. It is evident that there are still some signicant challenges in
this respect. While a dipentene-enriched fraction can be obtained
from the TDO by relatively straightforward distillation, dipentenes
with purities between 92 and 95 wt% have been reported using
more sophisticated separation principles. To get even purer fractions is very difcult due to other compounds present in the oil
(1,2,3-trimethylbenzene, m- and p-cymene and indane) that have
very similar properties as dipentene. Moreover, the removal of the
sulfur-containing compounds is essential, due to their foul odor,
especially when the dipentene is intended to be used as a fragrant
or avorant.
Acknowledgments
N.M. Mkhize and L. Mulaudzi are kindly acknowledged for their
contribution to the compilation of the literature database. Also
many thanks go to Dr. A. de Villiers and Prof. C.D. Woolard for sharing their extensive knowledge. Financial assistance of REDISA and
the National Research Foundation (NRF) towards this research is
hereby acknowledged. Opinions expressed and conclusions arrived
at are those of the authors and are not necessarily to be attributed
to the funding bodies.
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