188

Energy & Fuels 1999, 13, 188-196

Interaction of Plastics in Mixed-Plastics Pyrolysis

Paul T. Williams* and Elizabeth A. Williams
Department of Fuel and Energy, The University of Leeds, Leeds LS2 9JT, U.K.
Received July 31, 1998. Revised Manuscript Received November 3, 1998

The pyrolysis of mixed-plastic waste has been proposed as a means of recycling to produce
petrochemical feedstock. The interaction of the main plastic types in plastic mixtures is significant
in predicting the likely yield and composition of products from different plastic mixtures. The
six main plastics in municipal solid waste are high-density polyethylene (HDPE), low-density
polyethylene (LDPE), polypropylene (PP), polystyrene (PS), poly(vinyl chloride) (PVC), and poly(ethylene terephthalate) (PET). Each of the plastics was pyrolyzed individually in a fixed-bed
reactor heated at 25 C min-1 to a final temperature of 700 C. Polystyrene was then mixed with
each of the other five plastics in a ratio of 1:1 and pyrolyzed in the fixed-bed reactor under the
same pyrolysis conditions. The yield and composition of the derived oil/wax and gases was
determined. The main gases produced from the individual plastics were hydrogen, methane,
ethane, ethene, propane, propene, butane, and butene and for the PET plastic carbon dioxide
and carbon monoxide. Hydrogen chloride was also produced with PVC. Analysis of the oil/wax
showed that the polyalkene plastics, HDPE, LDPE, and PP, gave a mainly aliphatic composition
consisting of a series of alkanes, alkenes, and alkadienes. PVC gave a mainly aromatic oil, and
PS and PET, which have aromatic groups in their structures, also showed a more aromatic
composition. There was a higher gas yield from the mixtures of the plastics with PS than would
be expected from the pyrolysis of the individual plastics, coupled with a reduction in the oil/wax
phase. The average molecular weight of the oil/wax from the mixed plastics was less than expected
from the individual molecular weights. Compositional analysis of the oil/wax showed that changes
in the concentration of aromatic hydrocarbons and polycyclic aromatic hydrocarbons were produced
with the mixture compared to that expected from the individual plastics.

Introduction
Approximately 15 million tonnes of postconsumer
plastic waste is generated throughout Europe each
year,1 while in the United States 20 million tonnes of
waste is generated.1,2 The waste arises from a number
of sources including agriculture, automotive, construction, distribution, and domestic use. Most of the postconsumer plastic is landfilled or incinerated, and on
average, only 7% is recycled to produce low-grade plastic
products such as plastic sacks, pipes, plastic fencing,
and garden furniture. The low-grade uses for mixedplastic recycled materials has led to research into
alternative processing methods to produce higher value
products. One example is via tertiary recycling or
feedstock recycling where the plastic waste materials
are processed back to produce basic petrochemicals.3,4
Tertiary recycling can be via hydrogenation at high
temperature and pressure or via pyrolysis in an inert
atmosphere at atmospheric pressure to thermally degrade the plastics. A number of pyrolysis experimental
(1) Williams, P. T. Waste Treatment and Disposal; John Wiley &
Sons: Chichester, 1998.
(2) Rashid Khan, M.; Gorsuch, C. A. In Conversion and Utilisation
of Waste Materials; Rashid Khan, M., Ed.; Taylor and Francis Publications: Washington, DC, 1996.
(3) Lee, M. Chem. Brit. 1995, July, 515-516.
(4) Meszaros, M. W. In Plastics, Rubber and Paper Recycling; Rader,
C. P., Baldwin, S. D., Cornell, D. D., Sadler, G. D., Stockel, R. F., Eds.;
ACS Symposium Series 609; American Chemical Society: Washington,
DC, 1995; pp 170-182.

research rigs, pilot plants, and demonstration schemes

have been developed worldwide.5-13
There are six main plastics which arise in municipal
solid waste, high-density polyethylene (HDPE), lowdensity polyethylene (LDPE), polypropylene (PP), polystyrene (PS), poly(vinyl chloride) (PVC), and poly(ethylene terephthalate) (PET).14 In some cases, sources
of waste may generate a single type of plastic waste,
but in the majority of cases, the plastic will be a mixture
of types. There are many studies on the pyrolysis of
individual single types of plastic, simple plastic mixtures, and also mixed-plastic waste to generate either
a fuel or petrochemical feedstock. The yield and com(5) Basta, N.; Fouhy, K.; Moore, S. Chem. Eng. 1995, 31-35.
(6) Scott, D. S.; Czernik, S. R.; Piskorz, J.; Radlein, D. St. A. G.
Energy Fuels 1990, 4, 407-411.
(7) Collin, G. In Thermal Conversion of Solid wastes and Biomass;
Jones, J. L., Radding, S. B., Eds.; ACS Symposium Series 130;
American Chemical Society: Washington, DC, 1980; pp 479-484.
(8) Williams, P. T.; Horne, P. A.; Taylor, D. T. J. Anal. Appl. Pyrol.
1993, 25, 325-334.
(9) Roy, C.; Unsworth, J. In Pyrolysis and Gasification; Ferrero, G.
L., Maniatis, K., Buekens, A.; Bridgwater, A. V., Eds.; Elsevier Applied
Science: London, 1989; pp 180-189.
(10) Koo, J. K.; Kim, S. W.; Seo, Y. H. Resour. Conserv. Recycl. 1991,
5, 365-382.
(11) Kaminsky, W.; Sinn, H. In Thermal Conversion of Solid wastes
and Biomass; Jones, J. L., Radding, S. B., Eds.; ACS Symposium Series
130; American Chemical Society: Washington, DC, 1980; pp 423-440.
(12) Kaminsky, W. J. Anal. Appl. Pyrol. 1985, 8, 439-448.
(13) Conesa, J. A.; Font, R. F.; Marcilla, A.; Garcia, A. N. Energy
Fuels 1994, 8, 1238-1246.
(14) Plastics Recovery in Perspective; Association of Plastic Manufacturers in Europe (APME): Brussels, Belgium, 1993.

10.1021/ef980163x CCC: $18.00 1999 American Chemical Society

Published on Web 12/17/1998

Interaction of Plastics in Mixed-Plastics Pyrolysis

position of the products are influenced by plastic type

and process conditions. For example, the polyalkene
plastics, LDPE, HDPE, and PP, give an oil/wax product
dominated by alkenes, alkanes, and alkadienes, a gas
consisting of hydrogen, alkane and alkene gases, and
negligible char.6,15,16 Pyrolysis of polystyrene has been
shown to produce an oil consisting of mainly styrene
together with other aromatic and polycyclic aromatic
hydrocarbons with a low yield of gas and no char
formation.6,8,15 Pyrolysis of poly(vinyl chloride) produces
hydrogen chloride as the main product and an aromatic
oil with a significant formation of char.6,15,17 Pyrolysis
of poly(ethylene terephthalate) yields a gas mainly in
the form of carbon dioxide and carbon monoxide and a
significant production of char.15,17
There are less data on the influence of mixing of
different plastic types on the yield and composition of
products. Koo et al.10 and Koo and Kim18 characterized
the yield and composition of simple mixtures of polethylene with polystyrene. They showed that the presence
of polystyrene in the mixture resulted in a reduction in
the time required for maximum oil production from
polyethylene. Wilkins and Wilkins19 have reviewed the
pyrolysis of mixed-plastic wastes and reported that as
the temperature of pyrolysis was increased, the gaseous
products increase, the yield of oil/wax rises then falls,
and the yield of char first increases due to cracking
reactions but is then increased due to coking reactions.
Wenning20 also pyrolyzed mixed-plastic waste and found
that depending on the composition of the plastic mixture
and temperature of pyrolysis, the product yield was in
the range 30-50 wt % gases, 40-55 wt % oil/wax, and
5-15 wt % char.
While plastics have been pyrolyzed as individual
plastic types and as mixed-plastic waste, there are few
studies detailing the interaction of plastic types in a
mixture. In this paper the six main plastics occurring
in municipal solid waste were pyrolyzed individually in
a fixed-bed reactor heated at 25 C min-1 to a final
temperature of 700 C. Polystyrene was then mixed with
each of the other five plastics in a ratio of 1:1 and
pyrolyzed in the fixed-bed reactor under the same
pyrolysis conditions. The yield and composition of the
derived oils and gases was determined.
Experimental Section
Plastic Types. The plastics used were the six most common
plastic types found in municipal solid waste, high-density
polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), poly(vinyl chloride) (PVC), and
poly(ethylene terephthalate) (PET). The plastics were obtained
from BP Chemicals Ltd., Grangemouth, U.K., and were virgin
plastics of 2-5 mm diameter pellets. Where the mixture was
used, polystyrene was used as the plastic with which the other
five main plastics were mixed. A 1:1 mixture by weight of each
(15) Williams, P. T.; Williams, E. A. J. Inst. Energy 1998, 71, 8193.
(16) Kaminsky, W. In An assessment of Thermochemical Conversion
Systems for Processing Biomass and Refuse; Bridgwater, A. V., Evans,
G. D., Eds.; ETSU Report No. B/T1/00207/REP; Energy Technology
Support Unit: Harwell, Oxford, 1993; pp 122-129.
(17) Williams, E. A.; Williams, P. T. J. Chem. Technol. Biotechnol.
1997, 70, 9-20.
(18) Koo, J. K.; Kim, S. W. Waste Manage. Res. 1993, 11, 515-529.
(19) Wilkins, E. S.; Wilkins, M. G. J. Environ. Sci. Health 1983,
A18 (6), 747-772.
(20) Wenning, H. P. J. Anal. Appl. Pyrol. 1993, 25, 301-310.

Energy & Fuels, Vol. 13, No. 1, 1999 189

Figure 1. Schematic diagram of the fixed-bed pyrolysis

reactor.
of HDPE, LDPE, PP, PVC, and PET was mixed with PS. Onehalf the mass load of each polymer was used to make up the
one mass load of 3 g of the feedstock pyrolyzed. Polystyrene
was chosen as the base plastic with which the others were
mixed since pyrolysis of the individual plastics showed that
polystyrene gave the lowest viscosity oil.
Fixed-Bed Pyrolysis Reactor. A fixed-bed gas-purged
pyrolytic reactor was used to pyrolyze the plastics. The sample
was placed in a stainless steel crucible inside the reactor. This
avoided loss of sample during melting and before the pyrolysis
temperature was reached. The reactor consisted of a 200 cm3
stainless steel reactor externally heated by an electric ring
furnace. The furnace was controlled by a programmable
temperature controller which enabled the samples to be heated
at a fixed heating rate of 25 C min-1 to the final pyrolysis
temperature of 700 C. The sample was held at 700 C for 1 h
or until there was no significant yield of gas. Nitrogen was
used as the carrier gas at a fixed metered flow rate to sweep
the evolved products quickly from the reaction zone, to
minimize secondary reactions such as thermal cracking, repolymerization, and recondensation. The liquid oil/wax phase
was trapped in glass liners inside a series of cold traps,
maintained at -78 C temperature with the aid of a solid CO2/
acetone mixture. A condenser packed with glass wool was
placed in-line after the condensers to trap any oil particles.
Where PVC was used either as an individual plastic or in a
PVC-PS mixture, a further dreschel bottle with deionized
water was placed in-line to dissolve any hydrogen chloride
formed. The gas effluent from the condenser system was
collected in a 100 L Teflon gas sample bag which was filled
throughout the entire pyrolysis experiment. The bag was
sealed and analyzed immediately for a range of gases using
packed column gas chromatography. Figure 1 shows a schematic diagram of the fixed-bed reactor.
Gas Analysis. The gases collected in the Teflon gas sample
bag were analyzed off-line. Hydrocarbons including methane,
ethane, ethene, propane, propene, butane, and butene were
analyzed using packed column gas chromatography using a
GCD chromatograph with a 2.2 m long 6 mm diameter glass
column packed with 80-100 mesh n-octane Porasil C and with
a flame ionization detector. There were other C4 and C5 gases
detected on the system, but they were not identified in this
work. Hydrogen, carbon monoxide, nitrogen, and oxygen were
analyzed on a Pye 204 chromatograph with a 1.8 m long 6
mm diameter stainless steel column with molecular sieve 5 A
type packing using a thermal conductivity detector. Carbon
dioxide was analyzed using a Gow Mac chromatograph with
a 1.8 m long 6 mm diameter stainless steel column packed

190 Energy & Fuels, Vol. 13, No. 1, 1999

with 100-120 mesh chromatographic-grade silica gel with a
thermal conductivity detector. Data manipulation was carried
out using a Harley Peakmaster data analysis system. Where
PVC was pyrolyzed, the hydrogen chloride trapped in the
dreschel bubbler was analyzed using a Corning pH/ion meter
135 with a chloride electrode calibrated between 100 and 1000
ppm. The total weight of gases produced was calculated by
comparison to the known nitrogen flow rate, and gas chromatographic analysis was used to determine the total mass
balance rather than as gas by difference.
Functional-Group Compositional Analysis. Functionalgroup compositional analysis of each pyrolytic oil/wax was
carried out using Fourier transform infrared spectrometry. A
Perkin-Elmer 1750 spectrometer was used, which had data
processing and spectral library search facilities. A small
amount of the oil/wax derived from the plastics pyrolysis was
mounted on a handmade KBr disk which had been previously
scanned as a background. The infrared spectra of the sample
was then taken. The resulting spectra were normalized to the
C-H peak found at approximately 3000 cm-1. Direct comparisons of peak intensity could then be taken.
Molecular Weight Distribution. Size-exclusion chromatography or gel-permeation chromatography is a nondestructive method that gives information on the molecular weight
distribution of the sample. The system incorporated two 150
mm 4.6 mm i.d. columns with Polymer Laboratories 5 m
RPSEC 100 A type packing. A third column of the same
material was placed in-line between the pump and the
injection valve to ensure presaturation of the solvent with the
column packing material and also to avoid analytical column
dissolution and, hence, loss of performance. The solvent used
for the mobile phase was tetrahydrofuran (THF). The calibration system used was based on polystyrene samples of low
polydispersity in the MW range of 800 to 860 000, also included
was benzene for low MW calibration. Samples were introduced
through a 2 L loop injection valve. The detectors were an
ultraviolet (UV) detector from Merck-Hitachi and a refractive
index (RI) detector from Varian. Ultraviolet scanning of the
polystyrene MW fractions in THF indicated that the maximum
absorbance was at 262 nm, and all calibration and efficiency
measurements were taken at this wavelength. The use of two
detectors enables more information to be obtained from the
system. The output from the detectors was recorded on a
microcomputer which analyzed the data. The MW distribution
was determined as number and weight average MW, in
addition the polydispersity of the oils was calculated. The
number average molecular weight (Mn) is defined as the
average molecular weight according to the number of molecules present of each species.21 The weight average molecular
weight (Mw) is the sum of the product of the weight of each
species present and its molecular weight divided by the sum
of the weights of the species. The difference in the values of
Mn and Mw indicates the polydispersity of the sample, where
the closer the two measured average molecular weights are,
the narrower the molecular weight distribution. Single compounds have a polydispersity in the range 1.0-1.1, measured
on the system described in this work. The details of the system
have been reported previously.22
Detailed Oil and Wax Analysis. The oil/wax derived from
the pyrolysis of the plastics were analyzed in detail for their
content of aliphatic and aromatic compounds. The oil/waxes
were separated by liquid chromatography into chemical class
fractions followed by gas chromatography/flame ionization
detection and confirmation of identification by gas chromatography/mass spectrometry. The liquid chromatography consisted of 10 cm 1 cm glass columns packed with 5.0 g silica,
(21) Hatch, L. F.; Matar, S. Hydrocarbons to Petrochemicals; Gulf
Publishing Co.: London, 1981.
(22) Williams, P. T.; Taylor, D. T. J. Anal. Appl. Pyrol. 1994, 29,
111-128.

Williams and Williams

Table 1. Product Yield from Fixed-Bed Pyrolysis of
Individual Plastics (wt %)
plastic

HDPE

LDPE

PP

PS

PVC

PET

gases
oil/wax
char
HCl
total

18.0
79.7
0.0
0.0
97.7

15.1
84.3
0.0
0.0
99.4

15.3
84.4
0.2
0.0
99.9

3.4
83.8
3.5
0.0
90.7

2.5
31.7
13.8
52.9
100.9

38.7
41.3
15.6
0.0
95.6

Bondesil (sepralyte) sorbent, pretreated 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
infrared spectroscopy confirmed that these were the compositions of each fraction. Each fraction was evaporated to dryness
by nitrogen blow down and weighed, and the percentage mass
in each fraction was calculated. The evaporation of the solvent
would inevitably lead to some loss of volatile material,
consequently, this step in the analytical procedure was carefully carried out to minimize these losses. For the polyalkene
plastics, HDPE, LDPE, and PP, their derived oil/waxes were
found to contain negligible concentrations of aromatic and
polar species, and consequently, no chemical class separations
were carried out and the samples were analyzed directly by
gas chromatography/flame ionization detection.
The fractions were analyzed by capillary column gas chromatography with flame ionization detection, and also compound identifications for aromatic species were confirmed by
gas chromatography/mass spectrometry. Identification was
also by the extensive use of relative retention indices23-25 and
the use of internal standards and response factors. The gas
chromatography/flame ionization detection 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, aluminumcoated column with a 5% phenyl polycarborane-siloxane
stationary phase. The high-temperature column enabled oven
temperatures of 400 C to be used, which ensured that
hydrocarbons up to C60 could be analyzed. The temperature
program 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 benchtop ion-trap detector type manufactured by FinniganMAT. The ion-trap detector had a mass range from 20 to 650
m with scan times between 0.125 and 2 s, and it was linked
to a computer with a library containing 38 752 mass spectra.
The capillary column was a DB5, and the temperature
program was 60 C for 2 min followed by a 5 C min-1 heating
rate to 270 C.

Results and Discussion

Product Yield. Table 1 shows the product yields for
the pyrolysis of the six individual plastics. All the
plastics produced a hydrocarbon gas and an oil/wax. The
PVC and PET plastics produced a char, and PVC also
produced hydrogen chloride. The polyalkene plastics,
HDPE, LDPE, and PP, gave a light-colored waxy
product. PVC produced a black oil, PS produced a red/
brown oil, and PET gave a dark, almost black, viscous
oil.
(23) Vassilaros, D. L.; Kong, R. C.; Later, D. W.; Lee, M. L. J.
Chromatogr. 1982, 252, 1-20.
(24) Rostad, C. E.; Pereira, W. E. J. High Resolut. Chromatogr.
Chromatogr. Commun. 1986, 9, 328-333.
(25) Lee, M. L.; Vassilaros, D. L.; White, C. M.; Novotny, M. Anal.
Chem. 1979, 51, 768-773.

Interaction of Plastics in Mixed-Plastics Pyrolysis

Energy & Fuels, Vol. 13, No. 1, 1999 191

Table 2. Actual and Predicted Product Yield from

Fixed-Bed Pyrolysis of Individual Plastics Mixed 1:1 with
Polystyrene (wt %)
mixture

HDPE/PS

LDPE/PS

PP/PS

gases
oil/wax
char
HCl

31.5
67.3
1.2
0.0

Actual
33.8
16.0
64.0
83.6
2.2
0.4
0.0
0.0

gases
oil/wax
char
HCl

10.7
81.7
1.8
0.0

Predicted
9.3
9.4
84.1
84.1
1.8
1.9
0.0
0.0

PVC/PS

PET/PS

13.8
49.5
12.7
24.0

25.5
64.0
10.5
0.0

3.0
57.8
8.7
26.5

21.1
62.6
9.6
0.0

The three polyalkene plastics produced very similar

product yields, with high yields of wax and hydrocarbon
gas and negligible char yields. PS also produced a high
oil yield. PVC produced the lowest yield of oil with
higher conversion of the plastic to gas in the form of
hydrogen chloride and hydrocarbons and a significant
proportion of char. PET pyrolysis similarly produced a
significant amount of char and gases, dominated by
carbon dioxide and carbon monoxide.
Individual plastics have been pyrolyzed by other
researchers investigating the recycling of waste plastics
but mostly under fast pyrolysis conditions. For example,
Scott et al.6 pyrolyzed polyethylene (linear low-density
polyethylene, LLDPE) in a fluidized-bed reactor at
temperatures from 515 to 725 C. Their product yield
at 515 C included a significant production of char (5
wt %) and over 80% conversion to oil/wax. Fluidizedbed pyrolysis of polypropylene in the form of used
clinical syringes has been carried out by Kaminsky,16
who reported much higher gas yields of 59.3 wt %,
however, their fluidized bed was operated at 710 C,
which generates higher concentrations of gas. Scott et
al.6 pyrolyzed polystyrene in a fluidized-bed reactor at
532 C and reported a high conversion rate to oil which
consisted mainly of styrene. Williams et al.8 pyrolyzed
polystyrene in a fixed-bed reactor and also showed that
styrene was the main product of pyrolysis, although a
significant proportion of other aromatic hydrocarbons
were also formed. Scott et al.6 showed that in the fast
pyrolysis of PVC, 56 wt % of hydrogen chloride, 9.1 wt
% char, 6.3 wt % liquid, and 28.6 wt % of hydrocarbon
gases were formed. Kaminsky12 pyrolyzed PET in a
fluidized bed and found a similar high gas yield of over
50 wt % with a char yield of 7.1 wt % and wax yield of
40 wt %.
Table 2 shows the product yield when HDPE, LDPE,
PP, PVC, and PET were pyrolyzed individually in a 1:1
mixture with PS. Also shown are the predicted results
based on cummulation of the two individual plastics
pyrolysis results shown in Table 1. The results show
that there was a clear interaction of the plastics with
PS to produce a much higher than expected gas yield.
The oil/wax yields for HDPE/PS, LDPE/PS, and PVC/
PS were much lower than expected, whereas the PP/
PS and PET/PS oil/wax yields were almost as expected.
The char yields are lower than would be predicted for
the HDPE/PS and PP/PS mixtures and higher than
would be predicted for the LDPE/PS, PVC/PS, and PET/
PS mixtures. HCl formation for the PVC/PS mixture
was mostly as expected from mixing the two plastics.
The oil/wax yield in the case of the plastics mixed with

Table 3. Gas Composition from Fixed-Bed Pyrolysis of

Individual Plastics (wt %)
plastic

HDPE

LDPE

PP

PS

PVC

PET

hydrogen
methane
ethane
ethene
propane
propene
butane
butene
carbon dioxide
carbon monoxide
hydrogen chloride

0.12
1.90
2.21
6.08
1.31
4.56
0.22
0.36

0.05
1.14
1.67
4.00
1.33
4.00
0.32
2.00

0.05
0.93
1.45
3.52
1.00
3.53
0.23
1.29

0.04
0.53
0.08
0.26
0.02
0.05
0.00
0.06

0.12
0.77
0.47
0.15
0.24
0.19
0.11
0.15

0.00
0.00

0.00
0.00

0.00
0.00

0.00
0.00

0.00
52.93

0.31
0.71
0.03
1.41
0.13
0.09
0.00
0.00
22.71
13.29
0.00

PS produced a true oil in all cases, rather than a wax,

which was the case with HDPE, LDPE, and PP when
pyrolyzed alone. The oil was colored light yellow for the
HDPE/PS, LDPE/PS, and PP/PS mixtures, black for the
PVC/PS mixture, and dark brown and a more viscous
oil for the PET/PS mixture.
Koo et al.10 pyrolyzed mixtures of HDPE and PS at
ratios of 1:4 and 1:1, respectively. The maximum oil and
gas production were produced in shorter pyrolysis times
than for HDPE alone, suggesting an enhancement effect
from the presence of PS. Their results also showed that
there was clear evidence of interaction of the plastics,
since increasing the content of PS in the mixture from
1:1 to 1:4 did not result in an equivalent increase in oil
or gas yield.
Gas Analysis. Table 3 shows the composition of gases
derived from the fixed bed pyrolysis of the individual
plastics. The three polyalkene plastics, HDPE, LDPE,
and PP, behave quite similarly in that the main gases
to be formed were as expected, alkene gases derived
from the thermal degradation of their similar polyalkene
chemical structure. Ethene, propene, and butene were
by far the most common hydrocarbon gases. These
alkene gases represent the small molecular weight
range of the random scission process coupled with
stabilization of the resultant radical which leads to the
formation of carbon double bonds. Consequently this
results in a tendency of the thermal degradation process
to yield alkenes as the major product.26-28 The alkane
gases, methane, ethane, propane, and butane, were also
present in significant concentrations, again formed as
part of the random scission process of the thermal
degradation of the polymer.
Polystyrene gave a low gas yield overall, since there
was a much higher conversion of the plastic to oil/wax.
The derived hydrocarbon gas composition consisted
mainly of alkene gases, ethene, propene, and butene,
and also methane.
Poly(vinyl chloride) gave hydrogen chloride as the
main gas by far. The C-Cl bond in the PVC structure
has a lower bond energy than other bonds in its
structure, and upon heating it has a tendency to break
first. As a consequence, PVC thermal degradation
begins around 150 C, which is a much lower temperature than the other plastics used in this work. The
intermolecular chain-transfer reaction which follows
(26) Wampler, T. P. J. Anal. Appl. Pyrol. 1989, 5, 187-195.
(27) Shalaby, S. W. In Thermal Characterisation of Polymer Materials; Turin, E. A., Ed.; Academic Press: New York, 1981; pp 237-264.
(28) Driver, W. E. Plastics, Chemistry and Technology; Van Nostrand
Reinhold Co.: Germany, 1979.

192 Energy & Fuels, Vol. 13, No. 1, 1999

Williams and Williams

Table 4. Gas Composition from Fixed-Bed Pyrolysis of

Individual Plastics Mixed 1:1 with Polystyrene (wt %)a
mixture
hydrogen
methane
ethane
ethene
propane
propene
butane
butene
a

HDPE/PS
na
na
na
na
na
na
na
na

LDPE/PS

PP/PS

PVC/PS

0.33
2.48
2.08
7.48
1.01
6.44
0.36
9.21

0.19
1.11
1.12
2.82
0.69
2.81
0.21
5.26

0.28
1.26
0.56
0.49
0.21
0.48
0.10
7.83

PET/PS
na
na
na
na
na
na
na
na

na ) not available.

leads to dehydrochlorination, and hydrogen chloride is

produced.29
The pyrolysis of PET, in contrast to the other plastics
investigated, produced a gas consisting mainly of carbon
dioxide and carbon monoxide, due to the high oxygen
content of the original plastic polymer. In addition,
much lower concentrations of hydrocarbons were formed.
Carbon dioxide is formed from the decarboxylation of
the PET, and carbon monoxide may be formed via either
decarboxylation or reaction between carbon dioxide and
char.30 Other researchers have also shown that carbon
dioxide and carbon monoxide are the major gases
produced in the thermal degradation of PET.12,30
Detailed gas analysis was only available for hydrogen
and the hydrocarbon gases for the LDPE/PS, PP/PS, and
PVC/PS plastic mixtures, and the results are shown in
Table 4. The LDPE/PS mixture gave higher individual
gas concentrations than would be expected from the gas
data derived from the pyrolysis of the individual plastics
shown in Table 3. In particular, hydrogen, ethene,
propene and butene were markedly increased over that
which might be expected. The PP/PS mixture gave gases
somewhat higher than expected, again with respect to
the alkene gases. It may be predicted from the individual gas analysis data of Table 3 that of the hydrocarbon gases, the mixture of PVC/PS would produce
mainly methane and ethene. However, Table 4 shows
that by far the major gas is butene. Therefore, the
mixed-plastic degradation during pyrolysis favors the
formation of butene rather than methane and ethene.
The data of Table 4, therefore, show that mixing of
the plastics with polystyrene produces gases which are
not merely due to the individual plastics pyrolyzing
separately but there is clear evidence of interaction.
Functional-Group Compositional Analysis. Figure 2 shows the functional-group compositional analysis
of the oil/wax derived from the pyrolysis of HDPE,
LDPE, and PP, and Figure 3 shows the functional-group
compositional analysis of PVC, PS, and PET analyzed
by Fourier transform infrared (FT-IR) spectrometry.
The polyalkene plastics, HDPE, LDPE, and PP, gave
very similar FT-IR spectra since their polymer structures are very similar and their thermal degradations
are likely to produce similar compounds in the derived
oil/wax. The peak at 3050 cm-1 is an indication of the
presence of dC-H stretching vibrations typical of
alkene functional groups. The peaks between 3000 and
2800 cm-1 indicate the presence of -CH3, -CH2, and
C-H functional groups, which are indicative of aliphatic
(29) Lattimer, R. P.; Kroenke, W. J. J. Anal. Appl. Pyrol. 1980, 25,
101-110.
(30) Day, M.; Wiles, D. M. J. Anal. Appl. Pyrol. 1984, 7, 65-82.

Figure 2. Fourier transform infrared spectra of oil/wax

derived from the pyrolysis of HDPE, LDPE, and PP.

Figure 3. Fourier transform infrared spectra of oil/wax

derived from the pyrolysis of PVC, PS, and PET.

species such as alkanes and alkenes. The CdC absorbance peak between 1625 and 1675 cm-1 confirms that
alkene groups are present in the oil/wax. The presence
of peaks in the region from 1350 to 1500 cm-1 due to
the deformation vibrations of C-H bonds confirm the
presence of aliphatic groups. The peaks located at 980
and 920 cm-1 represent CH stretching and deformation
vibrations of alkene structures. Two peaks between 720
and 730 cm-1 indicate C-H cyclic deformations which
suggest either aromatic or more likely -CH2 which has
split due to interaction in long molecular chains, representing the presence of long oligomer chains. The
overall spectra of the polyalkene pyrolysis oil/wax is,
therefore, dominated by the presence of alkane and
alkene compounds, as found by other workers.12,13,15
Figure 3 shows that the functional-group compositional analysis of the pyrolysis oil/waxes from PVC, PS,
and PET are very different to the polyalkene plastic
pyrolysis oil/waxes. The spectra of the PVC pyrolysis
oil/wax shows that the characteristic peaks of alkanes
and alkenes are present as described for the polyalkene
plastics. Since the PVC plastic polymer is based on a
similar backbone structure to the polyalkene plastics,

Interaction of Plastics in Mixed-Plastics Pyrolysis

a similar degradation product oil/wax composition may

be expected. However, the spectra for PVC in Figure 3
shows that there are additional peaks in the region from
675 to 900 and 1575 to 1625 cm-1. The presence of these
peaks indicates the presence of monoaromatic, polycyclic
aromatic, and substituted aromatic groups. Benzene has
been identified as a major constituent in oils derived
from the pyrolysis of PVC, while other aromatic compounds identified included alkylated benzenes and
naphthalene and other polycyclic aromatic hydrocarbons.15,29,31
The pyrolysis oil/wax derived from the pyrolysis of PS
produced a strong presence of both aromatic and
aliphatic functional groups. The presence of CH3 and
CH2 are indicated by the peaks between 3000 and 2800
cm-1 and the peak in the region from 1350 to 1500 cm-1
due to the presence of C-H bonds confirm the presence
of aliphatic groups. In addition, there are strong peaks
present in the region from 675 to 900 cm-1 and three
strong peaks between 3000 and 3050 cm-1 showing a
very significant presence of aromatic compounds in the
oil/wax. It has been shown that pyrolysis oil/wax from
PS produces a mainly aromatic oil,6,8,15 consequently the
aliphatic functional groups indicated by the FT-IR
spectra probably indicates that these aliphatic groups
are present as alkyl groups attached to aromatic rings.
The FT-IR analysis for the oil/wax derived from PET
pyrolysis produced a complex spectra which included
oxygenated functional groups in addition to aliphatic
and aromatic groups. The oxygen atoms, aromatic ring,
and aliphatic groups in the original polymer structure
lead to a very complex composition of compounds in the
resultant pyrolysis oil/wax. The broad peak between
3300 and 2900 cm-1, may be due to intramolecular OH
or hydrogen-bonded OH groups. The presence of such
groups, coupled with the presence of CdO stretching
vibrations between 1650 and 1850 cm-1, indicates the
presence of carboxylic acids and their derivatives. The
presence of the CdO peaks between 1650 and 1850 cm-1
may also indicate the presence of ketones and aldehydes. Aromatic groups are indicated by the peaks
between 675 and 900 and 1575 to 1625 cm-1.
The FT-IR spectra from the oil/wax derived from the
pyrolysis of PS/HDPE, PS/LDPE, PS/PP, PS/PVC, and
PS/PET, are shown in Figure 4. The polyalkene plastics,
HDPE, LDPE, and PP, when mixed with PS gave very
similar FT-IR spectra, which consist essentially of the
mixed spectra from each component. Each of the spectra
contain the dominantly alkane and alkene peaks derived from the polyalkene plastics and the mainly
aromatic peaks derived from the PS. For example, the
alkane and alkene peaks are illustrated by the presence
of -CH3, -CH2, and C-H functional groups at 3000,
2800, and 1350-1500 cm-1 and the CdC absorbance
peak between 1625 and 1675 cm-1, and alkene structure
is indicated by the peaks at 980 and 920 cm-1. The
aromatic structures present in the oil from the mixtures
are clearly indicated by the strong peaks from 3000 to
3050 cm-1 and group of peaks between 675 and 900
cm-1.
The mixture of PET with PS shows a very complex
spectrum representing a mixture of the two individual
(31) Montaudo, G.; Puglisi, C. Polym. Degrad. Stab. 1991, 262, 229244.

Energy & Fuels, Vol. 13, No. 1, 1999 193

Figure 4. Fourier transform infrared spectra of oil/wax

derived from the pyrolysis of HDPE/PS, LDPE/PS, PP/PS,
PET/PS, and PVC/PS.

pyrolysis products. For example, the presence of the

broad peak between 3300 and 2900 cm-1, 1650 and 1850
cm-1, and 1650 and 1850 cm-1 indicates the presence
of carboxylic acids, ketones, and aldehydes derived from
the pyrolysis of PET. Aromatic functional groups were
present in the thermal degradation products of both
PET and PS and are clearly represented in the spectra.
PVC and PS produced a very aromatic oil with strong
peaks due to aromatic compounds shown by the presence of peaks between 3000 and 3050 cm-1 and the
group of peaks between 675 and 900 cm-1. Both plastics
when pyrolyzed individually gave a mainly aromatic oil/
wax.
Overall it may be concluded that on the basis of the
broad analysis of functional-group composition by FTIR that the derived oils from mixtures of HDPE, LDPE,
PP, PET, and PVC with PS gave spectra which indicate
that the compounds present are generally similar to
those found in a mixture of the individual plastics.
However, as will be shown later, there are some differences in the detailed analyses of the samples than that
which could be predicted by merely addition of the
individual components of the oil/wax.
Koo et al.10 also showed that the oil derived from the
pyrolysis of a mixture of HDPE and PS gave a mixture
of aliphatic and aromatic species. The PE fraction of the
mixture is largely responsible for the aliphatic material,
and the PS fraction is largely responsible for the
aromatic compounds in the mixture.
Molecular Weight Distribution of the Oils and
Waxes. Table 5 shows the number and weight averaged
molecular weights of the six individual plastics pyrolyzed in the fixed-bed reactor. The data are presented
as determined from both the RI and UV detectors. The
molecular weight distribution for the derived pyrolysis
oil/wax ranged from approximately 60 to 1500 Da for
the polyalkene derived samples, from 60 to 1000 Da for
PS, 60 to 1100 Da for PVC, and 60 to 500 Da for PET.
The highest average molecular weight data were associated with the oil/wax derived from PP, while the
lowest were associated with the oil from PS pyrolysis.
The liquid derived from PS was a low-viscosity oil,
whereas the liquid products from the other plastic

194 Energy & Fuels, Vol. 13, No. 1, 1999

Williams and Williams

Table 5. Number and Weight Average Molecular Weight

and Polydispersity of the Oil/Wax from Fixed-Bed
Pyrolysis of Individual Plasticsa
plastic

HDPE LDPE

PP

PS

PVC

PET

RI Detector
Mn
240
209
241
145
251
195
360
306
403
176
334
212
Mw
polydispersity
1.50
1.46
1.67
1.21
1.28
1.09
UV Detector
Mn
178
208
280
116
230
210
M
281
250
439
147
384
276
polydispersity
1.58
1.21
1.57
1.27
1.67
1.32
a M ) Number average molecular weight (Daltons). M
n
w )
Weight average molecular weight (Daltons).

Table 6. Number and Weight Average Molecular Weight

and Polydispersity of the Oil/Wax from Fixed-Bed
Pyrolysis of Individual Plastics Mixed 1:1 with
Polystyrene (wt %)a
mixture

HDPE/PS LDPE/PS PP/PS PVC/PS PET/PS

Mn
Mw
polydispersity

138
166
1.20

RI Detector
150
128
178
170
1.19
1.33

211
240
1.14

134
185
1.38

Mn
Mw
polydispersity

113
136
1.20

UV Detector
113
117
137
149
1.22
1.27

161
233
1.45

121
160
1.33

a M ) Number average molecular weight (Daltons). M

n
w )
Weight average molecular weight (Daltons).

pyrolysis were more viscous. Table 5 also shows the

polydispersity, which reflects the deviation of the molecular weight distribution from the Gaussian distribution of an ideal single compound. A higher polydispersity
for a sample indicates a broader range of molecular
weight distribution, reflecting a wider range of compounds present in the sample. The data suggest that
the oils are all quite complex containing a complex range
of compounds.
Table 5 shows that the UV detector gave consistently
lower molecular weight ranges and averaged data than
the RI detector. The use of two detectors enables more
information to be obtained from the system. While both
detectors will detect the full range of hydrocarbons,
whether aliphatic or aromatic, the UV may be tuned to
an optimum wavelength to give an enhanced signal for
aromatic compounds while still detecting all the aliphatic compounds present. The details of the two
detector systems have been reported previously.22 The
results suggest, on a qualitative basis, that the molecular weight range of the aromatic species in the oil/wax
have a lower molecular weight distribution compared
to the aliphatic compounds.
Table 6 shows the number and weight averaged
molecular weights of the derived oil/wax from the
pyrolysis of the HDPE/PS, LDPE/PS, PP/PS, PVC/PS,
and PET/PS mixtures. The data show that in all cases
the number and weight averaged molecular weights
were lower when the plastics were mixed 1:1 with PS
than when they were pyrolyzed individually. The oil/
wax derived from the plastics mixed with PS pyrolysis
in all cases produced an oil, even for the plastics such
as HDPE, LDPE, and PP, which when pyrolyzed individually produced a light wax. In addition, the polydispersity, apart from the PET/PS mixture, was reduced

compared to the oils derived from the individual plastics

pyrolysis.
The individual number and weight average data from
Table 5 may be used to calculate an expected average
set of data combining the individual plastic data with
that of PS. This gives a much higher averaged figure
than that shown in Table 6. This suggests that there is
a definite interaction of reacting species during pyrolysis
which produces a range of lower molecular weight
chemical species.
While the number and weight averaged data for the
oils was reduced for the pyrolysis oils derived from the
plastics mixed with PS, the molecular weight distribution was also reduced. The molecular weight range for
HDPE/PS, LDPE/PS, and PP/PS pyrolysis oils was from
a nominal 60-700 Da and for PVC/PS and PET/PS from
60 to 600 Da.
The averaged data analyzed using the UV detector
were again lower than those determined using the RI
detector, suggesting that in general terms the aromatic
compounds were of lower molecular weight than the
aliphatic material present in the oil/wax.
Detailed Oil/Wax Analysis. The oil/wax derived
from the pyrolysis of the six individual plastics pyrolyzed in the fixed-bed reactor were analyzed in detail
using gas chromatography with flame ionization and
mass spectrometric detection. The polyalkene (HDPE,
LDPE, and PP) derived oil/wax gave an almost exclusively aliphatic product consisting of a series of triplet
peaks of alkanes, alkenes, and alkadienes, as shown by
other researchers.15,26,32 The order of elution was diene,
alk-1-ene, and n-alkane with the alk-1-ene having the
highest concentration. The oil/wax contained hydrocarbons up to C53 for PP and up to C47 for LDPE and
HDPE. The data represents the carbon number limit
which could be chromatographed using the high-temperature column. However, the molecular weight distribution of the oil/waxes discussed previously has
shown that much higher molecular weight compounds
are present in the oil/waxs but were unable to be
analyzed by the gas chromatography system. No aromatic compounds were detected in the oil/wax derived
from the pyrolysis of HDPE, LDPE, or PP. A wide
spectrum of hydrocarbon fragments which may contain
any number of carbon atoms may be expected from the
thermal degradation of the polyalkene plastics, which
occurs through random scission.33,34 The C-C bond is
the weakest in the polyalkene structure, and during the
degradation process, the stabilization of the resultant
radical after chain scission leads to the formation of
carbon double bonds (CdC) in the structure.35 Consequently, a large number of compounds with carbon
double bonds, as shown by the higher concentration of
alkenes in the resultant pyrolysis oil/wax, would be
expected, as shown in this work. The thermal degradation of PP has also been assigned to a random scission
reaction which leads to the formation of a large number
of hydrocarbon species. PP is similar in structure to
(32) Wampler, T. P.; Levy, R. Analyst 1986, 111, 1065-1067.
(33) Albertson, A. C.; Karlsson, S. In Agricultural and Synthetic
Polymers; Glass, J. E., Swift, G., Eds.; ACS Symposium Series 433;
American Chemical Society: Washington, DC, 1990; pp 60-64.
(34) Wampler, T. P. Applied Polymer Handbook; Wampler, T. P.,
Ed.; Marcel Dekker Inc.: New York, 1995.
(35) Pacakova, V.; Leclercq, P. A. J. Chromatogr. 1991, 555, 229237.

Interaction of Plastics in Mixed-Plastics Pyrolysis

Energy & Fuels, Vol. 13, No. 1, 1999 195

Table 7. Aromatic Hydrocarbons in Derived Oils from

Fixed-Bed Pyrolysis of Polystyrene and Individual
Plastics Mixed 1:1 with Polystyrene
PS

HDPE/ LDPE/
PS
PS

PP/
PS

PVC/
PS

Aromatic Compounds (ppm)

benzene
1910
1760
2350
200 16610
toluene
1500
4770
2480
810 2030
o-xylene
390
1350
m-xylene
270
p-xylene
360
trimethylbenzenes
5100
1210
1890
150
indane
4400
550
120
indene
430
1330
900
130
tetramethylbenzenes
460
3390
1470
84
naphthalene
na
5390
3170
150
310
methylnaphthalenes
na
13290
6600 1460
620
dimethylnaphthalenes 2120
480
120
fluorene
260
540
phenanthrene
1420
1800
1910
130 1450
Oxygenated Aromatic Compounds (ppm)
phenol
ethylphenols
undecanol
tridecanone
dibenzofuran
dihydroanthracene

PET/
PS

310

340
230
290
420
130
3090
4810
3260
4590

na ) not available

HDPE, and LDPE thermal degradation via random

scission would also result in a series of dienes, alkenes,
and alkanes.36 However, because of the presence of the
CH3 side chain in the PP structure, different hydrocarbons may also form in addition to those found with
HDPE and LDPE pyrolysis, as shown by the differences
in gas composition and molecular weight distribution
discussed earlier.
The oil/wax from the pyrolysis of PS was a mainly
aromatic product dominated by styrene and styrene
oligomers. In addition, the oil/wax contained a significant proportion of benzene, toluene, xylenes, and alkylated benzenes, indene and indane. Polycyclic aromatic
hydrocarbons, including, naphthalene, fluorene, and
phenanthrene and their alkylated derivatives, were also
detected. Table 7 shows the concentration of aromatic
compounds found in the oil/wax from the pyrolysis of
PS. Styrene has been detected as the major product from
the pyrolysis of PS by a number of workers.6,8,15 Other
compounds identified included, benzene, toluene, and
alkylated benzenes. The thermal degradation mechanism for PS has been shown to be via first chain scission
and then random scission.37 This results in the formation of the styrene monomer and also styrene dimer,
trimer, and tetramer.38 Other hydrocarbons formed by
the degradation process have been identified as benzene,
toluene, ethyl- and methylbenzene, naphthalene, and
other polycyclic aromatic hydrocarbons.8,37,38
The pyrolysis of PVC produced an oil which contained
almost exclusively aromatic compounds, even though
the basic structure of the polymer was a vinyl type. The
thermal degradation mechanism of PVC is initiated by
a dechlorination reaction resulting in the formation of
hydrogen chloride. The process of the elimination of a
chloride atom from the structure results in the forma(36) Turi, E. Thermal Analysis; Brandrup and Immergut: Berlin,
1966.
(37) Raave, A. Organic Chemistry of Macromolecules-An Introductory Textbook; Edward Arnold: London, 1967.
(38) Madorsky, S. L. Thermal Degradation of Organic polymers;
Interscience Publishers: New York, 1964.

Figure 5. Gas chromatogram of the oil derived from the

pyrolysis of LDPE/PS.

tion of a carbon double bond in addition to hydrogen

chloride.38 Further carbon double bonds are formed as
more hydrogen chloride is evolved from the resultant
chain. Eventually the chain undergoes cyclization to
yield aromatic and alkylaromatic compounds.38 Lattimer and Kroenke29 have suggested that hydrogen
chloride may promote cross linking through a DielsAlder-type mechanism. Benzene was the dominant
compound found in the oil at 30.7 wt %. Other aromatic
compounds identified included toluene, alkylated benzenes, naphthalene and alkylated naphthalenes, and
phenanthrene. Benzene has been identified as the main
product of PVC pyrolysis by Lattimer and Kroenke.29
Montaudo and Puglisi31 identified benzene, naphthalene, and other polycyclic aromatic hydrocarbons in the
thermal degradation product of PVC.
The PET oil/wax sample was analyzed by gas chromatography with flame ionization and mass spectrometric detection. However, poorly resolved and unidentifiable peaks were produced. From the FT-IR analysis,
the oil/wax product contains oxygenated compounds
which would not be well-resolved using the HT-5 type,
5% phenyl polycarborane-siloxane stationary-phase
capillary column used in the gas chromatograph-flame
ionization detection system or the DB5 type, 5% phenyl,
dimethylsiloxane stationary-phase capillary column
used in the gas chromatograph-mass spectrometric
system.
The oils derived from the pyrolysis of the plastic
mixturessHDPE/PS, LDPE/PS, PP/PS, PVC/PS, and
PET/PSswere analyzed in detail using gas chromatography with flame ionization and mass spectrometric
detection. The analyses produced complex chromatograms; for example, Figure 5 shows the gas chromatogram for the LDPE/PS oil, and Figure 6 shows the gas
chromatogram for the PVC/PS oil. The oil derived from
the pyrolysis of HDPE/PS and LDPE/PS contained both
aliphatic and aromatic species. The characteristic triplet
peaks of alkadienes, alk-1-enes, and n-alkanes were
prominent, as found for the pyrolysis of the single HDPE
and LDPE plastics. The carbon number range was up
to C52. Superimposed on the series of aliphatic compounds were aromatic compounds derived from PS. The
main aromatic compounds were styrene and styrene
oligomers derived from the pyrolysis of PS. Table 7

196 Energy & Fuels, Vol. 13, No. 1, 1999

Figure 6. Gas chromatogram of the oil derived from the

pyrolysis of PVC/PS.

Williams and Williams

chromatographic system used in this work. Others have

shown that the degradation products from PET pyrolysis are aromatic hydrocarbons containing oxygen such
as carboxyl, hydroxyl, and aldehyde groups.30
Overall it can be concluded that the mixing of the
plastic types produces a different product slate compared to the individual plastics pyrolyzed singly. Depending on the mixture of types, there are marked
increases or decreases in the aromatic species present
in the derived oils. Koo et al.10 analyzed the pyrolysis
oil from the pyrolysis of a HDPE/PS mixture using fixedbed pyrolysis; they also showed that the mixing of the
two plastics resulted in a change in product formation
when compared to pyrolytic products from the individual plastics pyrolyzed singly. They also reported that
the major aromatic product in the HDPE/PS pyrolysis
oil was styrene with naphthalene, trimethylbenzene,
and xylene also being present.
Conclusions

shows the analysis of the oils for aromatic hydrocarbons

for the mixtures; also shown is the analysis for PS
pyrolysis oil alone. Since one-half of the PS was present
in the mixture compared to PS pyrolysis alone, then if
the aromatic compounds in the mixture were merely
from addition of the two individual plastics, the results
in Table 7 would reflect a 50% reduction from those of
PS alone. The HDPE/PS and LDPE/PS oils showed in
some cases that the mixture produced much higher
concentrations of aromatic compounds than the individual plastics pyrolyzed alone. For example, benzene,
toluene, tetramethylbenzenes, and methylnaphthalenes
are much increased over that expected. Additionally,
some compounds are more reduced than would be
expected, such as indane and the dimethylnaphthalenes.
The pyrolysis of PP/PS resulted in an oil which was
mainly aromatic, in contrast to that of PP pyrolysis oil/
wax. The dominant species were styrene and styrene
oligomers. In addition, other aromatic compounds were
present, for example, benzene, toluene, xylenes, naphthalene, and alkylated naphthalenes. In some cases, the
compounds present were less than would have been
expected from the mixture of the individual plastics
pyrolysis oils, such as, trimethylbenzenes, indane, dimethylnaphthalenes, and phenanthrene.
The oil from the pyrolysis of the PVC/PS mixture gave
a wholly aromatic oil. The benzene concentration for
PVC pyrolysis alone was 30.7 wt %; with PS present
this was markedly reduced to 1.7 wt %. Other aromatic
and polycyclic aromatic hydrocarbons were not significantly higher to account for the reduction in benzene.
However, examination of Table 6 shows that the number
and weight averaged molecular weight data for the PVC/
PS oil show that this oil had the highest averaged
molecular weight. This coupled with the FT-IR data
which showed a very aromatic oil suggests that higher
molecular weight aromatic species are present in the
oils which could not be successfully analyzed using the
gas chromatographic system in this work.
The oil from the pyrolysis of the PET/PS mixture gave
a mainly oxygenated and aromatic hydrocarbon product.
Table 7 shows that the PET/PS oil was the only oil
containing oxygenated hydrocarbons. Other hydrocarbons could not be successfully resolved using the gas

The pyrolysis of the polyalkene plastics, HDPE,

LDPE, and PP, in a fixed-bed reactor were similar in
that they produced a hydrocarbon gas consisting of
hydrogen, alkane, and alkene gases and an oil/wax with
negligible concentrations of aromatic species with alkenes, alkanes, and alkadienes with carbon numbers in
the wax up to C53 detected. Higher molecular weight
compounds were identified as being present from the
molecular weight distribution data. There was no char
formed during the process. Pyrolysis of PS produced an
oil consisting of mainly styrene together with other
aromatic and polycyclic aromatic hydrocarbons. There
was only a low yield of gas and no char formation.
Pyrolysis of PVC also produced an aromatic oil; there
was also a significant formation of char; the main
product was, however, hydrogen chloride gas. Pyrolysis
of PET produced a large yield of gas mainly in the form
of carbon dioxide and carbon monoxide and a significant
production of char. The derived oil/wax contained oxygenated hydrocarbons, aliphatic, and aromatic groups.
The influence of mixing HDPE, LDPE, PP, PVC, and
PET in a 1:1 mixture with PS resulted in a much higher
gas yield than would be predicted from the single plastic
pyrolysis data. Increased concentrations of alkene gases
were produced due to mixing. The liquid product from
the mixed-plastic pyrolysis was an oil. The molecular
weight distribution and number and weight averaged
molecular weights of the oil produced from the mixed
plastics pyrolysis was markedly reduced due to the
process of mixing compared to those of the individual
plastic pyrolysis oil/wax. The detailed analysis of the
oils confirmed that there was clear evidence that mixing
of the plastics influenced the concentrations of individual chemical compounds in the derived oils.
Acknowledgment. We thank the U.K. Department
of Trade and Industry via the Energy Technology
Support Unit, Harwell, Oxfordshire for support for this
work through research Contract No. B/T1/00347/00/00
and David Wilson of BP Chemicals for the supply of
polymer samples. We also thank University of Leeds
personnel, Peter Thompson and Ed Woodhouse.
EF980163X