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JTICE-920; No. of Pages 7

Journal of the Taiwan Institute of Chemical Engineers xxx (2014) xxx–xxx

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Journal of the Taiwan Institute of Chemical Engineers

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Thermo-catalytic pyrolysis of polystyrene in the presence of zinc bulk

catalysts
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: Zinc bulk catalysts (Zn, ZnO and ZnCl2) were used for the thermo-catalytic pyrolysis of EPSW and were
Received 21 January 2014 found with high activity and selectivity of products. Thermo-catalytic pyrolysis was carried out using an
Received in revised form 7 May 2014 efficient Pyrex batch reactor. Zn metal catalyst was found as the best catalyst amongst the zinc bulk
Accepted 11 May 2014
catalysts for the cost effective pyrolysis of EPSW (expanded polystyrene waste). The yield of liquid
Available online xxx
products at 450 8C, 120 min heating time and 1:0.2 feed to catalyst ratio was 96.73  0.12 wt.% with
2.47 wt.% toluene, 1.16 wt.% ethylbenzene, 47.96 wt.% styrene monomer and 1.90 wt.% a-methylstyrene. The
Keywords:
components of liquid products were separated by fractional distillation and found with further thermal
Catalytic pyrolysis
Recycling
pyrolysis in addition to cyclization and recombination reactions. During the fractional distillation, much
Resource recovery product variations were observed. High molecular weight aromatic hydrocarbons decreased with the
Polystyrene associated increase of low molecular weight aromatic hydrocarbons, particularly toluene and ethylbenzene.
ß 2014 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction ethylbenzene that are used in the production of new polymers or

Polystyrene (PS) is one of the large consuming plastics and
dispensed after use on a large scale in the US and other developing
countries. PS is used for households like toys, kitchen utensils,
coffee cups, and plates to industrial level, including insulation
material, packing material for breakable and food [1,2]. Expanded
polystyrene waste (EPSW) is a special goal of concern due its heavy
amount refusal by the public and its incredible bulk volume, which
causes environmental pollution called ‘‘white pollution’’. EPSW is
10 wt.% of the total plastic wastes, but by volume it could be 40% of
the total discarded plastics and occupy more space [2]. EPSW is
non-biodegradable, easily spread by wind and it also floats on the
surface of water bodies, demolishing the beauty of nature.
Throwing to landfill space may cause future construction cracks
of roads and buildings [3–7]. To handle polymer wastes, different
strategies have been developed, including incineration landfill
disposal, mechanical recycling and feed stock recycling. Feedstock
recycling via thermo-catalytic pyrolysis is the safe alternative to
overcome the problem and benefit the important carbon resources
into either energy sector or raw chemicals like styrene, toluene and
* Corresponding author. Tel.: +92 3339508730; fax: +92 919216652.
E-mail addresses: adnanchem@yahoo.com, adnanchem@upesh.edu.pk,
fa2358@yahoo.com (Adnan).
other substances [8–13].
In pyrolysis processes, the selection of proper reactor and
catalyst that affect the pyrolysis temperature and selectivity of
products. Various researchers worked on the pyrolysis of PS with
the effect of reactor and nature of reactor material, which include
various designs of reactors and material such as batch, autoclave
(stainless steel reactor), fixed bed, continuous flow and pressure
reactors [5,14–17]. Moreover, the addition of numerous types of
solvents, different plastic blends, additives, varying conditions and
catalysts have been reported to have its impact on the yield of
liquid products [18,19].
Huge amount of work is available on the pyrolysis of PS using
heterogeneous acidic and basic catalysts with the aim to increase
the yield and selectivity of products to a final low cost pyrolysis
method [2,20–24]. Among the acidic catalysts, the most commonly
used catalysts are zeolites like HZSM5 (acid treated Zeolite Socony
Mobil-5), activated charcoal (AC) and silica–alumina (SiO2/Al2O3),
fluid catalytic cracking (FCC) catalysts and MCM-41 (mobile
composition of matter) [25–29]. Karmore and Madras [26] worked
on the thermal pyrolysis of PS by Lewis acid i.e. aluminum chloride
(AlCl3), ferric chloride (FeCl3), boron triflouride (BF3) etherate, tin
(IV) chloride (SnCl4) in solution and reported that the pyrolysis rate
was the highest using AlCl3. Similarly, the heterogeneous basic
catalysts have also been reported. They are of good catalytic
activity for the pyrolysis of EPSW and enhance the selectivity of
component products. The common solid base catalysts are oxides

http://dx.doi.org/10.1016/j.jtice.2014.05.011
1876-1070/ß 2014 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article in press as: , et al. Thermo-catalytic pyrolysis of polystyrene in the presence of zinc bulk catalysts. J Taiwan Inst
Chem Eng (2014), http://dx.doi.org/10.1016/j.jtice.2014.05.011
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JTICE-920; No. of Pages 7
2 Adnan et al. / Journal of the Taiwan Institute of Chemical Engineers xxx (2014) xxx–xxx
of metals [20,30,31]. Ukei et al. [20] studied both heterogeneous
acid and base catalysts (metal oxides) for the pyrolysis of PS. It was
reported that among the acid and base catalysts, BaO was more
effective catalysts for the pyrolysis of PS. Tiwary et al. [32] studied
the effect of metal oxides (both alkali and transition metal oxides)
at elevated temperature and pressure using solvent.
The race of plastic pyrolysis was also continued using metals as
catalyst. Guoxi et al. [33] investigated the pyrolysis of PS using
metal powders of Al, Zn, Fe, Ni and Cu, benzene as solvent. It was
reported that the order of conversion to styrene monomer was
WPS + Al > WPS + Zn > WPS + Fe > WPS + Ni > WPS + Cu > WPS.
Hussain et al. [1] studied the pyrolysis of waste PS using Fe mesh by
microwave–metal interaction and found 80 wt.% liquid products
with rapid pyrolysis rate. It was reported that Fe not only catalyze
the reaction, but also work as a synergist. Hussain et al. [34] also
reported the co-pyrolysis of PS and Makarwal coal using Cu metal
antenna by microwave–metal interaction and obtained significant
results. Though a large amount of work is available on the
conversion of waste polymers, but most of the studies deal with
higher operating and capital cost using expensive solvents and
additives. The recent trends of metal investigation, especially of Zn
that has been reported to produce higher amounts of styrene
monomer after Al metal powder [33] and the high rate of PS
conversion using Lewis acid (AlCl3) made our interest to
investigate Zn metal, its oxide salt (ZnO) and its Lewis salt (ZnCl2)
as catalyst, which have been reported for the pyrolysis of biosludge
and kraft lignin [35–37].
The aim of the study was investigating the pyrolysis of EPSW for
best catalysts among the zinc bulk catalysts and their comparison
with literature reported studies to a final low cost pyrolysis
method with the effective catalytic activity and products
selectivity. The secondary aim of the work is to separate the
pyrolysis products.
2. Experimental
2.1. Materials and methods
EPSW was collected from local market and were used for the
pyrolysis experiments. Zn granules (99.9%), ZnO (99.0–100.5%) and
ZnCl2 (99%) were purchased from Merck KGaA 64271, Darmstadt,
Germany and were used as such for the pyrolysis of EPSW. The
pyrolysis experiments were carried out in a Pyrex batch reactor
having internal diameter 7 cm and height 22 cm and provided with
airtight lid shown in Fig. 1. The reactor was assembled in an
external electrical heating furnace coupled with temperature
controller, which could operate up to 1000 8C. The reaction
Fig. 1. Schematic diagram of the degradation assembly.
Please cite this article in press as: , et al. Thermo-catalytic pyrolysis of polystyrene in the presence of zinc bulk catalysts. J Taiwan Inst
Chem Eng (2014), http://dx.doi.org/10.1016/j.jtice.2014.05.011
temperature was measured by thermocouples that were in direct
contact with the reactor and reaction mixture. The pyrolysis
process was carried out at ambient conditions. The EPSW samples
were pretreated at 150 8C for 20 min to reduce its bulk volume by
20 times and to evolve any gases present. The EPSW samples (5 g
each) were pyrolyzed in a mixture with corresponding catalyst
(weight to weight percent ratio) without the addition of any
additives and solvents. The resultant pyrolysis products were
condensed by a water condenser and collected in a cold trap. The
pyrolysis products of EPSW were liquids, gases and residue. The
process flow of the setup is shown in Fig. 2. The deactivated
catalysts left at the bottom of the reactor were recovered by
washing several times with n-hexane and dried for 1 h at 120 8C
followed by heating at 500 8C for 5 h in the same heating assembly
[38].
2.2. Fractional distillation
After successful optimization of parameters like pyrolysis
temperature, heating time and feed to catalyst ratio, the EPSW
samples (100 g) were degraded and bulk liquid products were
collected using optimized conditions in the same pyrolysis
assembly shown in Fig. 1. The bulk liquid products were then
separated using fractional distillation in accordance with PN-81/C-
04012 on the basis of boiling point of the products. Fig. 3
demonstrates the distillation setup used in this study. The set-up
consists of almost the same assembly that were used in the
pyrolysis process with a modified reactor with the same
dimensions as mention in Section 2.1 and an additional
fractionating column fitted with thermometer. About 200 ml of
liquid products was poured in the fractionating reactor with
boiling chips to prevent bumping during the process. During the
fractional distillation temperature was continuously observed and
fractions were collected at various ranges of boiling points. Each
fraction was weighed and yield of component products was
calculated. The parent liquid products and distillates were also
Fig. 2. Schematic diagram of the fractional distillation assembly.
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Fig. 3. Process flow for the pyrolysis of EPSW and separation.
analyzed for component products using gas chromatography–
mass spectrometry (GC–MS).
2.3. Physical parameters study
The parent liquid and distillates were characterized using
different physiochemical parameters. The density (d) of both parent
liquid products and fractions was determined by standard method
using a pycnometer. The density of each sample was determined by
first weighing empty pycnometer followed by weighing filled
pycnometer with liquid products at 20 8C. The following relation of
Eq. (1) was used to calculate the density of the liquid products.
mass
Density ðdÞ ¼
volume
Refractive index (h20
D ) of the fractions were determined using
Abbe’s Refractometer (ATAGO DTM-1) at 20 8C, at first the prism of
the Refractometer was cleaned with acetone using damped cotton
and calibrated with distilled water. The measurement was
recorded up to four decimal points when the dark and bright
half circles were touching each other in the center clearly,
adjusted by adjustment knob. Using refractive index (h20
D ), density
(d20) and molecular weight of component compound predicted
the molar refraction (gM) of each substance was determined
using Eq. (2).
ðh2  1Þ M
Molar refraction ðg MÞ ¼  (2)
ðh2 þ 2Þ d
2.4. GC–MS analysis
The pyrolysis products were analyzed by Shimadzu QP2010 Plus
GC-MS. The instrument was fitted with DB-5MS (J&W Scientific)
fused silica capillary column (30 m  0.25 mm ID, 0.25 mm film
Please cite this article in press as: , et al. Thermo-catalytic pyrolysis of polystyrene in the presence of zinc bulk catalysts. J Taiwan Inst
Chem Eng (2014), http://dx.doi.org/10.1016/j.jtice.2014.05.011
3
thickness) with stationary phase of 95% dimethylpolysiloxane and
5% polyphenyl. Helium (flow rate of 1.5 ml/min) was used as the
inert carrier gas, the sample injector volume was 1 mL and the
injector temperature was 300 8C. The oven temperature was
programmed as: 35 8C (held time; 5 min), at the rate of 5 8C/min
increased to 100 8C (held time; 1 min), at the rate of 10 8C/min
increased to 150 8C (held time; 10 min) and again the temperature
was increased at the rate of 2.5 8C/min to 290 8C (held time; 10 min).
Ion source temperature: 280 8C and interface temperature: 290 8C.
3. Results and discussions
3.1. Pyrolysis of EPSW and catalytic activity studies
(1)
The thermo-catalytic experiments for the optimization of
different parameters were carried out in order to obtain maximum
amount of liquid products. The effect of pyrolysis temperature on
thermo-catalytic pyrolysis of EPSW were determined in a range of
250 8C–500 8C for all the three catalysts using 60 min heating time
and 1:0.2 feed to catalyst ratio. Results for the effect of pyrolysis
temperature are shown in Fig. 4. The pyrolysis of EPSW started
below 250 8C for the yield of gaseous product where the collection
of liquid products started at 250 8C, therefore it was the chosen
minimum temperature. Most of the reported work has been
carried out at fixed temperature either because of the limitation of
reactor (autoclave etc.) or heating assembly [32,39–41]. On the
other hand 500 8C is the adequate maximum temperature for the
optimization of maximum liquid products, which has been
reported by various researchers [7,8,42,43]. The yield of liquid
products at 250 8C was 0% with the formation of small amounts of
gaseous products. The yield of liquid products started at 350 8C in
the case of Zn metal and ZnO catalysts where it was 0 wt.% in the
case of ZnCl2 catalysts. However, the yield of gaseous product at
this temperature was more than Zn metal and ZnO catalysts. It is
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Fig. 4. Effect of temperature and comparison of liquid products yields using Zn, ZnO
and ZnCl2 catalyst (60 min heating time and 1:0.2 feed to catalyst ratio) for the
pyrolysis of EPSW.
because of the moderate Lewis character of ZnCl2, which catalyze
the polymer to yield only gaseous products (volatile light
hydrocarbons). It was confirmed by performing some additional
experiments with 10 g of feed material (feed to catalyst ratio of
1:0.05), the amount of gaseous products were almost the same
with the additional collection of 5.87  1.39 wt.% liquid products. It
was assumed that only ZnCl2 surrounded polymer molecules are
converted to gaseous products while the remaining are converting
due to thermal effects. The yield of liquid products increased with the
increase of pyrolysis temperature using constant heating time and
feed to catalyst ratio for all the three catalysts. The liquid product
yield reached to a maximum 82.93  2.00 wt.% and 84.73  2.31 wt.%
at 450 8C for the Zn and ZnO catalysts, respectively, and beyond
450 8C no significant increase was observed. The yield of liquid
products was 79.40  0.72 wt.% using ZnCl2 catalyst at 500 8C. The
total yield was 100% for all the used catalysts.
The effect of heating time on the pyrolysis of EPSW is shown in
Fig. 5. The pyrolysis experiment was carried out in 30, 60, 90, 120
Fig. 5. Effect of heating time and comparison of liquid products yields using Zn, ZnO
(450 8C and 1:0.2 feed to catalyst ratio) and ZnCl2 catalysts (500 8C and 1:0.2 feed to
catalyst ratio) for the pyrolysis of EPSW.
Please cite this article in press as: , et al. Thermo-catalytic pyrolysis of polystyrene in the presence of zinc bulk catalysts. J Taiwan Inst
Chem Eng (2014), http://dx.doi.org/10.1016/j.jtice.2014.05.011
and 150 min heating time at their respective optimized conditions
i.e. 450 8C pyrolysis temperature and 1:0.2 feed to catalyst ratio for
Zn and ZnO catalysts, and 500 8C pyrolysis temperature and 1:0.2
feed to catalyst ratio for ZnCl2 catalyst. The effect of heating time
changes the amount of products formed as well as alters
component products because of changing residence heating time.
Most of the literature reported methods have been reported with a
fixed heating time [32,40], therefore, the current method was
suggested to find the effect of heating time on the pyrolysis of
EPSW. The yield of the liquid products was increased with increase
of heating time for all the three catalysts and then with further
increase become either constant and or decreased. The decrease of
liquid products is due to the increase in residence time in the
reactor, which results inter product’s interaction and the formation
of gaseous products. The second cause is the escape of volatile
products from the liquid products receiver through the gas outlet
at a much longer time. In the case of Zn catalyst, the yield of liquid
products was increased from 30 min to 120 min, where it was
maximum i.e., 96.73  0.12 wt.% with 100% total yield. The yield of
liquid products was 84.73  2.31 wt.% and 79.40  0.72 wt.% maxi-
mum with 60 min heating time in the case of ZnO and ZnCl2 catalysts,
respectively. The total yield in case of Zn and ZnCl2 was 100%.
Catalyst nature and physical properties have a deep relation to
the activity and selectivity of products. However, feed to catalyst
ratio also plays an important role for catalytic activity and
selectivity of forming component products that has been reported
by literature [8,41]. The pyrolysis of EPSW was carried out using
the feed to catalyst ratio range of 1:0.1–1:0.5, other reaction
conditions are as follow: for Zn catalyst; 120 min heating time and
450 8C pyrolysis temperature, for ZnO catalyst; 60 min heating
time and 450 8C pyrolysis temperature, and for ZnCl2 catalysts;
60 min heating time and 500 8C pyrolysis temperature. The results
of the experiments are shown in Fig. 6. Changing the feed to
catalyst ratio in the case of Zn catalyst from 1:0.2 to 1:0.1, the yield
of liquids was 96.07  0.31 wt.% the same as with 1:0.2 feed to
catalyst ratio. No significant impact was recorded on the yield of
liquid products above 1:0.2 feed to catalyst ratio. Therefore, 1:0.2 was
chosen optimum feed to catalyst ratio. In the case of ZnO catalyst, the
yield of liquid products was 84.73  2.31 wt.% maximum with 1:0.2
and then a slight decrease was observed with the increase of catalyst
amount. In the case of ZnCl2 catalyst, the yield was 79.60  4.20 wt.%
maximum with 1:0.1 feed to catalyst ratio. The total yield was 100% at
Fig. 6. Effect of feed to catalyst ratio and comparison of liquid products yield using
Zn (450 8C and 120 min heating time), ZnO (450 8C and 60 min heating time) and
ZnCl2 catalysts (500 8C and 60 min heating time) for the pyrolysis EPSW.
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optimum conditions for all the three catalysts. The EPSW were Table 2
The list of products formed by the pyrolysis of EPSW using thermal pyrolysis, Zn,
degraded with the effect of pyrolysis temperature, heating time and
ZnO and ZnCl2 catalysts.
feed to catalyst ratio where optimum conditions were determined for
all the used catalyst for maximum conversion of EPSW into liquid Products Composition (wt.%)
products. The maximum yield of liquids was 96.07  0.31 wt.%, Thermal Zn ZnO ZnCl2
84.73  2.31 wt.% and 79.60  4.20 wt.% using Zn, ZnO and ZnCl2 Toluene 2.06 2.47 1.80 2.11
catalysts, respectively, at their respective optimized conditions. Ethylbenzene 0.85 1.16 0.60 1.93
Among the used catalysts the yield of liquids was the highest in the Styrene 39.31 47.96 41.45 40.88
case of Zn metal as catalyst. A comparative study describing reaction a-Methylstyrene 1.33 1.90 1.13 1.26
Benzene, 1,10 - 1.97 2.98 1.70 1.16
conditions and contents of products is given in Table 1 using thermal
(1,3-propanediyl)bis
pyrolysis and zinc bulk catalysts. The pyrolysis of EPSW using Zn Benzene, 3-butynyl 17.56 21.53 19.57 12.94
catalyst without the use of any solvent was found better than using Benzene (1-methyl-3- 1.16 1.57 1.02 0.59
benzene solvent [33]. The yield of liquid products of Zn catalyst was butenyl)
more than reported by Ukei et al. [20] using BaO catalyst (93.4 wt.%) 1,2-Propanediol, 3- 10.10 12.29 13.91 12.54

at 600 8C for 3 h and ZnO and ZnCl2 catalyst were also good from their
benzyloxy-1,2-diacetyl
reported acid and base catalysts due to low pyrolysis temperature and 1,10 :3,100 -Terphenyl, 50 -phenyl 0.48 0.71 0.34 0.35
small heating time. Other hydrocarbons 3.24 4.16 3.19 5.83

3.2. Catalytic selectivity studies

The pyrolysis liquid products of EPSW were analyzed by GC–MS.
The results of the analysis are given in Table 2 and are expressed in
terms of wt.% of EPSW samples. The analysis revealed that the
component products with all the three catalysts yielded nine major
aromatic hydrocarbons among which toluene; styrene monomer; a-
methylstyrene; benzene, 3-butynyl: benzene, 1,10 -(1,3-propane-
diyl)bis and 1,2-propanediol, 3-benzyloxy-1,2-diacetyl were the
major components. Like other literature reported methods, styrene
monomer in this study was also the major product with thermal
pyrolysis and as well as with zinc bulk catalysts [20,21,28]. The yield
of all the reported products was higher with Zn metal catalyst, as
compared to thermal, ZnO and ZnCl2 catalysts, except for 1,2-
propanediol, 3-benzyloxy-1,2-diacetyl, the composition of which
was high with ZnO catalyst (13.91 wt.%). Where the yield of styrene
monomer was 39.31 wt.%, 47.96 wt.%, 41.45 wt.% and 40.88 wt.%
with thermal, Zn, ZnO and ZnCl2 catalysts, respectively. The yield of
major products was maximum with Zn metal catalyst, for toluene it
was 2.47 wt.%, a-methylstyrene 1.90 wt.%, benzene, 1,10 -(1,3-
propanediyl)bis 2.98 wt.%, benzene, 3-butynyl 21.53 wt.% and 1,2-
propanediol, 3-benzyloxy-1,2-diacetyl 12.29 wt.%. In the current
study Zn metal as a catalyst was found with high activity for the
production of liquid products yielding minimum gases and residue
(Table 1) with 100% total yield as well as with high selectivity for
aromatic hydrocarbons than the other used catalysts. In thermo-
catalytic pyrolysis of polymers it produce numerous species leading
to hundreds of interactions, therefore, it is hard to divine a specific
mechanism but there are a few agreements using different types of
catalysts. A Lewis acid such as ZnCl2 catalyst detach a hydride anion
from the benzylic position in PS reported by Karmore et al. [26] and
basic catalysts like ZnO, activates PS through deprotonating with
Table 1
Reaction conditions comparison and contents of products using thermal pyrolysis,
Zn, ZnO and ZnCl2 catalysts.
Thermal Zn ZnO ZnCl2
Reaction conditions
Pyrolysis 500 450 450 500
temperature (8C)
Heating time (min) 150 120 60 60
Feed to catalyst ratio – 1:0.2 1:0.2 1:0.1
Contents of products (wt.%)
Liquids 78.07  0.64 96.73  0.12 84.73  2.31 79.60  4.20
Gases 20.40  0.72 3.27  0.12 15.27  2.31 20.40  4.20
Residue 1.53  0.61 0.00  0.00 0.00  0.00 0.00  0.00
Total yield 98.50 100 100 100
subsequent b-scission of the polymer backbone [22]. The low yield
of styrene monomer with ZnCl2 as compared to solid basic catalysts
(ZnO and Zn metal catalysts) is due to the numerous active Lewis
acidic sites causing further cracking of the styrene monomer and
hydrogenation with a competitive crosslinking reaction or side
reaction which ultimately increase the yield of gases with the
concomitant decrease of liquid product yield [20,28,40]. The yield of
styrene monomer and other component products are mostly
reported in terms of wt.% of the liquid or oil [20], while in this
study report, the yield of both liquid products and component
products in wt.% of the EPSW pyrolyzed. As a whole the selectivity of
low molecular weight aromatic hydrocarbons was better with zinc
bulk catalyst with small amount of heating time and pyrolysis
temperature without using any additive and solvent than reported
by literature [25,28], but the selectivity of styrene was smaller than
that of reported by Ukei et al. [20] and Guoxi et al. [33] and it was
because of their wt.% calculation method, high residence time,
pyrolysis temperature and use of additives or solvent, which
ultimately cause high production cost. Zn metal was found with
higher activity and selectivity for the production of low molecular
weight aromatic hydrocarbons, especially for styrene monomer
with a cost effective method.
3.3. Separation studies
Catalytic pyrolysis significantly increased the yield of liquid
products as compared to thermal cracking with remarkable
activities, where zinc bulk catalysts were also found with amazing
selectivity for desirable aromatic hydrocarbons. The effective
pyrolysis of EPSW was followed by the separation of component
products of bulk liquids using fractional distillation assembly.
Fractions were collected at various boiling point ranges i.e., (i) 70–
90 8C, (ii) 90–100 8C, (iii) 100–130 8C, (iv) 130–135 8C, (v) 135–150,
(vi) 150–250 8C, (vii) 250–310 8C, (viii) 310–340 8C, (ix) 340–
350 8C, (x) 350–360 8C, (xi) 360–380 8C and (xii) >380 8C. The
fractions were characterized using physiochemical techniques like
density (d20), refractive index (h20
D ), and molar refraction (gM) as
well as GC–MS analysis in order to identify different fractions
obtained, the results of the analysis are shown in Table 3 along
with fraction range. It was observed that during the fractional
distillation further cracking of huge molecules took place in
addition with cyclization and recombination reactions [44–46] in
the heating reactor and major variation in the products were
observed.
Each fraction separated was confirmed by the GC–MS analysis
and was found with the contamination of other aromatic
hydrocarbons in small percentage. The yield of styrene remains

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6 Adnan et al. / Journal of the Taiwan Institute of Chemical Engineers xxx (2014) xxx–xxx

Table 4

36.1155
41.8319
64.6428

68.2836
42.7477
35.6097

100.0417
Physical parameters of standards compounds.

31.83
–

–
gM Compound name Density Refractive Molar refraction
(d), g/ml index (h) (gM)

1.4967
1.5439
1.5481
1.5611

1.6151
1.4620

1.6409
1.5309
Benzene 0.873 1.5010 26.253
h25

2-Phenone, 4-hydroxy-4- 0.868 1.4970 35.802

D

–
methyl
Toluene 0.872 1.4967 31.078
d25 (g/ml)

Ethylbenzene 0.868 1.4970 35.802

0.8974
0.9835

0.9421
0.8720
0.9103
1.0033

1.0790

1.0690
Styrene 0.903 1.5460 37.177
a-Methylstyrene 0.872 1.5450 42.002
–

–
Benzene, 1,10 -(1,3-propanediyl)bis 0.984 1.5600 64.922
ZnCl2

%Age

Phenanthrene 1.130 1.7150 61.938

9.0

48.0
12.0
4.0

9.0

5.0
10.0

6.0
–

–
2-Phenylnaphthalene 1.082 1.6480 68.687
Benzene, 3-butynyl 0.936 1.5290 42.896
35.5349

64.7377

68.7928
42.8979

99.8418
36.0817
41.2620

1,2-Propanediol, 3-benzyloxy-1, 1.225 1.5420 68.393

2-diacetyl
gM

–
–

–
1,10 :3,100 -Terphenyl, 50 -phenyl 1.074 1.619 100.29
1.5463
1.5435

1.5585
1.5069

1.5670

1.6530

1.6150
h25
D

–
–

–
d25 (g/ml)

0.9144

0.9792
0.8890

0.9034
0.9905

1.0870

1.0710
Physical parameters of the fractions obtained by fractional distillation of the liquid derived from thermal, Zn, ZnO and ZnCl2 catalytic pyrolysis of EPSW.

almost constant, where benzene, 1,10 -(1,3-propanediyl)bis de-

–
–

creased using the liquid products obtained with Zn and ZnO

%Age

catalysts. The yield of styrene monomer increased from 40.88 wt.%

42.0
9.0

9.0
7.0

3.0
17.0

6.0
ZnO

–
–

to 48 wt.% and the yield of benzene, 1,10 -(1,3-propanediyl)bis

increased using the liquid product obtained with ZnCl2 catalyst.
35.6689

32.8176

100.1761
36.2280

42.7045

The yield of toluene, ethylbenzene and a-methylstyrene were

–
–

–
–
–

increased for all the liquid products. An increase in the yield of

gM

these components may be attributed to further thermal pyrolysis

1.5478
1.5523

1.5327

of higher molecular weight aromatic hydrocarbons. During

1.4970

1.6190

fractional distillation, last products obtained was 1,10 :3,100 -

h25
D

–
–

–
–
–

terphenyl, 50 -phenyl with apparent increase for all the three

d25 (g/ml)

liquids, it increased from 0.71 wt.% to 10 wt.%, 0.34 wt.% to 6 wt.%

D – refractive index, and gM molar refraction.
0.9128

0.9457
1.0337
0.8710

1.0730

and 0.35 wt.% to 6 wt.% using liquid products obtained with Zn,
ZnO and ZnCl2 catalysts, respectively. Increase in the yield of this
–
–

–
–
–

component and the formation of 2-phenylnaphthalene using

%Age

0.0

0.0
47.0
12.0

14.0
6.0

10.0

liquid products obtained with ZnCl2 catalysts might be due the

Zn

–
–

dehydrogenation/cyclization reaction [47]. From the separation

studies it is concluded that the Zn containing catalysts can be
30.93
27.18

36.45

61.52

87.88
36.07
gM

selectively used for the recovery of toluene, ethylbenzene, styrene

–

–
–

–
–

monomer and a-methylstyrene. Molar refraction of each compo-

1.5223

1.5363

1.5999

1.5273
1.5051
1.5510

nent was calculated from the measured refractive index and

h25
D

density as shown in Table 3. The data were compared with the

–

–
–

–
–

molar refraction of standards (Table 4) and found the data in close

0.9293
0.8731
0.9115
0.8770

0.9910

0.9320
(g/ml)

agreement with that of the standards.

d25

–
–

–
–

–
Thermal

(g/ml) – density, h20

%Age

51.0

35.0
1.0

2.0

6.0

3.0

4. Conclusion
–

–
–

–
–

–
range (8C)

The catalytic pyrolysis of EPSW was carried out using zinc bulk
>380
130–135
135–150
150–250
250–310
310–340
340–350
350–360
360–380
70–90
90–100

100–130
Fraction

catalysts in an efficient Pyrex batch reactor. It was found from the

catalytic activity and selectivity data that zinc bulk catalysts
enhanced the yield of liquid products and affected the formation of
Where, %Age – percentage of the fraction, d20
1,2-Propanediol, 3-benzyloxy-1,2-diacetyl

component products as compared to thermal pyrolysis, particu-

larly with Zn metal as catalysts. In comparison to thermal
pyrolysis, the catalysts decreased pyrolysis temperature and
Benzene, 1,10 -(1,3-propanediyl)bis

heating time while on the other hand it increased the yield of

liquid products from 78.07  0.64 wt.% to 96.73  0.12 wt.%. The
catalysts, not only enhanced liquid products, but also increased value
1,10 :3,100 -Terphenyl, 50 -
2-Phenylnaphthalene

added components of the liquid products including toluene,

hydroxy-4-methyl

Benzene, 3-butynyl

ethylbenzene and styrene. Overall, the zinc bulk catalysts enhanced

Compound name

a-Methylstyrene
2-Phenone, 4-

both the activity and selectivity of products. During fraction

Phenanthrene
Ethylbenzene

distillation thermal pyrolysis in addition to cyclization and recombi-

phenyl
Benzene

Toluene

Styrene

nation along with product variations was observed. The fractions

Table 3

were analyzed using physiochemical methods as well as GC–MS

characterization.

Please cite this article in press as: , et al. Thermo-catalytic pyrolysis of polystyrene in the presence of zinc bulk catalysts. J Taiwan Inst
Chem Eng (2014), http://dx.doi.org/10.1016/j.jtice.2014.05.011
G Model
JTICE-920; No. of Pages 7

Adnan et al. / Journal of the Taiwan Institute of Chemical Engineers xxx (2014) xxx–xxx 7

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Please cite this article in press as: , et al. Thermo-catalytic pyrolysis of polystyrene in the presence of zinc bulk catalysts. J Taiwan Inst
Chem Eng (2014), http://dx.doi.org/10.1016/j.jtice.2014.05.011