J. Anal. Appl.

Pyrolysis 72 (2004) 97–102

Pyrolysis of municipal plastic wastes for recovery

of gasoline-range hydrocarbons
Ayhan Demirbas∗
Department of Chemical Engineering, Selcuk University, Konya, Turkey

Accepted 2 March 2004

Available online 18 May 2004

Abstract

This paper describes non-catalytic pyrolysis of plastic waste materials. Three types of waste plastics were used in this study: polystyrene (PS),
polyethylene (PE) and polypropylene (PP). Under pyrolysis conditions, plastic wastes can be decomposed into three fractions: gas, liquid
and solid residue. The liquid products are usually composed of higher boiling point hydrocarbons. In order to obtain useful gasoline-range
hydrocarbons from the pyrolytic oil, fractional distillation is preferred for product separation. More valuable chemical raw materials including
benzene, toluene and other condensed aromatic hydrocarbons may be obtained by refining the pyrolytic oil. The results showed that waste PS
yielded higher liquid, and waste PE and PP yielded higher gaseous products. The dominant pyrolytic liquid product of PS waste was styrene.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Plastic waste; Plastic pyrolysis; Gasoline-range hydrocarbons; Re-refining; Municipal

1. Introduction formed. These pyrolytic products can be divided into a gas

In recent years the consumption of plastics has increased
drastically; as a consequence the responsible disposal of
plastic wastes has created serious social and environmen-
tal arguments [1]. Recycling and re-refining are the appli-
cable processes for upgrading of petroleum based plastic
wastes (PBPWs) by converting them into reusable products
such as gasoline and heavy oil. PBPW is a source of useful
energy (fuels) and/or chemicals and has many advantages
from an ecological point of view [2]. Possible acceptable
processes are cracking and pyrolysis. The cracking process
yields a highly unstable low-grade fuel oil which can be
acid-corrosive, tarry, and discolored along with a character-
istically foul odor.
The pyrolysis process consists of the thermal degradation
of the wastes in the absence of oxygen/air. Plastics pyrol-
ysis may provide for disposal of plastic wastes with recov-
ery of valuable gasoline-range hydrocarbons. In pyrolysis,
the polymeric materials are heated to high temperatures,
so their macromolecular structures are broken down into
smaller molecules and a wide range of hydrocarbons are
∗ Tel.: +90-462-230-7831; fax: +90-462-248-8508.
E-mail address: ayhandemirbas@hotmail.com (A. Demirbas).
fraction, a liquid fraction consisting of paraffins, olefins,
naphthenes and aromatics, and solid residues. Pyrolysis
appears to be a technique which is able to convert PBPWs
into gasoline-range hydrocarbons [3].
All human and industrial processes produce wastes, that
is, normally unused and undesirable products of a specific
process. Plastic wastes can be classified as industrial and
municipal plastic wastes (MPWs) according to their origins;
these groups have different qualities and properties and are
subjected to different management strategies. The municipal
solid waste (MSW) products include paper, containers, tin
cans, plastics, aluminum cans, and food scraps, as well as
sewage. MPWs normally remain a part of MSWs as they are
discarded and collected as household wastes. Plastics usually
account for about 7% of the total MSW by weight and much
more by volume. In order to recycle MPWs, separation of
plastics from other household wastes is required. The waste
products of industry and commerce include plastic, paper,
wood, and metal scraps, as well as agricultural waste prod-
ucts [4]. Table 1 shows the contents of municipal solid waste.
There are four major methods for conversion of organic
wastes to synthetic fuels: (1) hydrogenation; (2) pyrolysis;
(3) thermal and/or catalytic cracking, (4) gasification: and
(5) bioconversion [5,6].

0165-2370/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2004.03.001
98 A. Demirbas / J. Anal. Appl. Pyrolysis 72 (2004) 97–102
Table 1
Contents of municipal solid waste (wt.% of total)
Component Lower limit
Paper waste 33.2
Food waste 18.3
Plastic matter 7.8
Metal 7.3
Glass 8.6
Textile 2.0
Wood 1.8
Leather and rubber 0.6
Miscellaneous 1.2
Literature reports several papers on pyrolysis of plastics
[1,7–16]. The decomposition of a polymer mixture over
HZSM-5 and orthophosphoric acid modified (PZSM-5) zeo-
lite catalysts has been comparatively studied [10]. Catalytic
decomposition increased the amount of gaseous products,
lowered the condensate, and changed their composition with
respect to the non-catalytic at the same pyrolysis temper-
ature. The gaseous products contained a large C3 fraction,
while the liquid products contained mainly aromatic hydro-
carbons.
The influence of zeolite catalytic upgrading of the py-
rolysis gases derived from the pyrolysis of polyethylene
has been investigated [11]. The polyethylene was pyrol-
ysed at 775 K. Polyethylene was pyrolysed in a fixed bed
reactor and the pyrolysis gases passed to a secondary re-
actor containing Y-zeolite or zeolite ZSM-5 catalyst. The
oils consisted of mainly aliphatic compounds represented
by alkadiene, alkene and alkane hydrocarbons and their
branched chain derivatives. The Y-zeolite produced signifi-
cantly greater concentration of aromatic hydrocarbons in the
derived oils compared to when zeolite ZSM-5 catalyst was
used. Plastics wastes are converted into synthesis gas. The
crude synthesis gas is injected into exhausted oil reservoirs.
In this way atmospheric pollution is avoided. The oil reser-
voir has filtering capacities [12]. Plastic waste has become
an increased problem in many industrialized countries. Con-
cern over the volumes being created has lead to a number
Fig. 1. Simplified experimental device for plastic waste pyrolysis. (1) Digital balance, (2) temperature transmitter, (3) thermocouple, (4) external heater,
(5) steel reaction vessel, (6) ice baths, and (7) collection vessels for liquid products.
of governments introducing new legislation for its recovery
as a resource.
Upper limit Traditional recovery methods have generally concentrated
50.7
on recycling of materials or incineration for energy [13].
21.2 Pyrolysis is a tertiary recycling process and has an ability
11.2 to provide three end products: a gas, oil and a solid residue
10.5 which all have the potential to be further utilized [14]. The
10.2 polyvinylchloride (PVC) waste was pyrolyzed at 911, 963
2.8
2.9
and 1008 K in a technical-scale fluidized bed reactor [15].
1.0 At 911 K over 50 wt.% of the pyrolysis product was oil with
1.8 a boiling point less than 538 K. The experiment at 963 K
yielded about 40 wt.% of an oil, about the half of which
consists of benzene, toluene and xylene (BTX). At the high-
est pyrolysis temperature of 1008 K, the main product was
highly aromatized oil; the BTX-aromatics content is about
20 wt.% of the pyrolysis product.
The numerical simulations of the linear pyrolysis of
cellulosic and polyethylene waste were investigated [16].
The most common test method for cracking is described in
ASTM D-1693 “Standard Test Method for Environmental
Cracking of Ethylene Plastics.”
2. Experimental
Three types of waste plastics were used in this study.
Polystyrene (PS), polyethylene (PE) and polypropylene (PP)
wastes were collected from landfill in the form of cattery.
They were shredded into 3 mm × 5 mm size. In order to
assess the thermal behavior of the plastic samples, thermo-
gravimetric analysis (TGA) and pyrolysis runs were car-
ried out. For thermogravimetric analysis, Netzch 429/409
thermal analyzer was used. Isothermal conditions and a
controlled heating program of 10 K/min were used. The
heating was carried out from 298 to 1025 K in nitrogen
stream.
The pyrolysis experiments were carried out in a stain-
less steel tube with height 76.4 mm, i.d. 17.0 mm and o.d.
19.0 mm. A schematic representation of the apparatus used is
shown in Fig. 1. Plastic sample was weight for run 1.00 g and
 A. Demirbas / J. Anal. Appl. Pyrolysis 72 (2004) 97–102 99

pyrolyzed in the tube. Heat to tube was supplied from exter- Table 2
nal heater and the power was adjusted to give an appropriate Product distribution in plastic pyrolysis (wt.% of waste)
heat up time. The simple thermocouple (NiCr–Constantan) Waste Pyrolysis Gas Oil Residue Other
was placed directly in the pyrolysis medium. For each run, temperature
the heater was started at 298 K and terminated when the de- (K)
sired temperature. Polyethylene (PE) 1033 55.8 42.4 1.8 –
Polypropylene (PP) 1013 49.6 48.8 1.6 –
The pyrolysis products were collected within three dif-
Polystyrene (PS) 854 9.9 24.6 0.6 64.9 styrene
ferent groups as non-condensable gaseous products, con- Mixture PE/PP/PS 1023 52.0 46.6 1.4 –
densables as tarry liquids and wax degradation products and
Source: Ref. [23].
solid residue. The products were analyzed mainly in liquid
state using a Fisons Ins. gas chromatograph (model GC
8000) equipped with a flame ionization detector, 30 m long, proposed [21]:
and 0.25 i.d. ZB-625 capillary column. Some chromato-
graphic analysis of the gaseous products was also made. (1) End-chain scission or depolymerization.
(2) Random-chain scission.
(3) Chain-stripping.
(4) Cross-linking.
3. Results and discussion
Different mechanisms are to some extent related to bond
PE and PP are the main components of MPWs. The ther- dissociation energies, the chain defects of the polymers, and
mogravimetric (TG) curves for PE, PP and PS wastes are the aromaticity degrees, as well as the presence of halogen
depicted in Fig. 2. The TG behaviors of PE and PP are sim- and other hetero-atoms in the polymer chains [1]. The py-
ilar, but PS is different. The behavior of PE or PP and PS rolysis of PS occurs by both end-chain and random chain
shows one main distinct weight loss step, which show that scission and the monomer recovery is only some 45% [22].
both of them have a constant degradation behavior at the PS thermal degradation is a radical chain process including
involved temperature range. Degradation finished between initiation, transfer and termination steps [8]. The product
720 and 760 K for the plastic wastes. The differences in TG distribution from PS pyrolysis depends on initial molecular
curves could obviously be attributed to the macromolecular weight (MW) of the PS sample [9]. While initial MW in-
structure and pyrolysis mechanism. creases from 2200 to 50,000 the yield of styrene increases
Pyrolysis of plastics has been studied extensively from 67 to 78 wt.%. The pyrolysis of PE and PP occurs
in the past [17,18]. Conversion of plastic wastes into through the random-chain scission mechanism and a whole
gasoline-range hydrocarbons via pyrolysis in the absence spectrum of hydrocarbon products is obtained [17]. PE
of a catalyst has been reviewed by Kaminsky [19,20]. thermal degradation consists of free radical formation and
Four types of mechanisms of plastics pyrolysis have been hydrogen abstraction steps [8]. Table 2 shows the product

Fig. 2. TGA curves of PE, PP and PS wastes. Heating rate: 10 K/s.

100 A. Demirbas / J. Anal. Appl. Pyrolysis 72 (2004) 97–102

Fig. 3. Curves for yield distributions of pyrolytic products from municipal solid waste. Heating rate: 10 K/s.

distribution in plastic pyrolysis [23]. The residual products
from plastic pyrolysis are very low.
The yield distributions of the pyrolytic products from mu-
nicipal solid waste are given in Fig. 3. From Fig. 3, the
yields of gaseous products increase with increasing pyrolysis
temperature. The yields of liquid products increase with in-
creasing pyrolysis temperature up to 675 K and then slightly
decrease from 675 to 850 K. Fig. 4 shows the yields of the
gaseous products from pyrolysis of municipal solid waste.
Individual yield of each gas product with increasing pyrol-
ysis temperature is irregular.
The yield distributions of the pyrolytic products from
municipal plastic waste are given in Fig. 5. As seen from
Fig. 5, the yields of gaseous products increase from 12.3 to
42.4 wt.% with increasing pyrolysis temperature from 550
to 900 K. The yields of liquid products increase with in-
creasing pyrolysis temperature up to 750 K and then slightly
decrease with temperature increasing from 750 to 900 K.
The yield distributions of the pyrolytic products obtained
from PS at different temperatures are shown in Table 3. From
Table 3, the yields of styrene increase from 56 to 64% with
increasing pyrolysis temperature from 650 to 750 K and then
decrease from 64 to 49.6% with increasing pyrolysis tem-
perature from 650 to 875 K. While pyrolysis temperature in-
creases from 650 to 875 K the yield of C2 –C4 hydrocarbons
increases from 3.8 to 22.5 wt.%.

Fig. 4. Curves for yields of the gaseous products from pyrolysis of municipal solid waste.
 A. Demirbas / J. Anal. Appl. Pyrolysis 72 (2004) 97–102 101

Table 3
Yields of the products obtained by PS pyrolysis at different temperatures (K)
Compound 650 675 700 725 750 800 875

Styrene 56.2 58.0 59.5 61.8 64.6 58.2 49.6

C2 –C4 hydrocarbons 3.8 3.4 4.6 4.9 6.2 13.8 22.5
C5 –C8 hydrocarbons 21.4 19.0 17.2 15.8 10.3 10.5 9.5
Methane 7.1 7.5 6.8 7.4 8.2 7.0 6.8
Toluene 6.2 6.8 6.4 7.3 7.1 6.7 6.0
Benzene 5.3 5.3 5.5 4.6 3.6 3.8 5.6

Table 5
Yields of the products obtained by PP pyrolysis at different temperatures
(K)
Fraction 675 725 800 875
Total-paraffin 30.4 28.2 24.9 29.6
Total-olefin 44.7 42.1 39.5 35.5
Naphthene 21.5 22.8 24.4 23.5
Aromatics 1.4 4.5 8.6 10.2
Others 2.0 2.4 2.6 1.2

increases from 675 to 875 K the yield of total-olefin fraction

Fig. 5. Curves for yield distributions of pyrolytic products from municipal
plastic waste. Heating rate: 10 K/s.
The yield distributions of the pyrolytic products obtained
from PE at different temperatures are shown in Table 4. From
Table 4, while pyrolysis temperature increases from 675 to
875 K the yield of total-paraffin fraction increases from 35.6
to 44.2 wt.%. While pyrolysis temperature increases from
675 to 875 K the yield of total-olefin fraction decreases from
42.6 to 32.6 wt.%.
Table 5 shows the yield distributions of the pyrolytic
products obtained from PP at different temperatures. From
Table 5, while pyrolysis temperature increases from 675 to
875 K the yield of total-olefin fraction decreases from 44.7
to 35.5 wt.%. While pyrolysis temperature increases from
675 to 875 K the yield of aromatics fraction increases from
1.4 to 10.2 wt.%.
Table 6 shows the yield distributions of the pyrolytic prod-
ucts obtained from municipal plastic waste at different tem-
peratures. As seen from Table 6, while pyrolysis temperature
decreases from 37.3 to 31.6 wt.%. While pyrolysis tempera-
ture increases from 675 to 725 K the yield of aromatics frac-
tion increases from 7.9 to 13.6 wt.% and then it decreases to
11.6 wt.% with increasing temperature to 875 K. Relation-
ships between temperature and the yields of total-paraffin
and naphthene are irregular.
The pyrolysis of plastic wastes produces a whole spec-
trum of hydrocarbons including paraffins, olefins and aro-
matics. The total yields of paraffins and olefins of PE and
PP wastes obtained by pyrolysis are higher than that of
PS. However, hydrocarbons from plastic pyrolysis are not
suitable for gasoline usage. Gasoline qualities are usually
measured in terms of volatility and octane number of the
hydrocarbons. Adequate volatility is required for smooth
operation of petrol engines. Light hydrocarbons (LHs) have
higher volatilities than those of heavy hydrocarbons (HHc).
LHs may cause vapor lock when the engine is hot. HHs may
not be volatile enough to start the engine when the engine
is cold. Suitable hydrocarbons are in the C5 –C8 range.
Octane number a measure of the gasoline quality for pre-
vention of early ignition which leads to cylinder knocks.
Higher octane numbers are preferred in internal combus-
tion engines. For gasoline production, aromatics, naphthenes
and isoalkanes are highly desirable, whereas olefins and
n-paraffins are less desired.

Table 4 Table 6
Yields of the products obtained by PE pyrolysis at different temperatures Yields of the products obtained by municipal plastic waste pyrolysis at
(K) different temperatures (K)
Fraction 675 725 800 875 Fraction 675 725 800 875
Total-paraffin 35.6 39.8 43.7 44.2 Total-paraffin 32.5 31.4 31.1 33.2
Total-olefin 42.6 38.9 34.8 32.6 Total-olefin 37.3 33.6 32.3 31.6
Naphthene 19.6 18.5 17.6 17.2 Naphthene 20.7 21.5 23.0 22.7
Aromatics 5.8 1.7 3.5 5.8 Aromatics 7.9 13.6 12.5 11.6
Others 1.4 1.1 0.4 0.2 Others 1.6 1.9 1.1 0.9
102 A. Demirbas / J. Anal. Appl. Pyrolysis 72 (2004) 97–102
4. Conclusion
Municipal plastic wastes may be converted into gasoline-
range hydrocarbons by pyrolysis processes. Municipal solid
wastes are extremely heterogeneous and separate disposal is
required in the household in order to collect plastic wastes
in large quantities. Environmental issues include for exam-
ple dioxin formation in MSW incineration. The effects of
different plastic additives presented in the plastic wastes on
the gasoline quality from pyrolysis process are unclear.
More tests are needed to verify the pyrolysis process in
a pilot scale particularly for treatment of mixtures of bulk
plastics. Sometimes the chlorine content of PE wastes can
reach as high as 10 wt.%. The gasoline product from plas-
tics pyrolysis may have unacceptable high chlorine content,
so dechlorination and neutralization processing may be nec-
essary on some occasions. Currently, due to the moderate
oil prices, pyrolysis process is not likely to be econom-
ically competitive. However, environmental considerations
may hasten the industrial implementation of pyrolysis pro-
cess in the near future.
The liquid products from plastic wastes could thus be
considered as a mixture of heavy naphtha (C7 –C10 ), gasoline
(C8 –C10 ) and light gas oil (C10 –C20 ) fractions. The gaseous
products typically contain C1 –C4 paraffinic hydrocarbons
with some olefins. As such, most of the liquid products
formed would be ideally suited to further processing in a
petrochemical refinery, with the gases used directly as fuels.
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