Journal of Analytical and Applied Pyrolysis

63 (2002) 29 – 41
www.elsevier.com/locate/jaap

Catalytic pyrolysis of polyethylene

Ranbir Bagri, Paul T. Williams *
Department of Fuel and Energy, The Uni6ersity of Leeds, Leeds LS2 9JT, UK

Received 21 November 2000; accepted 2 March 2001

Abstract

The influence of zeolite catalytic upgrading of the pyrolysis gases derived from the
pyrolysis of polyethylene has been investigated. The yield and composition of the derived
hydrocarbon gases and oils have been investigated in terms of the temperature of the
catalyst. Polyethylene was pyrolysed in a fixed bed reactor and the pyrolysis gases passed to
a secondary reactor containing Y-zeolite or zeolite ZSM-5 catalyst. The polyethylene was
pyrolysed at 500°C and the temperature of the catalyst bed was 400, 450, 500, 550 or 600°C.
The oils consisted of mainly aliphatic compounds represented by alkadiene, alkene and
alkane hydrocarbons and their branched chain derivatives. The uncatalysed pyrolysis oil also
contained low concentrations of aromatic hydrocarbons. After catalysis there was a marked
increase in the concentration of aromatic compounds in the oil, which further increased in
concentration as the temperature of catalysis was raised. The single ring compounds
consisted of mainly toluene, ethylbenzene and xylenes and the two and three ring compounds
were mainly, naphthalene and phenanthrene and their methyl derivatives. The Y-zeolite
produced significantly greater concentration of aromatic hydrocarbons in the derived oils
compared to when zeolite ZSM-5 catalyst was used. © 2002 Elsevier Science B.V. All rights
reserved.

Keywords: Zeolite; Catalyst; Xylenes

1. Introduction

It is estimated that 100 million tonnes of plastics are produced world-wide each
year, with 24 million tonnes produced in Europe and 30 million tonnes in the
USA. The waste arising from this expanding use of plastics is enormous, yet only

* Corresponding author. Fax: + 44-113-2440572.

E-mail address: p.t.williams@leeds.ac.uk (P.T. Williams).

0165-2370/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 5 - 2 3 7 0 ( 0 1 ) 0 0 1 3 9 - 5
30 R. Bagri, P.T. Williams / J. Anal. Appl. Pyrolysis 63 (2002) 29–41

a small percentage is recycled, whilst the large majority is landfilled or incinerated

[1]. In addition, recycling is generally used only to produce low grade plastic
products, such as, sewer pipes, plastic fencing, industrial plastic pallets, traffic
cones, playground equipment and garden furniture.
The low-grade uses for recycled plastics have encouraged research into alternative
processing methods to produce higher value products. Pyrolysis of plastic waste has
been proposed as a tertiary or feedstock recycling route where the plastic waste
materials are processed to produce an oil feedstock for the petrochemicals industry
[1]. The oil may be used as a feed for a petroleum refinery catalytic cracker in the
manufacture of gasoline. Alternatively, the oil may act as a feedstock for the steam
cracker in the production of ethene and other alkenes which are used to make new
plastics. A number of plastics pyrolysis pilot plants and demonstration schemes
have been developed world-wide [1– 3].
Further developments in the process of feedstock recycling of plastics have
included the use of catalysts. The use of a catalyst has been proposed as a way of
producing a high aromatic product for the production of gasoline or as a chemical
feedstock or for the production of speciality chemicals [1– 5]. For example, Lin et
al. [5] found that the use of catalysts could reduce the required reaction tempera-
ture, improve the yield of volatile products and provide selectivity in the product
distributions. Zhao et al. [6] found that catalyst type altered the temperature of
thermal degradation of the plastic and could also be used to define the composition
of the derived hydrocarbon product. Williams et al. [3] pyrolysed polystyrene and
found that the influence of the catalyst was to markedly increase the concentration
of polycyclic aromatic hydrocarbons in the derived pyrolysis oil. Mordi et al. [7]
pyrolysed a number of plastic types over a zeolite ZSM-5 catalyst and showed that
the use of a catalyst increased the aromatic content of the derived products.
It can therefore be seen that catalysts can be used to increase the aromatic
content of the derived products from the pyrolysis– catalysis of plastics and thereby
perhaps enhance the economic potential of the process. However, there are less data
on the detailed analysis of the range and composition of the aromatic compounds
derived from the pyrolysis– catalysis process. This paper reports on the fixed bed
pyrolysis of polyethylene coupled with the catalytic upgrading of the hydrocarbon
products. Two catalysts were compared, Y-zeolite and zeolite ZSM-5 catalysts and
the temperature of the catalyst was also investigated. The derived oils and gases
were analysed in detail to determine the influence of process conditions on the
aromatic and polycyclic aromatic hydrocarbons in the derived products.

2. Materials and methods

The plastic used to investigate the influence of pyrolysis/catalytic upgrading was

low density polyethylene (LDPE), obtained from BP Chemicals, Grangemouth,
UK. The samples were virgin plastics of 2–3 mm diameter pellets.
Zeolite ZSM-5 and Y-zeolite were used and obtained from BDH (UK). The
cation present in the zeolite structure was hydrogen (H-ZSM-5). The Y-zeolite had
 R. Bagri, P.T. Williams / J. Anal. Appl. Pyrolysis 63 (2002) 29–41 31

a larger pore size and higher surface area compared to the ZSM-5 catalyst. The
pore size is significant in determining the size of the reactants and products, which
can enter and leave the active sites of the catalyst. Table 1 shows the characteristics
of the two zeolites with the data supplied by the manufacturer.
The fixed bed reactor was in two parts, a pyrolysis reactor and a catalyst reactor,
both constructed of stainless steel and separately heated externally by electric ring
furnaces. Thermocouples were used to measure the temperature throughout the
reactors. The pyrolysis reactor had an internal diameter of 37 mm and a height of
250 mm. The reactor was continually purged with nitrogen carrier gas at 200 ml
min − 1 which gave a maximum residence time of  30 s in the pyrolysis reactor and
10 s in the catalyst reactor. A stainless steel crucible was used to hold the plastic
feed in the pyrolysis reactor. The crucible was placed inside the reactor and held
there with a metal gauze. Pyrolysis was carried out in batches and a slow heating
rate of 10°C min − 1 was used to a final temperature of 500°C and held at that
temperature for 20 min to ensure complete pyrolysis. The catalyst reactor was
attached directly to the pyrolysis reactor so that the pyrolysis gases generated were
passed directly over the fixed catalyst bed. The relatively long residence times of
gases in each reactor and the separate heating regimes ensured that distinctly
separate temperatures in each reactor were maintained. The zeolite was placed in
the lower part of the reactor and held in place and away from the exit of the reactor
with a gauze. The condenser system consisted of a water cooled catchpot followed
by a series of glass condensers filled with glass wool cooled by CO2/acetone to trap
the volatile hydrocarbons. A 100 l Tedlar gas bag was used to collect all the gaseous
product. Exactly 10 g of catalyst was placed in the catalyst reactor and the catalyst
was maintained at the fixed bed temperatures of 400, 450, 500, 550 or 600°C. After
each experiment, the catalyst was removed and the formation of coke was deter-
mined by the difference in mass before and after catalytic regeneration. The
condenser system was weighed before and after the experiment to determine the
total oil yield. Oil from all the condensers was combined for analysis. A schematic
diagram of the reactor system is shown in Fig. 1.
The gas collected in the gas bag was analysed for hydrocarbon and non-hydro-
carbon gases. A Pye Unicam gas chromatograph with nitrogen carrier gas was used
to detect hydrocarbons ranging from C1 to C4 by Flame Ionisation detection (FID).

Table 1
Characteristics of the ZSM-5 and Y zeolite catalysts

Catalyst property ZSM-5 Y-Zeolite

Particle size (mm) 2 2

Pore size (m−10) 5.5 7.4
Pore volume (m−3 kg−1) 0.48 0.64
Surface area (m2 g−1) 300 440
Bulk density (kg m−3) 0.72 0.61
Silica: alumina ratio 50 11
Support Clay binder Clay binder
32 R. Bagri, P.T. Williams / J. Anal. Appl. Pyrolysis 63 (2002) 29–41

Fig. 1. Schematic diagram of reactor system.

A Pye Unicam 204-series gas chromatograph with argon carrier gas and thermal
conductivity detector was used to analyse nitrogen, hydrogen, oxygen, carbon
monoxide and carbon dioxide content from the collected gas sample.
The oils derived from the pyrolysis and catalytic pyrolysis of polyethylene were
analysed in detail for their content of aliphatic and aromatic compounds. The oils
were separated by liquid chromatography into chemical class fractions followed by
gas chromatography/flame ionisation detection and confirmation of identification
by gas chromatography/mass spectrometry. The liquid chromatography consisted
of 10×1 cm glass columns packed with 5.0 g silica, Bondesil (sepralyte) sorbent,
pre-treated at 105°C for 2 h prior to use. To enable efficient contacting with the
silica gel, the sample was dissolved in hexane and added to the analytical phase.
The column was then sequentially eluted under vacuum with hexane, benzene and
methanol to produce, aliphatic, aromatic and polar fractions respectively. Analysis
using gas chromatography/mass spectrometry and Fourier transform infra-red
spectrometry confirmed that these were the compositions of each fraction.
The fractions were analysed by capillary column gas chromatography with flame
ionisation detection and also compound identifications for aromatic species were
confirmed by gas chromatography/mass spectrometry. Identification was also by
 R. Bagri, P.T. Williams / J. Anal. Appl. Pyrolysis 63 (2002) 29–41 33

the extensive use of relative retention indices [8] and the use of internal standards
and response factors. The gas chromatograph/flame ionisation system was a Carlo
Erba 3500 chromatograph with cold on-column injection. The capillary column was
a HT-5 type, 25 m long × 0.32 mm internal diameter, high temperature, fused
silica, aluminium coated column with a 5% Phenyl Polycarborane-Siloxane station-
ary phase. The high temperature column enabled oven temperatures of 400°C to be
used which ensured that hydrocarbons up to C60 could be analysed. The tempera-
ture programme was 40°C for 8 min followed by a 5°C min − 1 heating rate to
400°C and dwell time of 20 min at 400°C. The mass spectrometer used for
confirmation of aromatic species was of the bench top ion trap detector type
manufactured by Finnigan-MAT. The ion trap detector had a mass range from 20
to 650 u with scan times between 0.125 and 2 s and it was linked to a computer
with a library containing 38752 mass spectra. The capillary column was a DB5 and
the temperature programme was 60°C for 2 min followed by a 5°C min − 1 heating
rate to 270°C.

3. Results and discussion

3.1. Product yield

Fig. 2 shows the product yields (product distribution) obtained from the pyroly-
sis of polyethylene with various Y zeolite bed temperatures. Pyrolysis at 500°C in
the absence of any catalyst produced a yield of 95 wt.% oil, negligible char and low
gas yield. Similar yields have been found by Isoda et al. [4]. In the presence of the
Y-zeolite catalyst, the oil yield was reduced to 85 wt.%. As the zeolite bed
temperature was increased, the gas yield increased with a consequent decrease in oil

Fig. 2. Product yields obtained from the pyrolysis of polyethylene using a fixed bed with various Y
zeolite bed temperatures.
34 R. Bagri, P.T. Williams / J. Anal. Appl. Pyrolysis 63 (2002) 29–41

Fig. 3. Product yields obtained from the pyrolysis of polyethylene with various ZSM-5 zeolite bed
temperatures.

yield. Other workers have also found a higher yield of hydrocarbon gases and a
decreased yield in oil after catalytic pyrolysis of polyethylene [10,11]. Coke forma-
tion on the catalyst showed a small decrease as the catalyst temperature was
increased. The pyrolysis of polyethylene in the absence of a catalyst produces no
residual carbon [9] and obviously no catalyst coke. Coke formation on zeolite
catalysts has largely been attributed to the reactions of asphaltenes, aromatic
compounds and alkenes [12]. Alkenes would certainly be in high concentration in
the pyrolysis products from the pyrolysis of polyethylene. In addition, Ono et al.
[13] found that the amount of coke was higher for lower temperatures of catalysis,
as was suggested, but not clearly demonstrated, in this work. Venuto and Habib
[12] also showed that coke formation was reduced as the catalyst temperature was
increased from 480 to 590°C for the zeolite catalytic cracking of petroleum. They
also showed that the gas yield, particularly alkene gases also increased with catalyst
temperature with a corresponding decrease in the yield of light oil.
Fig. 3 shows the product yields obtained from the pyrolysis of polyethylene with
varying ZSM-5 zeolite bed temperatures. The oil yield showed a reduction to 88
wt.% similar to that found with the Y-zeolite and showed a similar reduction in oil
yield and increase in gas yield with increasing catalyst temperature. Coke formation
on the catalyst showed a slight decrease with increasing catalyst temperature.
Sharratt et al. [10] carried out catalytic pyrolysis of high density polyethylene using
ZSM-5 zeolite and found that increasing the reaction temperature from 290 to
430°C, increased the gas yields, whereas the oil yields decreased. In addition, they
found that the coke yield remained virtually constant. Other workers have sup-
ported these findings by showing an increase in gas yields after catalytic degrada-
tion of polyethylene [14,15].
 R. Bagri, P.T. Williams / J. Anal. Appl. Pyrolysis 63 (2002) 29–41 35

3.2. Gas composition

Fig. 4 shows the gas yields obtained from the pyrolysis of polyethylene with
increasing Y zeolite bed temperature. It was found that propane and iso-butane
were the dominating alkane gases at low Y zeolite bed temperatures, yet at high bed
temperatures, propane and methane dominated the alkane gas yield. For the alkene
gases, it was evident that propene and ethene yields increased with increasing Y
zeolite bed temperature, whereas butene derivatives remained fairly constant.
Butene derivatives consisted of cis-butene, trans-butene and butadiene gases. The
yield of alkane gases were generally higher than the alkene gases. Many workers
have detected the presence of C1 – C4 hydrocarbon gases after thermal and catalytic
cracking of polyolefins [4,10,16].
Fig. 5 shows the gas yield from the pyrolysis of polyethylene with various zeolite
ZSM-5 bed temperatures. Propane was the highest alkane gas produced and
methane, ethane and propane gas yields increased with increasing zeolite bed
temperature. Isobutane and n-butane were in low concentration. The alkene gases
consisted of butene derivatives, ethene and propene. Propene and ethene dominated
the alkene gases, more so at higher zeolite bed temperature. At the high zeolite bed
temperatures, the alkene gases dominated the gas yields. Comparison of the
influence of the two catalysts shown in Figs. 4 and 5 shows that the ZSM-5 zeolite
catalyst produced a much high yield of gas compared to the Y-zeolite catalyst.

Fig. 4. Gas yield from the pyrolysis of polyethylene with various Y zeolite bed temperatures.
36 R. Bagri, P.T. Williams / J. Anal. Appl. Pyrolysis 63 (2002) 29–41

Fig. 5. Gas yield obtained from the pyrolysis of polyethylene with various ZSM-5 zeolite bed
temperatures.

3.3. Oil composition

The condensed oil samples were analysed for their aliphatic content and for their
content of aromatic and polycyclic aromatic hydrocarbons (PAHs). It was found
that the product oils from uncatalysed and catalysed experiments contained a large
amount of aliphatic compounds ranging from C9 to C50. In addition, aliphatic
compounds were in a distinct pattern of a series of triplet peaks as has been
previously shown for the derived oil from the thermal degradation of polyethylene
analysed by gas chromatography [17]. The triplets were identified as being alkadi-
ene, alkene, and alkane compounds [17]. In the presence of the catalysts, the
concentration of aliphatic compounds decreased and the carbon number distribu-
tion shifted to lower values, whilst still maintaining the distinctive set of triplet
peaks. Other workers have found that thermal and catalytic pyrolysis of polyolefins
produced oils, which contained alkane and alkene compounds and also showed a
shift in carbon numbers from high to low values [10,16,18]. For example, Ding et
al. [18] found that thermal degradation of polyethylene gave products with a carbon
number distribution of C1 – C27 and above, whereas catalytic cracking of
polyethylene gave products with an approximate distribution of C1 –C17.
Analysis of the aromatic fraction of the uncatalysed polyethylene pyrolysis oils
produced at 500°C pyrolysis temperature and the catalysis–pyrolysis oils with
Y-zeolite are shown in Tables 2 and 3. A range of single ring and polycyclic
aromatic hydrocarbons in the oils are shown in Table 2 and detailed analysis and
quantification of certain of the polycyclic aromatic hydrocarbons are shown in
Table 3. Table 4 shows the analysis of single ring and polycyclic aromatic
hydrocarbons and Table 5 shows certain polycyclic aromatic hydrocarbons in the
 R. Bagri, P.T. Williams / J. Anal. Appl. Pyrolysis 63 (2002) 29–41 37

oils derived from the zeolite ZSM-5 catalytic pyrolysis of polyethylene. Also shown
again in Tables 4 and 5 are the aromatic hydrocarbons found in the uncatalysed
pyrolysis oils. The uncatalysed oil contained minor concentrations of aromatic and
polycyclic aromatic hydrocarbons compared to the catalysed pyrolysis oils. How-
ever, in the presence of both the Y-zeolite and the ZSM-5 zeolite catalysts there was
a marked increase in the aromatic content of the derived oils. In addition, for both
catalysts there was a further marked increase in aromatic concentration with
increasing temperature of pyrolysis. For the Y-zeolite more than half of the total
aromatic content consisted of toluene and ethylbenzene.
Tables 3 and 5 show that most of the polycyclic aromatic hydrocarbons consisted
of naphthalene, phenanthrene and pyrene derivatives in addition to minor concen-
trations of biphenyl, fluorene and chrysene and their derivatives. It was also
apparent that the concentrations of polycyclic aromatic hydrocarbons consisted
mostly (at least 80%) of two ring aromatic hydrocarbons. The tri- and tetra- methyl
derivatives of naphthalene and phenanthrene showed a decrease in concentration
with increasing bed temperature for the Y-zeolite catalyst. However, the mono- and
di-methyl naphthalenes and phenanthrenes showed a distinct increase in concentra-
tion as the catalyst bed temperature was increased. It was clear that less branched
aromatic hydrocarbons were increasing whereas higher branched aromatics are
decreasing in concentration, with increasing Y zeolite bed temperature. However,
this trend was not found with the ZSM-5 zeolite where the tri- and tetra-methyl
naphthalenes and phenanthrenes as well as the mono-and di-methyl derivatives all
showed an increase with increasing catalyst bed temperature (Table 5).
Several workers have studied the catalytic thermal degradation of polyalkenes
using zeolite catalysts and also found aromatic hydrocarbons present in the product
oil samples [4,5,19– 23]. For example, Mordi et al. [7] carried out catalytic degrada-
tion of polyethylene and found that the oil contained benzene, toluene, para/meta/

Table 2
Total aromatic content present in the product oils from the Y-zeolite catalytic pyrolysis of
polyethylene (wt.%)

No catalyst (°C) Y-zeolite bed temperature (°C)

500 400 450 500 550 600

Toluene 0.01 3.16 4.58 7.93 8.95 12.96

Ethylbenzene 0.01 5.60 5.97 8.13 7.64 11.38
Xylenes 0.03 2.73 2.53 3.10 2.64 4.47
Single ring aromatics 0.10 2.05 4.01 4.00 4.15 3.85
(Excluding toluene, ethylbenzene, xylenes)
Two ring aromatics 0.16 1.10 2.02 2.24 2.72 4.00
Three ring aromatics 0.02 0.25 0.23 0.35 0.34 0.34
Four ring aromatics B0.01 0.08 0.12 0.16 0.14 0.20
Total PAH 0.19 1.42 2.37 2.74 3.19 4.54
Total aromatics 0.34 14.96 19.46 25.90 26.57 37.20
38 R. Bagri, P.T. Williams / J. Anal. Appl. Pyrolysis 63 (2002) 29–41

Table 3
Polycyclic aromatic hydrocarbons present in the product oils from the Y-zeolite catalytic pyrolysis of
polyethylene (ppm)

No catalyst (°C) Y-zeolite bed temperature (°C)

500 400 450 500 550 600

Naphthalene 170 110 380 1820 1960 1810

Methylnaph- 210 950 3970 6850 11500 29770
thalene
Dimethylnaph- 730 3130 6980 6500 7200 5250
thalene
Trimethylnaph- 320 4710 6710 5880 5030 2410
thalene
Tetramethylnaph- 190 2110 2150 1300 1460 740
thalene
Phenanthrene 25 200 310 790 1010 1290
Methylphenan- 60 230 570 1070 960 1000
threne
Dimethylphenan- 70 1360 800 1100 1230 980
threne
Trimethylphenan- 50 440 440 390 200 120
threne
Tetramethylphen- 40 230 200 140 10 30
anthrene
Pyrene B10 240 290 500 550 1030
Methylpyrene 20 230 360 660 610 610
Dimethylpyrene 30 290 510 430 240 330
Total (wt.%) 0.19 1.42 2.37 2.74 3.19 4.54

ortho-xylene compounds. Toluene was found to be the dominant single ring

hydrocarbon formed with catalytic pyrolysis. Negelein et al. [20] investigated the
catalytic cracking of polyalkenes and found that alkyl aromatic hydrocarbons were
formed. They found that product oils contained C6 –C11 aromatic compounds,
which indicated the presence of single ring and polycyclic aromatic hydrocarbons.
Garforth et al. [22] investigated the catalytic degradation of high density
polyethylene and found that the product oil contained a gasoline fraction with the
presence of benzene, toluene and xylene compounds. In addition, they carried out
a series of experiments that studied the effect of temperature on the product yields.
They found that the aromatic content of the oil increased with increasing reactor
temperature. Uemichi et al. [23] reported on the deactivation behaviour of zeolites
in the degradation of polyethylene and found that increasing the zeolite bed loading
increased the aromatic content, consequently decreasing the alkene and alkane yield
of the product oils.
The Y-zeolite produced much higher concentrations of single ring aromatic and
polycyclic aromatic hydrocarbons compared to the ZSM-5 zeolite. Table 1 shows
that the Y-zeolite exhibited a larger selective pore size than the ZSM-5 zeolite
catalyst. The higher pore size allows larger molecules to enter the catalyst and
 R. Bagri, P.T. Williams / J. Anal. Appl. Pyrolysis 63 (2002) 29–41 39

Table 4
Aromatic and polycyclic aromatic hydrocarbons present in the product oils from the zeolite ZSM-5
catalytic pyrolysis of polyethylene (wt.%)

No catalyst (°C) Zeolite ZSM-5 bed temperature (°C)

500 400 500 600

Toluene 0.01 0.12 0.22 0.50

Ethylbenzene 0.01 0.05 0.55 0.69
Xylenes 0.03 0.35 0.37 0.38
Single ring aromatics 0.10 2.12 2.87 2.80
(Excluding toluene, ethylbenzene, xylenes)
Two ring aromatics 0.16 1.37 1.81 2.94
Three ring aromatics 0.02 0.10 0.17 0.32
Four ring aromatics B0.01 0.02 0.02 0.06
Total PAH 0.19 1.49 2.00 3.32
Total aromatics 0.34 4.13 6.01 7.69

undergo catalytic aromatising reactions, thereby increasing the quantities of single

ring and aromatic compounds present in the derived oil. In addition, the Y-zeolite
catalyst had a silica:alumina ratio much lower than that of the ZSM-5 zeolite
catalyst; 11 compared to 50. Reducing the silica:alumina ratio serves to increase the
surface acidity of the catalyst by increasing the relative surface concentration of
aluminium [12,24] The acidity of a catalyst providing the catalytic activity whilst
the pore size provides the shape selectivity. By changing the silica:alumina ratio it

Table 5
Polycyclic aromatic hydrocarbons present in the product oils from the zeolite ZSM-5 catalytic
pyrolysis of polyethylene (ppm)

No catalyst (°C) Zeolite ZSM-5 bed temperature (°C)

500 400 500 600

Naphthalene 170 480 1370 2710

Methylnaphthalene 210 3250 2620 9780
Dimethylnaphthalene 730 5220 8500 10770
Trimethylnaphthalene 320 3580 4400 4770
Tetramethylnaphthalene 190 1150 1200 1370
Phenanthrene 25 140 180 500
Methylphenanthrene 60 310 650 1350
Dimethylphenanthrene 70 420 660 770
Trimethylphenanthrene 50 110 140 220
Tetramethylphenanthrene 40 60 80 310
Pyrene B10 60 50 280
Methylpyrene 20 50 70 190
Dimethylpyrene 30 50 60 170
Total (wt.%) 0.19 1.45 2.00 3.32
40 R. Bagri, P.T. Williams / J. Anal. Appl. Pyrolysis 63 (2002) 29–41

is possible to vary both the number and strength of the acid sites. The Y-zeolite in
this work with a lower silica:alumina ratio and consequent higher surface acidity
than the ZSM-5 catalyst, produced higher yields of the single ring and polycyclic
aromatic hydrocarbons. Dejaifve [25] also showed the influence of the sil-
ica:alumina ratio on the yields of aromatic hydrocarbons using zeolite to catalyse
methanol. As the silica:alumina ratio was decreased, and thereby increasing surface
activity, there was a clear and significant increase in the yield of aromatic hydrocar-
bons produced. Kuehler also found that reducing the Si:Al ratio of zeolite from 850
to 40 radically enhanced the yield of aromatic hydrocarbons found in the product
oil [26]. In addition, it should also be noted that the two catalysts differ in their
surface areas, the Y-zeolite having a higher surface area than the ZSM-5 catalyst.
Therefore, a number of factors contribute to the higher production of aromatic
hydrocarbons in the derived pyrolysis-catalysis oil for the Y-zeolite catalyst includ-
ing the larger pore size, higher surface acidity and higher surface area compared to
the ZSM-5 zeolite catalyst.

4. Conclusions

Polyethylene has been pyrolysed in a fixed bed reactor and the pyrolysis gases
passed to a secondary reactor containing zeolite catalyst, either Y-zeolite or ZSM-5
zeolite. In the presence of both the Y-zeolite and ZSM-5 catalyst, the oil yield
decreased with a consequent increase in the gas yield and formation of carbon on
the catalyst. As the temperature of the catalyst was increased from 400 to 600°C
there was a further decrease in oil yield and increase in gas yield. The influence of
both catalysts was to markedly increase the yield of aromatic compounds in the
derived pyrolysis oil with a further increase in aromatic content with increase in
catalyst temperature. The main aromatic hydrocarbons in the oils were toluene,
ethylbenzene and xylenes, and the higher molecular weight aromatic hydrocarbons
were mainly naphthalene and phenanthrene and their methyl derivatives. The main
gases formed were largely the alkanes, methane, ethane, propane and the alkenes,
ethene, propene and butene. Comparison of the two catalysts showed that the
ZSM-5 catalyst gave higher concentrations of gases than the Y-zeolite catalyst but
the Y-zeolite produced much higher concentrations of aromatic compounds, partic-
ularly toluene and ethylbenzene, in the derived oils. The high yield of aromatic
compounds with the Y-zeolite compared to the ZSM-5 catalyst was attributed to
the difference in pore size, surface acidity and surface area of the two catalysts

Acknowledgements

The authors would like to acknowledge the support of an EPSRC Research

Scholarship to R. Bagri. We would also like to thank David Wilson, BP Chemical,
Grangemouth, for the supply of polymer samples and technical discussions.
 R. Bagri, P.T. Williams / J. Anal. Appl. Pyrolysis 63 (2002) 29–41 41

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