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Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 1–7

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Journal of the Taiwan Institute of Chemical Engineers

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Effect of polyethylene terephthalate on the catalytic pyrolysis

of polystyrene: Investigation of the liquid products
Adnan∗, Jasmin Shah, Muhammad Rasul Jan
Institute of Chemical Sciences, University of Peshawar, Peshawar 25120, Khyber Pakhtunkhwa, Pakistan

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

Article history: Safe and environmentally benign treatment and disposal of waste plastics are growing challenges of our
Received 21 May 2014 society. In this paper, the influence and reactivity of polyethylene terephthalate (PET) on the pyrolysis of
Revised 12 January 2015
polystyrene (PS) is reported. The experiments were performed in a quartz glass reactor to determine the
Accepted 13 January 2015
effects of temperature (250–500 °C), reaction time (20–90 min), and feed to catalyst ratio (1:0–1:0.3) using 20%
Available online xxx
Al-Al2 O3 catalyst. PS pyrolyzed at a lower temperature than thermogravimetric (TG) pyrolysis in the presence
Keywords: of catalysts. Significant interactions between the polymers were noted based on the composition of liquid
Catalysis product. Increasing the composition of PET reduced the liquid products formed. Many useful compounds such
Polyethylene terephthalate as benzene, styrene, α -methylstyrene, indene, biphenyl, naphthalene, naphthalene derivatives and terphenyls
Polystyrene etc. and some oxygenated compounds such as 2-pentanone, 4-hydroxy-4-methyl, acetophenone, 2-buten-
Pyrolysis 1-one, 1-phenyl and 1,2-propanediol, 3-benzyloxy-1,2-diacetyl etc. were identified. Single ring aromatic
Recycling
hydrocarbons (C6 –C9 fraction) particularly that of styrene monomer, were dominant products.
Plastics
© 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction Municipal solid wastes comprise a variety of plastics in differ-

Polyethylene terephthalate (PET) and polystyrene (PS) are among
the most widely used plastics. Increasing demand for these plas-
tics and their subsequent disposal is a major environmental concern,
since they pose many adverse effects on living organisms [1,2]. Plastic
wastes are currently landfilled or incinerated. These wastes are non-
biodegradable and remain in landfill sites for hundreds of years. They
also emit toxic gases such as greenhouse gases, benzene, dioxins and
furan to the environment upon incineration [3–5].
Therefore, alternative routes for the treatment of plastic wastes
such as chemical recycling have gained attention [1,6]. In chemical
recycling, the pyrolysis of plastic wastes in the presence of catalysts
has gained increasing attention [7], because the proper selection of
catalysts enables the control of the yield of the process and the kind
of products obtained. The effects of various types of catalysts, their
chemical compositions, and morphology on the chemical recycling
of plastic wastes have been reported in literature [5,8,9]. The use of
supported catalysts to replace conventional catalysts has garnered
interest due to their high activity, product selectivity, and ease of
regeneration [5,8].
∗
Corresponding author. Tel.: +92 333 950 8730.
E-mail address: adnanchem@yahoo.com, fa2358@columbia.edu, adnanchem@
upesh.edu.pk (Adnan).
ent ratios for applications such as plastic fencing, pipes, and damp-
proof membranes [10]. The existence of these mixed plastics in mu-
nicipal solid wastes motivated us to study the co-pyrolysis of PET
and PS. Various studies have reported on the thermal and thermo-
catalytic pyrolysis of polyolefin [7], thermo-catalytic pyrolysis of PS
into styrene monomer, dimers, oligomers and other products like
benzene, toluene and ethylbenzene [8,11–13]. Vasile et al. [14] car-
ried out both thermal and catalytic pyrolysis of mixed plastics (24 wt.%
high density polyethylene (HDPE), 39 wt.% low density polyethylene
(LDPE), 21.5 wt.% polypropylene (PP), 10 wt.% PS, 4 wt.% acrylonitrile–
butadiene–styrene (ABS) copolymer and 1.5 wt.% PET using H ZSM-5
and PZSM-51 catalysts. Catalysts were reported to increase gaseous
products and changed the composition of liquid products depend-
ing on the activity and selectivity of the catalyst. Aromatic hydro-
carbons were reported in the majority with catalytic pyrolysis at
400–450 °C. Bhaskar et al. [15] performed studies on the pyrolysis of
PP/PE/PS/PVC/high impact polystyrene with brominated flame retar-
dant (HIPS-Br) mixed plastics and dehalogenation of liquid products.
It was reported that the presence of PET affected the pyrolysis behav-
ior and formation of liquid products. They reported that the addition
of PET reduced the yield of liquid products, while the yield of gaseous
products and residue increased. Williams and Slaney [10] studied the
pyrolysis of single and mixed waste plastics (PE, PP, PS, PET and PVC)
under nitrogen (N2 ) and hydrogen (H2 ) pressure, and reported that
the liquids primarily contain aromatic hydrocarbons formed due to
the significant interactions between the mixtures of plastics. Siddiqui

http://dx.doi.org/10.1016/j.jtice.2015.01.015
1876-1070/© 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: Adnan et al., Effect of polyethylene terephthalate on the catalytic pyrolysis of polystyrene: Investigation of the
liquid products, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.01.015
JID: JTICE
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2 Adnan et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 1–7

and Redhwi [7] investigated the pyrolysis of LDPE, HDPE, PP and PET
mixed with PS for the recovery of valuable products using hydropro-
cessing catalysts, solvents, 1 wt.% catalyst on the basis of feed, 60 min
reaction time, 5.5–6.0 MPa pressure and 430–440 °C temperature.
PS in mixture with other plastic was reported to produce many im-
portant compounds such as benzoic acid, naphthalene, naphthalene
derivatives, biphenyls, terphenyls and quaterphenyls etc., which were
dominant with aromatic hydrocarbons particularly styrene monomer
and styrene oligomers. It was reported that a ratio 1:1 gave the
best yields in the form of pyrolytic liquids. Lopez-Urionabarrenechea
et al. [16] also reported the pyrolysis of waste plastic packing ma-
terial comprising a mixture of PE, PP, PS, PET, and PVC at 440 °C for
30 min using ZSM-5 as catalyst. They also observed many commer- Fig. 1. Schematic diagram of the pyrolysis assembly for PS and xPET + PS.
cially useful compounds for industrial applications such as toluene,
ethylbenzene, xylenes, styrene, methylstyrene, indenes, naphthalene
and naphthalene derivatives.
Although, a significant amount of work is available on the pyrolysis
of a multi-mixture of plastics while some literature is available on the
binary mixture plastics including PS and PET in the presence of various
solvents and additives [17–19], but no specific work is available on the
binary interaction of PS and PET. The aim to this study is to determine
the effects of PS and PET interaction on the pyrolysis products of PS
in the presence of 20% Al-Al2 O3 supported catalysts, which has been
reported to have good activity and selectivity for the pyrolysis of
virgin PS [20].

2. Experimental methodology

2.1. Materials
Al2 O3 (ࣙ98%), AlCl3 (99.99%) and polystyrene (PS) were purchased
from Sigma–Aldrich. Polyethylene terephthalate (PET) was supplied
by DuPont Teijin film. PS and PET were with average molecular
weights (MW) ~192,000 and ~24,900, respectively and with parti-
cle size 0.2–0.4 mm. The proportions of PET and PS in the mixtures
were denoted as xPET + PS, where x represents the wt.% of PET with
respect to PS. Three different mixtures of PET and PS were prepared:
10PET + PS, 20PET + PS and 30PET + PS.
Fig. 2. TGA curves of PS and PET.
the bottom of the reactor was recovered and regenerated by washing
with n-hexane several times. It was then dried for at 120 °C for 1 h
[21]. The n-hexane was evaporated and the weight of the residue was
determined. The liquid products and residue are expressed in terms
of wt.% of the feed material.
2.4. Thermogravimetric analysis

2.2. Catalyst preparation PS and PET samples monitored by thermogravimetric analysis

20% Al-Al2 O3 crystalline catalyst was prepared in the laboratory
by a method that was reported in our previous study [20]. The catalyst
was prepared by a wet impregnation method using Al2 O3 as support
and AlCl3 as precursor metal salt. About 20 wt.% of AlCl3 was dissolved
in 50 ml of deionized water while stirring for 15 min at 700 rpm, after
which 5.0 g of Al2 O3 powder was added to the slurry. The resultant
mixture was continuously stirred for 1 h at 60 °C, and then dried
overnight at 110 °C followed by calcination at 300 °C for 4 h. The
sample was ground to a fine powder and then screened to a particle
size ࣘ0.44 mm.
2.3. Pyrolysis experiments
The pyrolysis experiments were carried out in a quartz tube reac-
tor (height 30 cm and internal diameter 2.5 cm) set in a furnace op-
erated at ambient pressure. The schematic of the experimental setup
is shown in Fig. 1. For each experiment, 5 g of feed material was py-
rolyzed in the reactor in a mixture of solid catalyst (a weight by weight
blend) without the use of any solvent or additives. The reactor was
heated up to the desired temperature at a rate of 25 °C/min and the
final temperature was held constant for specified durations of time.
All the experiments were carried out using triplicate analysis. The
products of pyrolysis experiments were cooled by water condenser
and collected in an ice cold trap. The liquid products and residue left
in the reactor were then collected and weighed. The catalyst left at
(TGA) using Rigaku TAS 100 data station. Approximately 10 mg sam-
ples were heated. The temperature was maintained for 10 min at
ambient temperature (30 °C) and then linearly increased from 30 °C
to 1000 °C at the rate of 25 °C/min in a nitrogen (N2 ) flow rate of
20 ml/min.
2.5. GC–MS analysis
The analysis was carried out by coupled gas chromatography and
mass spectrometry analyzer (GC–MS, QP2010 Shimadzu). The instru-
ment was fitted with DB-5MS column from Agilent Technologies
(30 m × 0.25 mm, internal diameter 0.25 μm). Helium (99.99% pure)
was used as carrier gas with a flow rate of 1.5 ml/min and split ratio 30.
The sample injection volume was 1 μl and the injector temperature
was 300 °C. The oven was programmed as follows: initial temperature
35 °C (held for 5 min), first ramp from 35 °C to 100 °C at 5 °C/min (held
for 1 min), second ramp from 100 °C to 150 °C at 10 °C/min (held for
10 min) and third ramp from 150 °C to 290 °C at 2.5 °C/min (held for
10 min).
3. Results and discussion
3.1. Thermogravimetric analysis
The TGA results of virgin PS and PET are shown in Fig. 2. The initial
thermal decomposition of both PS and PET was endothermic due to

Please cite this article as: Adnan et al., Effect of polyethylene terephthalate on the catalytic pyrolysis of polystyrene: Investigation of the
liquid products, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.01.015
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Adnan et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 1–7
Fig. 3. Effect of temperature on the yields of liquid and gas products for the pyrolysis
of PS, 10PET + PS, 20PET + PS and 30PET + PS.
C–C and C–O (for PET only) bond rupture. The weight loss versus
temperature curves of both, PS and PET shows single step pyrolysis
in N2 [22]. It shows the onset temperature of 369 °C, 401 °C, and end
set temperature of 471 °C and 494 °C for PS and PET, respectively. The
curve shows 100 wt.% loss in the case of PS and 82 wt.% loss in the case
of PET at their respective end set temperatures. This was also reported
in other studies [7]. PET in the process of thermal pyrolysis left much
amount of solid residue that did not decompose even at 1000 °C.
This phenomenon is supported by several studies of PET pyrolysis in
the N2 environment at high temperature. The residue left even at a
high temperature in the case of PET is attributed to the interlinking
reaction between the decomposed products of PET forming stabilized
products [23].
3.2. Yield of products
The amount of PET was varied to understand and explore its role
and reactivity on the pyrolysis of PS. The pyrolysis products were
liquids, gases, and solid residue in the case of all materials. Prelimi-
nary experiments were also performed with the pyrolysis of only PET
under the same initial reaction condition but very small amount of liq-
uid products were formed that deposited over the walls of the reactor
and/or condenser, and were not collected [23]. The effect of pyroly-
sis temperature, reaction time and feed to catalyst ratio on thermo-
catalytic pyrolysis of PS, 10PET + PS, 20PET + PS and 30PET + PS
were studied to determine the conditions that favor the formation of
maximum liquid products and to compare the products and product
compositions formed at the optimized reaction conditions.
3.2.1. Effect of pyrolysis temperature
The effect of pyrolysis temperature over a wide range of 250 °C
to 500 °C at a reaction time of 30 min, and feed to catalyst ratio of
1:0.05 on the distribution of liquids and gases was determined (Fig. 3).
This temperature range was selected because the decomposition of PS
and PET occurred after 250 °C as shown by the TGA and a temperature
range of 400 °C to 500 °C was reported to achieve a maximum yield
of liquid products [10,12,14,24,25].
During the pyrolysis of the feedstock two different events in the
production of the liquid production was occurred, especially for PS: a
large increase occurring up to 350 °C (from nearly 30 wt.% for 300 °C
up to 55 wt.% for 350 °C) and a less pronounced increase in a wider
temperature interval from 350 to 500 °C (from 55 to 82 wt.%). For
liquid products, the yield increased linearly with the increase in tem-
perature reaching its maximum of 82.4 wt.% and 67.3 wt.% at 500 °C in
the case of PS and 10PET + PS, respectively. In the case of 20PET + PS
and 30PET + PS, the yield initially increased up to a maximum of
37.3 wt.% and 19.2 wt.% at 450 °C, respectively but further increase
in the pyrolysis temperature slightly reduced the yield. For gases, the
Please cite this article as: Adnan et al., Effect of polyethylene terephthalate on the catalytic pyrolysis of polystyrene: Investigation of the
liquid products, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.01.015
[m5G;February 14, 2015;14:54]
3
Fig. 4. Effect of reaction time on the yields of liquid and gas products for the pyrolysis
of PS, 10PET + PS, 20PET + PS and 30PET + PS.
maximum yield was achieved at 250 °C and it decreased with the
rise in temperature in the pyrolysis of PS and 10PET + PS. In the case
of 20PET + PS, however, the yield of gases increased initially with
the rise in temperature reaching its upper limit at 300 °C and then
decreased with further ramp. In the case of 30PET + PS, the yield of
gases increased up to 350 °C then decreased a little and eventually
increased up to its upper limit at 500 °C. The maximum total yields in
the cases of PS, 10PET + PS, 20PET + PS and 30PET + PS was 98.4 wt.%
at 500 °C, 98.4 wt.% at 450 °C, 95.9 wt.% at 450 °C and 96.7 wt.% at
500 °C, respectively. In the presence of 20% Al-Al2 O3 , the produc-
tion of gases at 250 °C in the case of all materials indicates that the
decomposition process started before 250 °C instead of 369.3 °C or
401.5 °C for PS and PET, respectively as identified by the TGA (Fig. 2).
Interestingly, the increase in PET percentage dramatically reduced
the yield of liquid products with the concomitant increase in gases. At
higher temperature, the decrease in the liquid products and increase
in gases produced might be due to the further cracking of the pre-
formed products, the same observations were also reported by Vasile
et al. [14]. PET has been reported to produce more gases and residue
compared to liquid products and some studies have reported the for-
mation of negligible amount of liquid products [23]. In some plastic
mixtures, PET was also reported to increase in the carbon residue by
up to 25 wt.% [15].
3.2.2. Effect of reaction time
The effect of the reaction time on the pyrolysis of virgin PS and
mixed plastics (xPET + PS) was investigated. Experiments were per-
formed at reaction times of 20, 30, 60 and 90 min, at an optimized
pyrolysis temperature of 500 °C for PS and 10PET + PS, and 450 °C
for 20PET + PS and 30PET + PS determined based on the experiments
reported in Section 3.2.1, and a feed to catalyst ratio of 1:0.05 (Fig. 4).
This criterion was adopted based on the maximum amount of liquids
produced from the feedstocks. For liquids, it was observed that the
yield increased significantly when the reaction time was increased
from 20 min to 60 min in the cases of PS, 10PET + PS and 20PET + PS.
In the case of 30PET + PS, however, a very small increase was observed
when the reaction time was increased to 90 min. The maximum yield
was 86.3 wt.%, 70.0 wt.% and 40.6 wt.% in 60 min in the cases of PS,
10PET + PS and 20PET + PS, respectively. In the case of 30PET + PS,
the maximum yield was 21.1 wt.% in 90 min. The maximum total
yield in the cases of PS, 10PET + PS, 20PET + PS and 30PET + PS was
99.3 wt.%, 97.7 wt.%, 95.4 wt.% and 93.5 wt.%, respectively at reaction
conditions of: pyrolysis temperature 500 °C for PS and 10PET + PS,
and 450 °C for 20PET + PS and 30PET + PS; reaction time 60 min for
PS, 10PET + PS and 20PET + PS and 90 min for 30PET + PS).
Beyond the described optimum time, a further increase in reaction
time showed no apparent change in the yield of liquid products. The
yield of gases was observed to increase initially up to 30 min and then
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4 Adnan et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 1–7
Fig. 5. Effect of feed to catalyst ratio of the yields of liquid and gas products for the
pyrolysis of PS, 10PET + PS, 20PET + PS and 30PET + PS.
decrease, it is suggested due to the interaction of gaseous products
with other compounds which ultimately form high molecular weight
aromatic hydrocarbons. However, in some cases the yield of gases also
increased beyond the optimized time (for liquid products), which
resulted in an increase in the total yield. The increase in the liquid
product in cases of longer reaction time indicates the completion of
the pyrolysis reaction, whereas an increase in the yield of gases with
further increase in reaction time may be due to the further pyrolysis
of some pre-formed products or the decomposition of some part of
the residue.
3.2.3. Effect of feed to catalyst ratio
Catalysts play an important role in the pyrolysis of plastics and
modify the pyrolytic pathways. The incorporation of a catalyst influ-
ences pyrolysis by (i) reducing pyrolysis temperature, (ii) reducing
reaction time, and (iii) providing suitable control of selectivity for the
formation of value added products [25]. The amount of catalysts per
fixed feed material has also been reported to affect the conversion
process [26]. The influence of feed to catalyst ratio was investigated
in 1:0 (without catalysts), 1:0.05, 1:0.1, 1:0.2 and 1:0.3 feed to cata-
lyst ratio at optimized pyrolysis temperature and reaction time, the
results are shown in Fig. 5. A significant increase was observed in the
yield of liquid products when the catalyst was added using the same
reaction conditions as compared to thermal pyrolysis without the use
of catalyst. The liquid products was increased from 78.1 to 86.3 wt.%
in the case of PS, from 56.2 to 70.0 wt.% in the case of 10PET + PS, from
21.6 to 40.60 wt.% in the case of 20PET + PS and from 6.3 to 21.1 wt.%
in the case of 30PET + PS. In the presence of 20% Al-Al2 O3 catalysts,
the yield of liquid products increased significantly when the feed to
catalyst ratio was increased and a maximum was achieved with a
feed to catalyst ratio of 1:0.2 in all cases. The yield was increased
significantly from 86.3 wt.% to 92.5 wt.% in the case of PS and from
70.0 wt.% to 76.5 wt.% in the case of 10PET + PS. The conversion of PS
into liquid products was practically the same as those obtained with
20% Al-Al2 O3 in our previous method [20]. The yield was increased
slightly from 40.6 wt.% to 42.7 wt.% in the case of 20PET + PS and it
increased from 21.1 wt.% to 22.7 wt.% in the case of 30PET + PS.
The yield of gases was also affected by the increase in the feed to
catalyst ratio. Unlike in the case of PS and 10PET + PS pyrolysis when
the yield of gases decreased with an increase in the feed to catalyst
ratio, the yield of gases was first decreased and then increased with
associated increase in liquid products in the cases of 20PET + PS and
30PET + PS. The feed to catalyst ratio also raised the total yield, which
was 100.00 wt.%, 97.7 wt.%, 95.1 wt.% and 88.9 wt.% maximum with
1:0.2 feed to catalyst ratio in the cases of PS, 10PET + PS, 20PET + PS
and 30PET + PS. A further increase in the feed to catalyst ratio of 1:0.2
reduced the yield of liquid products. It is suggested that this may be
due to the availability of more reaction sites due to an increase in the
Please cite this article as: Adnan et al., Effect of polyethylene terephthalate on the catalytic pyrolysis of polystyrene: Investigation of the
liquid products, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.01.015
[m5G;February 14, 2015;14:54]
Table 1
Comparison of optimized reaction condition and the yield of products for the pyrolysis
of PS, 10PET + PS, 20PET + PS and 30PET + PS.
PS 10PET + PS 20PET + PS 30PET + PS
Reaction conditions
Pyrolysis temperature (°C) 500 500 450 450
Reaction time (min) 60 60 60 90
Feed to catalyst ratio 1:0.2 1:0.2 1:0.2 1:0.2
Contents of products (wt.%)
Liquid yield 92.69 76.40 44.60 22.50
Gas yield 7.31 21.30 50.51 71.80
Residue left 0.00 2.30 3.89 5.70
Total conversion 100.00 97.70 95.11 94.30
Reaction conditions: For PS and 10PET + PS (500 °C, 60 min and feed to catalyst ratio
of 1:0.2), for 20PET + PS (450 °C, 60 min and feed to catalyst ratio of 1:0.2) and for
30PET + PS (450 °C, 90 min and feed to catalyst ratio of 1:0.2).
amount of acidic catalysts, which impacts the reaction mechanism
leading to the production of more gaseous products [27]. Collectively
the addition of PET resulted in a significant decrease in the yield
of liquid products, and a small decrease in the total percentage of
conversion with concomitant increase in the yield of gases.
The maximum yield of products and total yield along with the
optimized conditions for the pyrolysis of PS, 10PET + PS, 20PET + PS
and 30PET + PS using 20% Al-Al2 O3 catalyst is given in Table 1. The
increase in gases with associated decrease in the liquid products is
attributed to the presence of PET and an increase in the amount of
high activity catalysts which bear a large number of Brönsted acid
sites [16]. The pyrolysis of pure PET has been reported to produce high
amount of solid residue [23]. Therefore, the increase in PET content
during the pyrolysis of xPET + PS produced more residue. The residue
may deposit over the catalysts causing to deactivate it, as a result of
which thermal pyrolysis is promoted.
3.3. GC–MS analysis
The products obtained from the pyrolysis of PS and xPET + PS were
identified by GC–MS and classified in three different ways i.e., classi-
fication on the basis of (i) carbon number, (ii) depolymerization, and
(iii) identified component of the products. The distribution of liquid
products obtained from the pyrolysis of PS, 10PET + PS, 20PET + PS
and 30PET + PS at optimized conditions are represented in Tables
2–4 and expressed in terms of wt.% of the liquids. The liquid products
derived from the pyrolysis of virgin PS and xPET + PS gave almost
exclusively substituted aromatic hydrocarbons. Generally the pyrol-
ysis of polymers due to their poly-disperse nature and high molecular
weight lead to reactions with thousands of species, which often result
in the formation of a wide spectrum of compounds. Furthermore, the
catalytic pyrolysis of polymers is also accompanied by thermal pro-
cesses, which result in more complex mechanisms [25]. As discussed
in the earlier section, increasing the concentration of PET increases
the amount of residue left, which in turn results in the deactivation
of catalysts and leads to thermal transformation.
Table 2 shows classification on the basis of the carbon number
and the distribution of aromatic and non-aromatic hydrocarbons in
the range of C6 –C24 which are grouped in three categories: C6 –C9 ,
C10 –C18 , and C19 –C24 fractions. As can be seen in Table 2, the yield
of C6 –C9 non-aromatic fraction was 12.0 wt.%, 0.3 wt.%, 0.5 wt.% and
0.6 wt.%, where the yield of C6 –C9 aromatic fractions was 85.0 wt.%,
56.8 wt.%, 71.9 wt.% and 74.3 wt.% in the cases of PS, 10PET + PS,
20PET + PS and 30PET + PS pyrolysis, respectively. The yield of frac-
tions are increasing (in terms of wt.% of the liquid products) but they
in fact they are decreasing (in terms of wt.% of the feedstock) i.e.
the yield of C6 –C9 fraction with 10PET + PS was 43.38 wt.%, with
20PET + PS was 32.08 wt.% and with 30PET + PS was 16.7 wt.%. The
degradation of PS in the presence of 20% Al-Al2 O3 is already reported
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Adnan et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 1–7 5

Table 2
Fractions of interest identified by GC–MS in the liquid products obtained from the pyrolysis
of PS, 10PET + PS, 20PET + PS and 30PET + PS.

Carbon no. Type PS 10PET + PS 20PET + PS 30PET + PS

C6 –C9 Non-aromatic 12.00 0.28 0.54 0.61

Aromatic 85.01 56.75 71.93 74.32
C10 –C18 Aromatic 2.99 40.59 22.37 22.27
C21 –C24 Aromatic 0.00 2.38 5.16 2.80

Reaction conditions: For PS and 10PET + PS (500 °C, 60 min and feed to catalyst ratio of
1:0.2), for 20PET + PS (450 °C, 60 min and feed to catalyst ratio of 1:0.2) and for 30PET + PS
(450 °C, 90 min and feed to catalyst ratio of 1:0.2).

Table 3
Depolymerization products identified by GC–MS in the liquid products obtained from the
pyrolysis of PS, 10PET + PS, 20PET + PS and 30PET + PS.

Products PS 10PET + PS 20PET + PS 30PET + PS

Styrene monomeric products 84.24 65.77 78.06 80.60

Styrene dimeric products 2.94 18.52 12.19 13.07
Styrene oligomers 0.00 5.11 4.51 1.80
Naphthalene and its derivatives 0.82 8.36 0.60 0.95
Anthracene and its derivatives 0.00 2.47 2.76 2.98
Other components 12.00 0.77 1.88 0.60

Reaction conditions: For PS and 10PET + PS (500 °C, 60 min and feed to catalyst ratio of 1:0.2),
for 20PET + PS (450 °C, 60 min and feed to catalyst ratio of 1:0.2) and for 30PET + PS (450 °C,
90 min and feed to catalyst ratio of 1:0.2).

that it produce styrene monomeric products (C6 –C9 ) in abundance
[20,28], while the addition of 10% PET promoted depolymerization
reaction that yielded mostly dimeric products ranging from C10 –C18 ,
while a further addition of PET caused to produce more gases and
thus decreased the abundance of liquid product that ultimately de-
creased the yield of this fraction. Consequently, the yield of C10 –C18
fraction was 3.0 wt.%, 40.6 wt.%, 22.4 wt.% and 22.3 wt.% in the cases
of PS, 10PET + PS, 20PET + PS and 30PET + PS, respectively. Con-
cerning the pyrolysis of PS, C21 –C24 fraction did not form at all and
it was 2.4 wt. %, 5.2 wt.% and 2.8 wt.% in the cases of 10PET + PS,
20PET + PS and 30PET + PS, respectively. The C6 –C9 fraction was the
main fraction and mostly comprised of aromatic hydrocarbons, more
specifically single ring aromatic hydrocarbons like benzene, toluene,
ethylbenzene styrene, and α -methylstyrene etc. However, the addi-
tion of PET caused an increase in the yield of C10 –C18 and C21 –C24
fractions, which comprise double ring, triple ring and quartet ring
products. The presence of non-aromatic fraction in liquid products
has also been reported by Lopez-Urionabarrenechea et al. [16]. The
high yield of low molecular weight aromatic hydrocarbons in the
presence of acidic catalyst has been reported and it was suggested
that it is due to the acidic catalyst that led the reaction through
an end-chain scission pathway without promoting thermal crack-
ing [16,29]. The results indicate the formation of higher fraction in
the case of PET addition. This is attributed to the deactivation of the
catalyst is due to deposition of cracked and melted fragments of poly-
mer that ultimately promoted thermal pyrolysis that resulted in the
formation of a large number of aromatic hydrocarbons with a random
scission mechanism. Similarly, Carniti et al. [30] suggested that the
formation of aromatic hydrocarbons from the pyrolysis of polyolefins
is due to the saturation of aromatic compounds at ethylenic double
bonds which leads to the formation of a large number of aromatic
compounds.
The classification of component products based on the depolymer-
ization of PS is shown in Table 3. The main families identified were sin-
gle styrene monomeric products, styrene dimeric products, styrene
oligomers, naphthalenes and naphthalene derivatives, anthracene,
and anthracene derivatives. Styrene monomeric products were abun-
dant in all the pyrolysis liquids. Their compositions were 84.2 wt.%,
65.8 wt.%, 78.1 wt.% and 80.6 wt.% in the cases of PS, 10PET + PS,
20PET + PS and 30PET + PS, respectively. Among the monomeric
products, benzene, toluene, ethylbenzene, styrene, benzaldehyde, α -
methylstyrene, α -ethylstyrene and benzene, 3-butenyl were domi-
nant compounds. The depolymerization of PS is of carbonium nature
which involves the attack of a proton to the aromatic rings of PS. The
resulting carbenium species undergo continuous decomposition fol-
lowed by a hydrogen transfer. Therefore, styrene monomer was abun-
dant in all the liquid products [27,31]. The formation of benzene and
its hydrogenation to form toluene and ethylbenzene or the formation
of other products decreased the yield of styrene monomer [9,32]. The
preformed compounds upon isomerization and further decomposi-
tion can form final products such as benzene, toluene, ethylbenzene,
α -methylstyrene, benzene, (1-methylethyl), naphthalene, and others
have been discussed in several studies using acidic catalysts [25,33].
The higher content of styrene monomeric products in the liquid prod-
ucts derived from the pyrolysis of xPET + PS was suggested by Serrano
et al. [29] is due to the catalyst has lost its activity. Terephthalic acid is
also reported as a rich source of aromatic hydrocarbons like benzene,
toluene, biphenyls, naphthalene and their derivatives [7,23,34]. The
cracking of PET on its ester bond results in the formation of tereph-
thalic acid, which on decarboxylation produces benzoic acid, and then
benzene. These products are the sources of aromatic hydrocarbons.
The highest compositions of styrene dimers, oligomers, naph-
thalenes, naphthalene derivatives and some other products were
noted in the case of 10PET + PS. These compositions were lower
in the case of 20PET + PS and 30PET + PS. The dominant
dimeric products detected were: benzene,1,1 -(1,1,2,2-tetramethyl-
1,2-ethanediyl)bis; benzene, 1,1 -(1-methyl-1,2-ethanediyl)bis; ben-
zene, 1,1 -(1,3-propanediyl)bis; benzene, 1,1 -(3-methyl-1-propene-
1,3-diyl)bis and benzene, 1,1 -(2-methyl-1-propenylidene)bis. The
formation of some styrene oligomers (trimers and tetramers) was
also noted. Their compositions were the highest (5.1 wt.%) in the
case of liquid products with the pyrolysis of 10PET + PS. The highest
yield of naphthalene and its derivatives were also achieved in the
case of liquid products obtained from the pyrolysis of 10PET + PS.
The production of a considerable amount of naphthalene and naph-
thalene derivatives have also been reported by Vasile et al. [14] dur-
ing the pyrolysis of mixed plastics. The formation of products like
benzene, naphthalene, indane and indene, and diphenyl derivatives

Please cite this article as: Adnan et al., Effect of polyethylene terephthalate on the catalytic pyrolysis of polystyrene: Investigation of the
liquid products, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.01.015
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6 Adnan et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 1–7

Table 4
Chemical composition of liquid products identified by GC–MS obtained from the pyrolysis of PS, 10PET + PS, 20PET + PS
and 30PET + PS.

Composition (wt.%)

S. no. Component name PS 10PET + PS 20PET + PS 30PET + PS

1 Benzene 1.26 0.98 1.73 1.07

2 Toluene 10.51 0.06 1.28 1.49
3 3-Hexen-2-one 6.69 0.00 0.00 0.00
4 2-Pentanone, 4-hydroxy-4-methyl- 0.00 0.28 0.54 0.69
5 Ethylbenzene 7.17 1.58 3.01 3.30
6 Styrene 62.54 46.97 59.86 64.31
7 Benzaldehyde 0.00 1.44 1.09 0.29
8 α -Methylstyrene 1.90 3.50 2.48 1.65
9 Methyl-styrene 0.30 0.61 0.41 0.10
10 Indene 0.79 0.54 0.54 0.55
12 α -Ethylstyrene 0.02 0.06 2.97 3.84
13 Benzenemethanol,α ,α -dimethyl 0.00 0.00 0.21 0.17
14 Acetophenone 0.00 0.71 0.77 0.87
15 Benzene,1,1 -(1,1,2,2-tetramethyl-1,2-ethanediyl)bis 2.15 0.65 0.76 0.84
16 Naphthalene 0.82 1.88 0.21 0.16
17 2-Butanone, 4-phenyl 0.00 0.00 0.18 0.23
18 2-Buten-1-one, 1-phenyl 0.00 0.35 0.58 1.08
19 Diphenylmethane 0.00 0.52 3.00 3.89
20 Ethylene, 1,1-diphenyl 0.00 0.39 0.00 1.14
21 Biphenyl 0.00 6.64 0.17 0.00
22 1,2-Diphenylethylene 0.00 0.16 1.75 2.22
23 Benzene, 1,1 -(1-methyl-1,2-ethanediyl)bis 0.00 3.89 0.59 0.00
24 Benzene, 1,1 -(1,3-propanediyl)bis 0.00 1.11 0.35 0.29
25 1,2-Diphenylcyclopropane 0.00 0.18 0.00 0.00
26 Benzene, 1,1 -(3-methyl-1-propene-1,3-diyl)bis 0.00 0.49 0.55 0.57
27 Phenanthrene 0.00 1.11 0.42 0.10
29 Benzene, 3-butynyl 0.00 4.39 0.00 0.00
30 Benzene, (1-methyl-3-butenyl) 0.00 1.21 0.32 0.05
31 Anthracene 0.00 0.13 0.96 1.39
32 Benzene, 1,1 -(3-methyl-1-propene-1,3-diyl)bis 0.00 0.18 1.07 1.18
33 1-Methylanthracene 0.00 0.02 1.08 1.38
34 Benzene, 1,1 -(2-methyl-1-propenylidene)bis 0.00 1.87 0.18 0.02
35 Benzene, (1-ethyl-2-propenyl) 0.00 0.46 0.47 0.96
36 Anthracene, 9-ethenyl- 0.00 0.87 0.12 0.09
37 o-Terphenyl 0.00 0.36 0.26 0.15
38 Naphthalene, 1,2-dihydro-4-phenyl 0.00 0.31 0.14 0.07
39 Anthracene, 9-methyl 0.00 0.31 0.13 0.02
40 2-Phenylnaphthalene 0.00 5.68 0.07 0.57
41 1-(4-Methylphenyl)-4-phenylbuta-1,3-diene 0.00 0.24 0.43 0.74
42 9-Phenyl-5H-benzocycloheptene 0.00 0.60 0.61 0.63
43 p-Terphenyl 0.00 1.35 0.27 0.15
44 m-Terphenyl 0.00 0.65 0.00 0.00
45 1,2-Propanediol, 3-benzyloxy-1,2-diacetyl 0.00 2.31 0.63 0.00
46 Di-n-octyl phthalate 0.00 0.52 0.96 1.08
47 1,1 :2 ,1 :2 .1-Quaterphenyl 0.00 0.13 1.48 1.59
48 1,1 :3,1 -Terphenyl, 5 -phenyl 0.00 1.33 2.31 0.00
Other aromatic hydrocarbons 5.84 3.00 5.08 1.08

Reaction conditions: For PS and 10PET + PS (500 °C, 60 min and feed to catalyst ratio of 1:0.2), for 20PET + PS (450 ºC, 60 min
and feed to catalyst ratio of 1:0.2) and for 30PET + PS (450 ºC, 90 min and feed to catalyst ratio of 1:0.2).

have been reported during the pyrolysis of virgin PS over acidic cata-
lysts [25]. The depolymerization of PS in the presence of PET is again
attributed to the loss of activity of catalyst that resulted in the for-
mation of dimers, trimers and oligomers with prolonged heating in
thermal pyrolysis [35]. The yield of important compounds in the case
of 10PET + PS in significant amounts is due to pyrolysis at a suffi-
ciently high temperature of 500 °C for a sufficient amount of reaction
time, which is 60 min in this case. The yield of anthracene and its
derivatives slightly increased with the increase in PET percentage.
This might be due to the interaction of styrene oligomers with the
reactive groups of PET products or further competitive interactions
between the pyrolyzed products.
The main identified components of the pyrolysis liquids are shown
in Table 4. This table shows that a small number of hydrocarbons
were formed in the case of PS pyrolysis i.e. only C6 –C18 fraction was
formed. This was also observed and reported in a previous study by
the author [20]. The addition of PET resulted in the production of
higher fractions i.e., C10 –C24 . The production of a wide spectrum of
hydrocarbons with the addition of PET on the catalytic pyrolysis of PS
resembles the thermal pyrolysis of PS reported in our previous paper
[20]. The yield of styrene monomer was dominant in all the liquids.
These yields were 62.5 wt.%, 47.0 wt.%, 59.86 wt.% and 64.31 wt.% in
the cases of PS, 10PET + PS, 20PET + PS and 30PET + PS, respectively.
Other studies have also reported the formation of styrene as a
major product during the pyrolysis of mixed plastics [16]. The ad-
dition of PET reduced the yield of benzene, toluene and ethylben-
zene, which was slightly increased with the further addition of PET
among the liquid products, comparatively. High concentrations of
ethylbenzene in all the liquid products formed in the presence of
acidic catalyst as a result of pyrolysis of styrene oligomers, which
was also reported by Marczewski et al. [25] who studied the pyrol-
ysis of PS. The insignificant yield of liquid in the addition of PET is
due to the formation of large amount of gaseous (COx and aliphatic)
products. On the other hand, the competing reaction between

Please cite this article as: Adnan et al., Effect of polyethylene terephthalate on the catalytic pyrolysis of polystyrene: Investigation of the
liquid products, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.01.015
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Adnan et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 1–7 7

cross-linking of polymers (PS and PET) and cracking at elevated to increasing concentrations of PET, the yield of these products in-
temperature might be the cause of residue. The yield of aromatic creased with the increase of PET percentage. In the presence of PET
hydrocarbons particularly benzene, toluene, ethylbenzene, styrene, the catalytic pyrolysis was accompanied with thermal pyrolysis due
α -methylstyrene, naphthalene and anthracene represent a poten- to which wide spectrum of compounds were formed. 10% PET was
tially significant route from waste plastics as an alternative source of found to have effective interaction with PS with the yield of maxi-
useful hydrocarbons, which deliver a variety of industrial applications mum liquid and component products after PS.
in the production of dyestuffs, surfactants, pharmaceutical products,
pesticides and as solvents [16]. Siddiqui and Redhwi [7] proposed the Acknowledgments
same conclusion for the primary production of aromatic hydrocar-
bons from the pyrolysis of mixed plastics. This study was supported by the Higher Education Commission
It can be seen that the component products of liquid derived of Pakistan under International Research Support Initiative Program
from the pyrolysis of virgin PS are different from those derived (IRSIP) under the grant number 1-8/HEC/HRD/2013/2807. The au-
with the addition of PET (xPET + PS). The results of Tables 2–4 thors also acknowledge the help and support of Greeshma Gadikota,
indicate significant interactions between PET and PS materials Post Doctorial Fellow at Department of Earth and Environmental En-
that contributed to the formation of new and important organic gineering, Columbia University, New York, USA.
compounds. These compounds include acetophenone, 2-buten-1-
one, 1-phenyl; diphenylmethane; ethylene, 1,1-diphenyl; biphenyl;
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Please cite this article as: Adnan et al., Effect of polyethylene terephthalate on the catalytic pyrolysis of polystyrene: Investigation of the
liquid products, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.01.015