Fuel 191 (2017) 403–410

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Full Length Article

Fuel production from pyrolysis of natural and synthetic rubbers

Tao Kan ⇑, Vladimir Strezov, Tim Evans
Department of Environmental Sciences, Faculty of Science and Engineering, Macquarie University, Sydney, NSW 2109, Australia

h i g h l i g h t s

Different rubber materials were pyrolysed to produce fuels.

Product fuels were characterised by GC, FT-IR and GC–MS, respectively.

Mass change of rubbers during pyrolysis was tested by thermogravimetric analysis.

Heat change during rubber pyrolysis was tested by computer aided thermal analysis.

Natural and synthetic rubber tyres and natural rubber mat were compared.

a r t i c l e i n f o a b s t r a c t

Article history: Pyrolysis of rubber wastes is an efficient thermo-chemical means of generating high-value energy and
Received 31 October 2016 fuels. In this work, a variety of technological tools were employed to characterise the pyrolysis of natural
Received in revised form 23 November 2016 and synthetic rubbers, which included three tyres (natural rubber tyre, pneumatic tyre and synthetic rub-
Accepted 24 November 2016
ber tyre) and one natural rubber mat. The composition of gas products was determined by gas chro-
Available online 1 December 2016
matography (GC). H2 and CO were the major gases released from the pyrolysis process although the
evolution rates of gas species differed for the four samples. The organic compounds contained in the
Keywords:
resulting pyrolysis oils were analysed by gas chromatography–mass spectrometry (GC–MS), and the
Waste management
Rubber
results confirmed the existence of large amounts of hydrocarbons and nitrogen-containing compounds
Tyre as well as some sulphur-containing compounds. The raw rubbers and solid char products were analysed
Pyrolysis by Fourier transform-infrared (FT-IR) spectrometry to determine the change in functional groups, which
Energy and fuels indicated the loss of organics after pyrolysis at different temperatures. Distinct mass and heat change
behaviour of the selected rubber samples was also detected through thermogravimetric analysis and
computer aided thermal analysis, respectively. The pyrolysis behaviour and fuel product properties of
the rubbers were compared in this work. The obtained data will provide important reference information
for energy and fuel generation from rubber pyrolysis.
Ó 2016 Published by Elsevier Ltd.

1. Introduction
Waste management is a global issue which impacts the sustain-
ability of environmental and economic developments. Rubber
waste in the forms of tyres, gloves or others have been a problem-
atic material for treatment as it is highly resistant to bio-
degradation. Natural rubber (NR) consists of an elastic polymer
(cis-1, 4 polyisoprene) from latex which is almost all from the rub-
ber tree (Hevea brasiliensis). Due to the shortage of natural rubber
and purpose of various applications, currently the majority of the
rubber market share is held by vulcanized synthetic rubber (SR)
which is generally comprised of cross-linked long-chain man-
made polymers (e.g., tyrene/butadiene and isobutylene/isoprene)
⇑ Corresponding author.
E-mail address: tao.kan@mq.edu.au (T. Kan).
with sulphur atoms. These artificial polymers are synthesised from
fossil petroleum and then primarily used to make tyres. For
instance, cis-polybutadiene rubber (CBR), isobutylene–isoprene
copolymer rubber (i.e., butyl rubber, abbr. BR) and styrene–butadi-
ene copolymer rubber (SBR) are three of the most common syn-
thetic rubbers used in tyre manufacturing. A tyre may contain
synthetic rubber, natural rubber, carbon black, steel, fabric, plasti-
cizers, lubricants, antioxidants, antiozonants, inorganic materials
(e.g., calcium carbonate and silica), and other components.
As the most abundant rubber waste, approximately 4  109
end-of-life tyres (equivalent to 3.2  108 tonnes) are estimated to
be disposed through landfills and stockpiles worldwide [1]. In Aus-
tralia, an annual estimate of more than 2  105 tonnes of waste
tyres are landfilled or stockpiled [2].
According to the hierarchy of sustainable waste management
by US EPA, the priority decreases in the order: source reduction

http://dx.doi.org/10.1016/j.fuel.2016.11.100
0016-2361/Ó 2016 Published by Elsevier Ltd.
404 T. Kan et al. / Fuel 191 (2017) 403–410
and reuse > recycling and composting > energy recovery > treat-
ment and disposal [3]. Considering the difficulties for the reuse
or recycling of rubber wastes, energy and fuel generation through
several thermo-chemical conversion technologies is gaining
increased interest. In the EU, incineration for production of heat
and/or electricity is the most common treatment technology fol-
lowed by reuse and export [4]. Additional advanced technologies
have been applied to recover fuels or chemicals from rubber
wastes, such as gasification [5] and pyrolysis [6].
Pyrolysis technology thermally decomposes rubber or other
organic wastes (e.g., biomass), in an inert atmosphere at tempera-
tures of around 350–550 °C or higher, to give fuel products contain-
ing liquid pyrolysis oil, solid char and pyrolytic gas. The resulting
products can be further and selectively upgraded into value-added
fuels or chemicals [7–10]. Many studies have been conducted on
the pyrolysis of rubber materials. Choi [11] applied pyrolysis-GC to
study the volatile pyrolysis products from 15 patterns of SBRs with
different microstructures. It was found that butadiene, 4-
vinylcyclohexene and styrene are the dominant products with the
ratios affected by relative contents of styrene, 1,2, cis-1,4-, and
trans-1,4-units. Danon et al. [12] identified the primary pyrolysis
products of monomers and dimers from three different rubbers of
NR, CBR and SBR using the instrument of combined thermogravi-
metric analyser and mass spectrometer (TGA-MS). However, in their
research, the heat changes of the rubbers during pyrolysis, including
specific and latent heats, and the properties of other products were
not characterised. Lah et al. [13] modelled the pyrolysis kinetics of
different tyre components of NR, BR, SBR and other fabric, oil and
additives in scrap tyre rubber using a thermogravimetric analyser.
Miranda et al. [14] also investigated the kinetics of waste tyre mainly
consisting of NR, BR and SBR and determined the effect of tempera-
ture on the composition of pyrolysis oil products. It was observed
that the lower temperature (<390 °C) favoured the formation of
alkene products while the higher temperature favoured formation
of aromatics. Williams [15] compared the waste tyre pyrolysis in
various reactor types, such as fixed bed, moving screw bed, rotary
kiln, vacuum, conical spouted bed, fluidised bed and drop tube reac-
tor, and the oil, char and gas yields fell in the ranges of 5–63%, 22–
49% and 3–73%, respectively.
The previous studies were mainly focused on the pyrolysis
kinetics modelling of major components in lump waste tyres, char-
acterisation of products (especially pyrolysis oil) from pyrolysis of
a lump rubber tyre, or pyrolysis of NR products (e.g., latex gloves)
[16,17]. Few studies have been performed on the comprehensive
comparison on the pyrolysis characteristics and differences
between NR tyres and mats, and between NR and SR tyres. In this
work, rubber materials from different resources including three
tyre types (i.e., NR tyre, pneumatic tyre and SR tyre) and one NR
mat, were subjected to slow pyrolysis process wherein the product
properties were characterised. Mass and heat changes of the
selected rubber materials were also investigated. The work will
facilitate further understanding of pyrolysis of different rubber
materials to generate fuels, which is beneficial in meeting the
increasing global fuel demand.
2. Experimental
2.1. Feedstock
All black rubber materials in the original forms were purchased
from the distributor of J Blackwood & Son Pty Limited (Australia),
including natural rubber tyre F50 coupling (abbr. NR–Tyre), natural
rubber mat of 1200 mm  1.59 mm (abbr. NR–Mat), pneumatic
black rubber tyre (abbr. PR–Tyre, supplier: EHI Australia PTY
LTD) and synthetic rubber tyre FRAS (fire resistant & anti-static)
F40 (abbr. SR–Tyre). Rubber pieces were shredded from the
tyres/mat and then ground with the assistance of liquid nitrogen,
followed by sieving to obtain fine particles of below 212 lm. The
particles were dried at 60 °C in a vacuum oven prior to the exper-
iments. The proximate analysis was performed in a thermogravi-
metric analyser (model: TGA/DSC 1 STARe System, Mettler Toledo
Ltd.) according to ASTM E1131. Table 1 lists the analysis results.
2.2. Characterisation of products from rubber pyrolysis
An infrared furnace with temperature-programming was used
to generate gaseous (pyrolytic gas), liquid (mainly pyrolysis oils)
and solid (chars) from the pyrolysis of different rubbers. The fine
particles of each rubber type were packed in a quartz tube fixed-
bed reactor at a heating rate of 10 °C/min in an inert helium
atmosphere.
2.2.1. Pyrolytic gas
During the pyrolysis process from room temperature to 600 °C,
the composition of released pyrolytic gas with temperature was
analysed by an online micro gas chromatograph (Model: M200,
MTI Analytical Instruments) with two thermal conductivity detec-
tors. Ultra-high purity He was used as the carrier gas. The H2 and
CO peaks were determined by a molecular sieve 5A column at
60 °C with CO2, CH4, C2H4, and C2H6 peaks by a Poraplot U column
at 40 °C. Chromatographic spectra were recorded at an interval of
100 s.
2.2.2. Pyrolysis oils
The condensable organic vapours (i.e., pyrolysis oils) from the
rubber pyrolysis were continuously swept out of the reactor and
condensed on cool quartz wool placed at the reactor exit until
the temperature reached 500 °C. Subsequently, the quartz wool
was washed using dichloromethane (DCM) solvent to extract the
pyrolysis oil components which were then derivatised by N,O-bis
(trimethylsilyl)trifluoroacetamide with 1% trimethylchlorosilane
(BSTFA + 1%TMCS). A GC–MS (gas chromatography–mass spec-
trometry, model: Agilent 7890B GC coupled with 5977A MS) sys-
tem equipped with a HP-5MS column (60 m  0.25 lm) was
used to test the detailed components of pyrolysis oils. The GC oven
was initially set to 40 °C for 2 min, then heated to 310 °C at
2 °C/min and kept at 310 °C for 30 min.
2.2.3. Chars
Rubber samples were heated to different target temperatures
(300 and 500 °C) for char production. The functional groups of
the raw rubber samples and the chars after pyrolysis were acquired
by a Fourier transform-infrared (FT-IR) spectrometer (model: Nico-
let 6700 FT-IR) with an attenuated total reflectance (ATR).
2.3. Thermal behaviour of rubbers
2.3.1. Mass loss during pyrolysis
The mass loss of rubbers presented as thermogravimetric (TG,
wt.%) data during pyrolysis from room temperature to 600 °C at
Table 1
Proximate analyses of rubbers.
Proximate analysis Results/wt.%
NR–Tyre NR–Mat PR–Tyre SR–Tyre
Moisture 0.21 0.27 0.47 0.69
Volatiles 54.05 57.46 59.97 47.18
Ash
a
10.66 27.38 18.84 12.36
Fixed carbon 35.08 14.89 20.72 39.77
a
By difference.
 T. Kan et al. / Fuel 191 (2017) 403–410 405

0.02 10 °C/min was recorded by a thermogravimetric analyser (model:

TGA/DSC 1 STARe System, Mettler Toledo Ltd.). The carrier gas
Evolution rate (wt.%/ C)

NR-Tyre
o

and protective gas (both nitrogen) were set at 20 and 50 ml/min,

2

Gas yield (wt.%)

respectively. Mass loss rate of each rubber during pyrolysis pre-
sented as differential thermogravimetric (DTG, wt.%/°C) curves
were acquired by differentiating the TG data.
0.01
1
2.3.2. Heat change during pyrolysis
Specific heats of rubbers during pyrolysis were tested by com-
puter aided thermal analysis (CATA) as previously described [18–
20]. The CATA setup mainly included an infrared (IR) image gold
0.00 0 furnace (SINKU-RIKO), one graphite tube and two silica tubes.
0 150 300 450 600 Two silica tubes with different sizes of 10 and 50 mm were coaxi-
o ally assembled with another graphite tube installed between them.
Temperature ( C)
Argon at 50 mL/min purged continuously along the graphite tube
0.02 to keep it under inert atmosphere while argon at 5 mL/min flowed
Evolution rate (wt.%/ C)

NR-Mat through the smaller silica tube where 2.4 cm3 of rubber sample
o

2 was packed. The controlling temperature (i.e., the graphite tube

Gas yield (wt.%)

temperature), sample surface temperature and sample centre tem-
perature were recorded by the LabVIEW interface and then used to
calculate the sample specific heat. The mathematical calculation
0.01 process was described previously [19]. The IR furnace was cali-
1 brated before experiments and the estimated error was within
±2% as reported [19].

0.00 0 Table 2
0 150 300 450 600 Major compounds in pyrolysis oil of NR–Tyre.
o
Temperature ( C) Name Formula Area percent %

0.02 a-Methylstyrene C9H10 0.95

Evolution rate (wt.%/ C)

PR-Tyre Santolina triene C10H16 0.62

d-Limonene C10H16 8.33
o

2 Benzene, 1-methyl-4-(1-methylethenyl)- C10H12 0.79

Gas yield (wt.%)

1,3-Cyclopentadiene, 1,2,3,4,5-pentamethyl- C10H16 0.57

Benzothiazole C7H5NS 1.05
a-Bulnesene C15H24 0.73
0.01
Quinoline, 1,2-dihydro-2,2,4-trimethyl- C12H15N 5.76
1 c-Himachalene C15H24 1.02
1H-Benzocycloheptene, 2,4a,5,6,7,8,9,9a- C15H24 1.44
octahydro-3,5,5-trimethyl-9-methylene-,
(4aS-cis)-
(1R,4R,4aS,8aR)-4,7-dimethyl-1-(prop-1-en- C15H24 0.68
0.00 0 2-yl)-1,2,3,4,4a,5,6,8a-
0 150 300 450 600 octahydronaphthalene
o (1R,4S,5S)-1,8-dimethyl-4-(prop-1-en-2-yl) C15H24 0.71
Temperature ( C)
spiro[4.5]dec-7-ene
0.02 1H-3a,7-Methanoazulene, octahydro-1,4,9,9- C15H26 0.59
Evolution rate (wt.%/ C)

SR-Tyre tetramethyl-
o

1H-Cycloprop[e]azulene, decahydro-1,1,4,7- C15H26 0.62

2 tetramethyl-, [1aR-
Gas yield (wt.%)

(1aa,4b,4ab,7b,7ab,7ba)]-
3-(2-methyl-propenyl)-1H-indene C13H14 0.53
0.01 cis-Thujopsene C15H24 0.91
cis-a-Bisabolene C15H24 0.57
1 Benzene, 1,10 -(1,3-propanediyl)bis- C15H16 5.82
1,4,9-Decatriene, 1-phenyl-, (E,E)- C16H20 0.64
trans-geranylgeraniol C20H34O 0.97
Geranyl-.alpha.-terpinene C20H32 2.28
Benzene, 1,10 -[3-(2-phenylethylidene)-1,5- C25H26 0.68
0.00 0 pentanediyl]bis-
0 150 300 450 600 2,6,10,14,18-pentamethyl-2,6,10,14,18- C25H42 0.80
o
Temperature ( C) eicosapentaene
Ethane, 1,2-bis(1-phenylcyclopropyl)- C20H22 0.67
1,4-benzenediamine, N-(1,3-dimethylbutyl)- C18H24N2 13.93
N0 -phenyl-
Squalene C30H50 6.38
Spiro[androstane-3,20 -thiazolidine], (5a)- C21H35NS 1.32
Fig. 1. Gas evolution rates (wt.%/min) and CO/CO2 ratio from rubber pyrolysis with
Phenol, 2,4-bis(1-methyl-1-phenylethyl)- C24H26O 2.34
temperature.
406 T. Kan et al. / Fuel 191 (2017) 403–410

3. Results and discussion Despite the above distinctions of gas evolution behaviour
among the four samples, there are some common points:
3.1. Product properties
i. H2 and CO were basically the two major gas components
3.1.1. Pyrolytic gas which can be potentially used as syngas in some
The evolution rates of the major gas components including H2, applications.
CO2, CO, CH4, C2H4, and C2H6 during pyrolysis of different rubbers ii. The gas yield generally ranged at a low level of maximum
are depicted in Fig. 1. The overall gas yield (wt.% of raw rubber 1–2 wt.% at the final temperature of 600 °C.
feed, in black broken line) versus temperature was obtained by
integrating the total evolution rate of all gases with temperature. 3.1.2. Pyrolysis oils
For NR–Tyre, the CO2 evolution rate formed a wide but low The major compounds in the pyrolysis oils derived from differ-
hump at around 225–450 °C. Between 350 and 525 °C, H2 was ent rubbers at 500 °C are shown in Tables 2–5. The compounds are
the dominant gas species, shaping a double-peak curve with a listed in order of the appearance of the corresponding peaks in
maximum evolution rate of 0.012 wt.%/°C at 364 °C. each GC spectrum.
Compared to NR–Tyre, NR–Mat obtained the equivalent CO evo- The pyrolysis oils from the investigated rubbers mainly
lution curve but much lower H2 release. During the whole process, contained:
no obvious CO2 evolution was observed. The gas yield over the
entire temperature range was also generally lower than that of i. aromatic, cyclic and aliphatic hydrocarbons (CxHy) which
NR–Tyre. accounted for the majority of the listed compounds in Tables
For PR–Tyre and SR–Tyre, a peak of H2 evolution between 300 2–5.
and 500 °C was also noticed, which was similar to NR–Tyre. How- ii. nitrogen-containing compounds with large contents.
ever, the H2 evolution after 500 °C was more noticeable than NR– iii. sulphur-containing compounds, e.g., benzene, 1-
Tyre with the opposite change trend of much less CO evolution. thiobenzoyl-2,4,6-trimethyl- (C16H16S), and compounds
The most outstanding difference between SR–Tyre and other three with different heteroatoms of sulphur and nitrogen.
samples was the obvious evolution of hydrocarbons (mainly CH4 Sulphur-containing compounds are derived from the
and C2H6) during 400–600 °C. decomposition of additives (e.g., vulcanisation agents) and/
or accelerator materials [21]. For fuel use applications, the
Table 3 sulphur content in the pyrolysis oils is supposed to be
Major compounds in pyrolysis oil of NR–Mat. reduced.
Compound name Formula Area
iv. small amounts of oxygen-containing compounds, such as
percent % alcohols, acids, cyclic ethers and their derivatives [22].
d-Limonene C10H16 2.37
Benzothiazole C7H5NS 1.50 Table 4
Caprolactam C6H11NO 1.08 Major compounds in pyrolysis oil of PR–Tyre.
a-Ylangene C15H24 1.27
Compound name Formula Area
1H-Cycloprop[e]azulene, 1a,2,3,5,6,7,7a,7b- C15H24 0.69
percent %
octahydro-1,1,4,7-tetramethyl-, [1aR-(1a.alpha.,7.
alpha.,7a.beta.,7b.alpha.)]- Benzothiazole C7H5NS 0.84
1H-3a,7-Methanoazulene, octahydro-1,4,9,9- C15H26 0.47 Quinoline, 1,2-dihydro-2,2,4-trimethyl- C12H15N 1.40
tetramethyl- 1H-Cycloprop[e]azulene, decahydro-1,1,4,7- C15H26 0.87
1H-Cycloprop[e]azulene, decahydro-1,1,4,7- C15H26 1.14 tetramethyl-, [1aR-(1aa,4b,4ab,7b,7ab,7ba)]-
tetramethyl-, [1aR-(1aa,4b,4ab,7b,7ab,7ba)]- c-Himachalene C15H24 0.98
1H-Cycloprop[e]azulene, 1a,2,3,5,6,7,7a,7b- C15H24 1.16 Spiro[5.5]undec-2-ene, 3,7,7-trimethyl-11- C15H24 2.19
octahydro-1,1,4,7-tetramethyl-, [1aR-(1a.alpha.,7. methylene-, (-)-
alpha.,7a.beta.,7b.alpha.)]- (R)-1-Methyl-4-(6-methylhept-5-en-2-yl)cyclohexa- C15H24 0.94
1H-Benzocycloheptene, 2,4a,5,6,7,8,9,9a-octahydro- C15H24 3.60 1,4-diene
3,5,5-trimethyl-9-methylene-, (4aS-cis)- 5-Pentadecen-7-yne, (Z)- C15H26 0.70
(1R,4S,5S)-1,8-Dimethyl-4-(prop-1-en-2-yl)spiro C15H24 1.53 4,5-Di-epi-aristolochene C15H24 0.93
[4.5]dec-7-ene 2,4,4,6,6,8,8-Heptamethyl-2-nonene C16H32 0.81
Methyl 4,7,10,13-hexadecatetraenoate C17H26O2 0.67 Phenanthrene C14H10 1.47
b-Santalol C15H24O 0.82 cis-Z-a-bisabolene epoxide C15H24O 0.99
4a-Methyl-1-methylene-1,2,3,4,4a,9,10,10a- C16H20 1.05 Geranyl-a-terpinene C20H32 1.18
octahydrophenanthrene 1,3,6,10-Cyclotetradecatetraene, 3,7,11-trimethyl- C20H32 0.58
2,4-Di-tert-butylphenol C14H22O 2.14 14-(1-methylethyl)-, [S-(E,Z,E,E)]-
cis-Thujopsene C15H24 1.49 Androst-5,7-dien-3-ol-17-one C19H26O2 0.90
Gamma-himachalene C15H24 0.51 Estra-1,3,5(10)-trien-17.beta.-ol C18H24O 5.16
Geranyl-a-terpinene C20H32 0.50 Fluoranthene C16H10 0.96
2,6,10,14,18-Pentamethyl-2,6,10,14,18- C25H42 0.95 Pyrene C16H10 1.11
eicosapentaene 1,4-Benzenediamine, N-(1-methylethyl)-N0 -phenyl- C15H18N2 10.03
1,3,6,10-Cyclotetradecatetraene, 3,7,11-trimethyl- C20H32 0.66 7,10,13-Eicosatrienoic acid, methyl ester C21H36O2 0.73
14-(1-methylethyl)-, [S-(E,Z,E,E)]- 2-[4-Methyl-6-(2,6,6-trimethylcyclohex-1-enyl) C23H32O 0.81
(R,1E,5E,9E)-1,5,9-Trimethyl-12-(prop-1-en-2- C20H32 1.24 hexa-1,3,5-trienyl]cyclohex-1-en-1-
yl)cyclotetradeca-1,5,9-triene carboxaldehyde
2H-Pyran, 2-(7-heptadecynyloxy)tetrahydro- C22H40O2 1.02 1,4-Benzenediamine, N-(1,3-dimethylbutyl)-N0 - C18H24N2 10.85
Estra-1,3,5(10)-trien-17.beta.-ol C18H24O 7.83 phenyl-
Eicosanoic acid C20H40O2 1.25 Retinoic acid, methyl ester C21H30O2 0.76
Androstan-17-one, 3-ethyl-3-hydroxy-, (5a)- C21H34O2 0.97 Heptadecane, 9-octyl- C25H52 0.76
6,9,12,15-Docosatetraenoic acid, methyl ester C23H38O 1.07 Octadecane, 3-ethyl-5-(2-ethylbutyl)- C26H54 0.87
1,4-Benzenediamine, N-(1,3-dimethylbutyl)-N0 - C18H24N2 1.62 Octadecane, 9-ethyl-9-heptyl- C27H56 1.06
phenyl- Eicosane, 9-octyl- C28H58 1.02
Octadecane, 3-ethyl-5-(2-ethylbutyl)- C26H54 0.65 Docosane, 9-octyl- C30H62 0.67
Stigmasterol C29H48O 1.14 Docosane, 11-decyl- C32H66 0.62
 T. Kan et al. / Fuel 191 (2017) 403–410 407

Table 5 For pyrolysis oil of NR–Tyre, 1,4-benzenediamine, N-(1,3-dime

Major compounds in pyrolysis oil of SR–Tyre.
thylbutyl)-N0 -phenyl- (C18H24N2, peak area % = 13.93),
Name Formula Area D-limonene (C10H16, peak area% = 8.33), squalene (C30H50, peak
percent % area% = 6.38), benzene, 1,10 -(1,3-propanediyl)bis- (C15H16, peak
Cyclohexene C6H10 4.64 area% = 5.82) and quinoline, 1,2-dihydro-2,2,4-trimethyl-
Cyclohexene, 1-chloro-4-(1-chloroethenyl)- C8H10Cl2 1.27 (C12H15N, peak area% = 5.76) were the most abundant compounds.
Naphthalene, 5-ethyl-1,2,3,4-tetrahydro- C12H16 0.84
Naphthalene, 1,2,3,4-tetrahydro-6-methyl- C11H14 1.18
For pyrolysis oil of NR–Mat, estra-1,3,5(10)-trien-17.beta.-ol
Naphthalene, 2-methyl- C11H10 1.23 (C18H24O, peak area% = 7.83), 1H-benzocycloheptene, 2,4a,5,6,7,8,
Naphthalene, 1,2,3,4-tetrahydro-1,5-dimethyl- C12H16 0.76 9,9a-octahydro-3,5,5-trimethyl-9-methylene-, (4aS-cis)- (C15H24,
Naphthalene, 1,2,3,4-tetrahydro-1,1,6-trimethyl- C13H18 3.48 peak area% = 3.60), D-limonene (C10H16, peak area% = 2.37), and
Naphthalene, 1,2,3,4-tetrahydro-6,7-dimethyl- C12H16 0.70
2,4-di-tert-butylphenol (C14H22O, peak area% = 2.14) were the
Naphthalene, 1,2,3,4-tetrahydro-5,6-dimethyl- C12H16 2.25
Naphthalene, 1,7-dimethyl- C12H12 0.77 most outstanding ones.
Tricyclo[6.4.0.0(3,7)]dodeca-1,9,11-triene C12H14 1.58 With regards to the produced pyrolysis oil of PR–Tyre, the most
Naphthalene, 1,4-dihydro-2,5,8-trimethyl- C13H16 0.88 abundant components were 1,4-benzenediamine, N-(1,3-dimethyl
Naphthalene, 1,2-dihydro-1,5,8-trimethyl- C13H16 0.63 butyl)-N0 -phenyl- (C18H24N2, peak area% = 10.85), 1,4-
Isolongifolene, 4,5,9,10-dehydro- C15H20 0.70
1,10 -Biphenyl, 2-methyl- C13H12 0.89
benzenediamine, N-(1-methylethyl)-N0 -phenyl- (C15H18N2, peak
1,7-Dimethyl-3-phenyltricyclo[4.1.0.0(2,7)]hept-3- C15H16 0.76 area% = 10.03), estra-1,3,5(10)-trien-17.beta.-ol (C18H24O, peak
ene area% = 5.16) and spiro [5.5]undec-2-ene, 3,7,7-trimethyl-11-
Pimaric acid C20H30O2 2.01 methylene-, (-)- (C15H24, peak area% = 2.19).
1-Methyl-10,18-bisnorabieta-8,11,13-triene C19H28 1.82
The dominant compounds in the pyrolysis oil produced from
1-(p-cumenyl)adamantane C19H26 1.63
Phenol, 2,6-di(t-butyl)-4-(cyclohexanylidene)amino- C20H31NO 0.60 SR–Tyre were 1,4-benzenediamine, N-(1,3-dimethylbutyl)-N0 -phe
Cyclopropa[3,4]cyclohepta[1,2-a]naphthalene, C18H22O 1.54 nyl- (C18H24N2, peak area% = 33.99), cyclohexene (C6H10, peak
1,1a,1b,2,3,7b,8,9,10,10a-decahydro-5-methoxy- area% = 4.64), androstane, (5a)- (C19H32, peak area% = 3.96), 1-me
10-methylene- thyl-10,18-bisnorabieta-8,11,13-triene (C19H28, peak area% = 3.62)
Androstane, (5a)- C19H32 3.96
and naphthalene, 1,2,3,4-tetrahydro-1,1,6-trimethyl- (C13H18, peak
1-Methyl-10,18-bisnorabieta-8,11,13-triene C19H28 3.62
Heptamethyl-3-phenyl-1,4-cyclohexadiene C19H26 0.96 area% = 3.48).
Benzene, 1-thiobenzoyl-2,4,6-trimethyl- C16H16S 0.65 For both NR–Tyre and NR–Mat, a high concentration of d-
(6-isopropyl-3,4-bis(methylamino)-2,4,6- C15H18N4 1.15 limonene was detected which was primarily generated from the
cycloheptatrienylidene)malononitrile
major NR monomers of isoprene through radical reactions, such
1,4-Benzenediamine, N-(1,3-dimethylbutyl)-N0 - C18H24N2 33.99
phenyl- as scission of b bond in cis-1, 4 polyisoprene and intramolecular
2,6,10,14,18,22-Tetracosahexaene, 2,6,10,15,19,23- C30H48 0.53 cyclization [23]. Series of hydrocarbons with carbon number of
hexamethyl-, (all-E)-, didehydro deriv. 15, e.g. derivatives of cycloprop [e]azulene, were also identified,
indicating the similarity of pyrolysis mechanisms for NR–Tyre

NR-tyre (A) NR-Mat (B)

ο
Transmittance (%)

Transmittance (%)

ο 300 C
300 C
ο ο
500 C 500 C

4000 3000 2000 1000 4000 3000 2000 1000

-1
Wavenumber (cm ) Wavenumber (cm-1)

PR-Tyre (C) SR-Tyre (D)

ο
300 C
Transmittance (%)

Transmittance (%)

ο
300 C
ο ο
500 C 500 C

4000 3000 2000 1000 4000 3000 2000 1000

-1
Wavenumber ( cm-1 ) Wavenumber (cm )
Fig. 2. FT-IR spectra of raw rubbers and bio-chars produced at different final temperatures of 300 °C and 500 °C: (A) NR–Tyre, (B) NR–Mat, (C) PR–Tyre, and (D) SR–Tyre.
408 T. Kan et al. / Fuel 191 (2017) 403–410

and NR–Mat. Compared to the oil from NR–Tyre, NR–Mat oil con- Table 6
tained more oxygenated compounds and volatiles (e.g., oil, plasti- Peak wavenumbers and assignations for rubber samples.

cizer and additives). Similar to NR–Tyre, PR–Tyre also produced Sample Peak Assignation Ref.
oil with some C15 hydrocarbons. However, a series of name wavenumber
naphthalene-based C11–13 hydrocarbons were found in the (cm1)

SR–Tyre oil. Comparing the three tyre materials (i.e., NR–Tyre, NR- 3022 AOH [24]
PR–Tyre and SR–Tyre) to the NR–mat, it can be noted that the Tyre CAH stretching in aromatic [25]
compounds
pyrolysis oils from tyre materials contained much more nitrogen- 2950 CAH aliphatic stretching [26]
containing compounds. 2914 CAH from alkyl [27]
2845 Symmetrical CH2 stretching of [28]
3.1.3. Chars methylene
1711 Carbonyl C@O stretching [27,29]
The FT-IR spectra of the raw rubbers and chars from rubber
1536 C@C aromatic ring stretching [30]
pyrolysis at different temperatures are presented in Fig. 2. The vibration
peak wavenumbers and assignations for each rubber sample are 1418 Aromatic ring [24]
listed in Table 6. 692 CAS stretching vibrations of [31]
The peaks of the raw rubbers with wavenumbers higher than monosulfidic linkages

1600 cm1 were greatly reduced or eliminated after rubber pyrol- NR-Mat 3290 AOH and/or NAH symmetric stretch [27,32]
ysis. For NR–Tyre, no obvious peaks can be observed after pyrolysis 2914 CAH from alkyl [27]
2845 Symmetrical CH2 stretching of [28]
at 500 °C. In the case of NR-Mat, after pyrolysis, a small sharp peak
methylene
presents at 3640 cm1, which should be due to the O—H stretching 1731 AC@O stretching vibration in [25]
of non-bonded hydroxyl in absorbed water [37]. The wide peak at halogenated carboxyl group
around 1418 cm1 still presenting in the IR spectra is due to the 1634 Carbonyl C@O [27]
1596 SiAOAC [27]
residual of aromatic structures in chars. The peaks at 973 and
1535 C@C aromatic ring stretching [30]
873 cm1 are likely due to the presence of SiAO [38] and aromatic 1408 CH2 scissoring vibration of [33]
CAH bonds [25], respectively. In the case of PR-Tyre, the presence RASASACH2AR0 and/or
of RASASACH2AR0 and/or RASACH2AR0 is also confirmed at RASACH2AR0
1408 cm1. With regards to the SR-Tyre, the organic groups were 1372 CAH bending vibrations of ACH3 in [28]
propylene unit
gradually removed when increasing the final pyrolysis tempera-
1163 CAN stretching [27]
ture from 300 to 500 °C. Compared to the spectra of the three tyre 994 Out of plane bending vibrations of [28,34]
rubbers and related chars, those of NR–Mat and chars presented @CAH of vinyl groups
different IR peaks below 1200 cm1. 962 ACAH vibrations of butadiene [29,34,35]
double bond
870 & 710 Out-of-plane aromatic CAH [25]
3.2. Behaviour of rubbers during pyrolysis vibration
PR-Tyre 2914 CAH from alkyl [27]
3.2.1. Mass change of rubbers during pyrolysis 2845 Symmetrical CH2 stretching of [28]
Fig. 3 shows the thermogravimetric (TG, wt.%) as well as the dif- methylene
ferential thermogravimetric (DTG, wt.%/°C) results of the four rub- 1538 C@C aromatic ring stretching [30]
bers during their heating from room temperature to 600 °C at the vibration
1408 CH2 scissoring vibration of [33]
heating rate of 10 °C/min.
RASASACH2AR0 and/or
It can be observed that different percentages of raw materials RASACH2AR0
remained as residual for the four rubbers at 600 °C. The mass loss 1372 CAH bending vibrations of ACH3 in [28]
rate (wt.%/°C) of rubber samples were detailed by DTG profiles. No propylene unit
1072 Symmetric CASAC group stretching [28]
obvious mass changes were recorded prior to 200 °C, indicating the
vibrations in the two CAS bonds
negligible moisture content in all rubbers. The rubbers experienced 959 ACAH vibrations of butadiene [29,34,35]
the major mass loss in the temperature range of 200–500 °C due to double bond
release of organic vapours and formation of coal-like residue 868 Aromatic CAH bending [24]
[13,39]. The overlapped curve can be approximately divided into SR-Tyre 2900 Alkyl CAH stretching [24]
three main peaks through de-convolution, which was also an indi- 2846 CAH from alkyl [27]
cator of the complexity of reactions. The first peak (around 200– 1418 Aromatic ring [24]
1000–1008 Unsymmetric SiAOASi stretching [36]
350 °C) is related to decomposition of the volatiles (e.g., oil, plasti-
cizer and additives) in rubbers and the mass loss at around 300–
450 °C is due to the decomposition of the major NR component
which takes place at lower temperatures than SBR and BR [40]. plier (i.e., EHI Australia PTY LTD). For SR–Tyre an extreme sharp
The third peak (around 400–500 °C) is not obvious for NR–Tyre peak of mass loss rate formed, reaching its maximum value of
and NR–Mat, while for PR–Tyre and SR–Tyre the obvious formation 1.24 wt.%/°C at 326 °C. This is probably caused by the fast degrada-
of the third peak should be mainly due to the degradation of the tion of the organic additives in SR–Tyre. An independent much
common SBR and/or BR components in tyres [41]. lower peak was also observed at 435 °C, which should be due to
Specifically, NR–Tyre (black) showed an even higher mass loss the degradation of BR component [40]. The mass decreased slightly
rate with the peak value of 0.64 wt.%/°C at 380 °C while its mass and constantly after 500 °C without the formation of obvious
almost remained unchanged during 500–600 °C. The DTG curve peaks.
of NR–Mat is similar to that of NR–Tyre but shows lower maximum
mass loss rate of 0.38 wt.%/°C. 3.2.2. Heat change of rubbers during pyrolysis
The DTG peak of PR–Tyre at 380 °C also indicates the existence The specific heat of a substance represents the amount of
of NR and the obvious side peak centring at around 426 °C should energy the substance takes in when its temperature is raised by
be ascribed to the decomposition of SBR [34]. The existence of SBR one unit degree Celsius. The specific heats of the rubbers versus
as a major component in PR–Tyre was also confirmed by its sup- temperature during pyrolysis are shown in Fig. 4.
 T. Kan et al. / Fuel 191 (2017) 403–410 409

100 2.0 pared to the PR–Tyre and SR–Tyre, the natural rubber materials
NR-Tyre

Mass loss rate (DTG, %/ C)

(NR–Tyre and NR–Mat) exhibited lower heat changes at both lower
Mass remaining (TG, %)
NR-Mat

o
80 PR-Tyre 1.5
temperatures (abbr. LT, around 280–420 °C in Fig. 3) and higher
SR-Tyre temperatures (abbr. HT, around 390–490 °C in Fig. 3) in the main
60 pyrolysis zone. The NR-Mat sample exhibited differences compar-
1.0 ing to the three tyre rubbers with no obvious peaks identified at
40 the HT zone for the NR–Mat., The heat changes increased from
the NR–Tyre to PR–Tyre and then SR–Tyre in both LT and HT zones.
0.5 The extreme exothermic peak occurred at lower temperatures of
20
295–371 °C in the SR–Tyre, which is consistent with the DTG
0 0.0 results in Fig. 3.
200 400 600
o
Temperature ( C) 4. Conclusion
Fig. 3. TG and DTG curves of rubber.
In this study, four different rubber samples including natural
rubber tyre, pneumatic tyre, synthetic rubber tyre and one natural
rubber mat were pyrolysed at 10 °C/min to generate fuel products
4
NR-Tyre of pyrolytic gas, pyrolysis oil and char. H2 and CO were basically
NR-Mat the primary gas species in the gas product, indicating the potential
Specific heat (MJ/m K)

PR-Tyre of using the pyrolytic gas for syngas or hydrogen production. Com-
3

2 lower H2 release. More obvious H2 generation but much less CO
0
200
o and heat change behaviour of the investigated rubbers were quan-
Temperature ( C)
Fig. 4. Specific heat of rubbers with temperature during pyrolysis.
The volumetric heat of reaction (DHv) for each peak was quan-
tified through integration of the corresponding peaks in the curve.
The DHv results are shown in Table 7.
The specific heat is affected by the material type and form. In
our work, the specific heat capacity of rubbers didn’t change much
with temperature during pyrolysis except for the occasions where
violent reactions took place (roughly 300–500 °C). When heating
the rubbers from room temperature to 600 °C at 10 °C/min, the
rubber components underwent gradual degradation and charring.
The solid material structure also changed gradually and obviously
the formed chars at 600 °C had the similar specific heat capacity to
the raw rubber samples.
The positive peaks and negative troughs are indicators for
endothermic and exothermic events, respectively. The absence of
endothermic peaks before 200 °C indicates the negligible moisture
content of all rubbers. In all samples, an endothermic change
occurred between 380 and 500 °C as reflected by the formed low
positive peak. The heat changes were in the range of 15 to
44 MJ/m3. Between 400 and 500 °C, a small endothermic peak
occurred for all samples, ranging from 1.6 to 11.2 MJ/m3. After
500 °C, no obvious energy changes were identified. When com-
Table 7
Heats of reactions of rubber pyrolysis.
Sample Temperature range (°C)
NR–Tyre 298–394
401–445
NR–Mat 298–424
PR–Tyre 289–412
412–470
SR–Tyre 295–371
391–464
SR-Tyre
pared to NR–Tyre, NR–Mat had similar CO evolution but much
evolution was observed in PR–Tyre and SR–Tyre after 500 °C than
NR–Tyre. For both NR–Tyre and NR–Mat, a high concentration of
d-limonene and a series of C15 hydrocarbons were detected.
Noticeable naphthalene derivatives were found in the SR–Tyre
oil. In addition, much less nitrogen-containing compounds were
identified in the NR–Mat derived oil than the oils from the three
tyre materials (i.e., NR–Tyre, PR–Tyre and SR–Tyre). Distinct mass
400 600
tified, which showed the complexity and variability in the pyroly-
sis process of different rubber sources. Compared to the natural
rubber materials (NR–Mat and NR–Tyre), synthetic polymer-
bearing materials (PR–Tyre and SR–Tyre) exhibited more intensive
heat changes.
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