J. Chem. T ech. Biotechnol.

1997, 70, 920

The Pyrolysis of Individual Plastics and a Plastic

Mixture in a Fixed Bed Reactor*
Elizabeth A. Williams & Paul T. Williams
Department of Fuel and Energy, University of Leeds, Leeds LS2 9JT, UK
(Received 21 June 1996 ; revised version received 18 November 1996 ; accepted 5 December 1996)
Abstract : Six thermoplastics, which represent more than two-thirds of all
polymer production in western Europe, were pyrolysed in a static batch reactor
in a nitrogen atmosphere. These were high density polyethylene (HDPE), low
density polyethylene (LDPE), polystyrene (PS), polypropylene (PP), polyethylene
terephthalate (PET) and polyvinyl chloride (PVC). The heating rate used was
25C min~1 to a nal temperature of 700C. These six plastics were then mixed
together to simulate the plastic fraction of municipal solid waste found in
Europe. The eect of mixing on the product yield and composition was examined. The results showed that the polymers studied did not react independently,
but some interaction between samples was observed. The product yield for the
mixture of plastics at 700C was 963% gas, 7511% oil, 287% char and 231%
HCl. The gases identied were H , CH , C H , C H , C H , C H , C H ,
2
4of oils
2 4were2 determined
6
3 6 using
3 8 Fourier
4 8
C H , CO and CO. The composition
4
10
2
Transform infra-red spectrometry and size exclusion chromatography. Analysis
showed the presence mainly of aliphatic compounds with small amounts of aromatic compounds.
J. Chem. T ech. Biotechnol. 70, 920 (1997)
No. of Figures : 11. No. of Tables : 7. No. of Refs : 26
Key words : plastics, pyrolysis, Fourier Transform infra-red spectrometry, chemical production

INTRODUCTION

government in the UK has set a challenge of recycling

25% of all household waste by the year 20006 and to
recover value from 40% of municipal waste by the year
2005.7
In the UK 74% of polymers were recycled via secondary recycling in 1991.18 The polymers used are
those separated from other waste. Uses of such recycled
materials are similar to those for the original virgin
polymer. However, in many cases the physical properties are inferior. In addition, in the food and drinks
industries for example, government legislation makes
recycled plastics unusable in food applications. Taking
into account the markets available for recycled plastic
materials it has been estimated that material recycling
rates can increase no higher than between 15 and 20%
of total waste generated.4,8,9 Therefore if government
targets are to be met, more mixed, and possibly contaminated, plastic will have to be dealt with. Current
technology for secondary recycling would nd it difficult to produce a product with enough added value for
the materials market.

In western Europe total plastic consumption in 1991

was over 24 million tonnes1 with packaging representing 39% of this. The amount wasted was estimated at
almost 17 million tonnes.1 Less than 4% of petroleum
resources are currently being used for polymer production,2 though this gure looks set to increase with
the development of new applications for both polymers
and copolymers multiplying. The car industry, for
example, is tending towards signicantly increasing
polymer usage in new vehicles.3
In 1990, less than 2% of eight major commodity
polymers were recycled, the rest being landlled or
incinerated.4 Recent gures show that 80% of waste
goes to landll, 10% is recycled and 10% is incinerated.5 Many governments have identied the plastic
waste problem as an area to be carefully controlled. The
* Presented in part at Clean Tech 96, London, 1921 June
1996.
To whom correspondence should be addressed.

9
( 1997 SCI.

J. Chem. T ech. Biotechnol. 0268-2575/97/$17.50.

Printed in Great Britain

E. A. W illiams, P. T . W illiams

10
TABLE 1
Caloric Value of Some Major Plastics Compared with Fuels

MATERIALS AND METHODS

Pyrolysis reactor

Sample

Caloric value (MJ kg~1)

Polyethylene
Polypropylene
Polystyrene

4650
4650
4190

Kerosene
Gas oil
Heavy oil

4650
4520
4250

Source : Ref. 23.

Table 1 lists the caloric values of some polymers

compared with some conventional fuels. The caloric
value of those polymers are comparable to the fuels
themselves, making their utilisation conceivable. Therefore, alternatives such as tertiary recycling are being
examined. This is dened as the recovery of monomers
or oil from waste plastic by a depolymerisation
process.4
Pyrolysis is such a tertiary recycling process. The
polymer sample is heated in an inert atmosphere
causing the carboncarbon bonds to break along the
polymer backbone. This depolymerisation process
results in monomers or short chained compounds being
formed. Generally three product types are formed from
a pyrolysis reaction, that is a gas, oil and char. All have
the potential for use as a fuel or chemical feedstock and
thus bring an intrinsic value to the whole process.
More research concerning plastic pyrolysis has been
carried out in the last decade than ever before. Japan
has developed a method for decomposing polyolens.
The Fuji process uses catalysts to form a gasoline-rich
oil from polyethylene, polypropylene and polystyrene.10
Work in Europe has dominated the area and
researchers at Hamburg University have played an
important role. Polymers such as polyethylene, polypropylene and tyres under dierent reaction conditions
have been pyrolysed.11 Also in Germany, the energy
and chemical company, Veba, is operating a plastic
recycling process by which used polymers are hydrocracked into a synthetic oil.8 BASF has recently built a
pilot plant for the production of naphthas, olens and
aromatics from mixed plastic wastes.8 In the UK, BP
Chemicals is leading a consortium in developing a plastics recycling plant. Their process is based on uid bed
technology and the resultant waxes have been shown to
be suitable for feeding straight into a steam cracker for
ethylene production.8 Pinto et al. pyrolysed plastic
waste at 430C in an autoclave to yield more than 80%
liquid and less than 5% gas. Roy13 in Canada has
focused on plastic pyrolysis using vacuum technology.
Much of the previous research has mainly concentrated on the pyrolysis of single polymers. This paper
examines the issue of pyrolysing both single and mixed
plastic wastes for further utilisation

The pyrolysis unit used was a xed bed, batch reactor.

A schematic diagram of it is presented in Fig. 1. This
was stainless steel, having an internal diameter of
37 mm and being 250 mm in length. The top was sealed
with a stainless steel ange and reinforced gasket. The
carrier gas was nitrogen and this was passed into the
top of the reactor at a rate of 200 cm3 min~1. This
purge gas removed the reaction products from the reaction site and reduced the extent of secondary reactions.
These can occur if volatiles are subjected to long
residence times in the hot reactor.14 The nitrogen ow
rate used gave a residence time of 25 s through the hot
reaction zone.
High density polyethylene (HDPE), low density polyethylene (LDPE), polystyrene (PS), polypropylene (PP),
polyethylene terephthalate (PET), and polyvinyl chloride (PVC) were the thermoplastics used. These are the
six polymers most commonly found in domestic waste
and represent more than two-thirds of all polymer production in western Europe.15 A mixture of these which
represented 95% of the plastic fraction of municipal
waste found in Europe1 was also used. The composition
of this fraction is shown together with the normalised
percentages for the polymers actually pyrolysed in this
study in Table 2. The polymer 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 temperature of the
sample was measured using a type K thermocouple.
This was in direct contact with the sample. The whole
reactor was externally heated by an electrically heated
ring furnace. The temperature programme used was
25C min~1 to a nal temperature of 700C. This temperature was held until no more gas was produced.
The pyrolysis vapours were swept down through the
bottom of the reactor and rapidly condensed in a series
of four glass condensers. Dry ice and acetone was used
as the cooling agent giving an approximate temperature
of [78C. A glass wool trap was put in series after the
TABLE 2
Percentage of Each Polymer Used in the Simulated Plastic
Fraction of Municipal Solid Waste Used in this Study
Polymer

Percentage (%)

LDPE
HDPE
PP
PS
PVC
PET

3125
3125
729
135
1146
521

Source : Ref. 1.

Pyrolysis of plastics in a xed bed reactor

11

Fig. 1. Schematic diagram of xed bed reactor.

condensers to catch any oil particles which were not

trapped in the condensers. The remaining gases were
then collected in a gas bag.

HCl analysis
During the pyrolysis of PVC and the plastic mixture, a
dreschel bottle of de-ionised water was placed in-line.
All the gas was bubbled through with the aim of dissolving any HCl produced by PVC degradation. The
HCl in H O samples were analysed using a Corning
2
pH/ion meter 135 with a chloride electrode calibrated
between 100 and 1000 ppm. A double junction reference
electrode lled with 1 molar KNO with a xed poten3
tial was used in conjunction with the chloride electrode.
The chloride ions migrating to the chloride electrode
resulted in a dierence in potential compared with the
reference and a direct ppm reading could be taken.

Gas analysis
The evolved gas was collected in a 10 dm3 Teon bag
and then analysed o-line using three packed column
gas chromatographs. Hydrocarbons were analysed
using a GCD chromatograph with a 22 m ] 6 mm

glass column packed with 80100 mesh n-octane

Porasil C. Permanent gases were identied on a Pye 204
chromatograph with a 18 m ] 6 mm stainless steel
column packed with molecular sieve 5 . Carbon
dioxide analysis was carried out on a Gow Mac chromatograph with a 18 m ] 6 mm stainless steel column
packed with 100120 mesh silica gel. A ame ionisation
detector identied the hydrocarbons and thermal conductivity detectors were used to determine the other
gases. Data manipulation was carried out using a
Harley Peakmaster data analysis system. Three samples
were injected into each gas chromatograph to increase
the condence of the results. The gases identied were
permanent gases, CO and CO and hydrocarbons up to
2
C . The total weight of gas produced was calculated by
4
comparison to the known nitrogen ow rate.
Elemental analysis (CHN)
During pyrolysis a char was formed in the metal crucible where, after cooling, it was retrieved and analysed.
Polyvinyl chloride and polyethylene terephthalate were
the only polymers to produce signicant amounts of
char. Chars were analysed on a Perkin-Elmer model
240C elemental analyser. Each sample was analysed
twice.

E. A. W illiams, P. T . W illiams

12
Fourier Transform infra-red spectrometry (FTIR)
Functional group analysis of each pyrolytic oil and wax
was carried out using Fourier Transform infra-red spectrometry. A Perkin-Elmer 1750 spectrometer was used
which had data processing and spectral library search
facilities. A small amount of the liquid fraction derived
from the polymer pyrolysis was mounted on a handmade potassium bromide (KBr) disc which had been
previously scanned as a background. The infra-red
spectra of the sample was then taken. The resulting
spectra were normalised to the CwH peak around
3000 cm~1. Direct comparisons of peak intensity could
then be taken.
Size exclusion chromatography (SEC)
Size exclusion chromatography, also known as gelpermeation chromatography, is a non-destructive
method which gives information on the molecular
weight distribution of the sample. The equipment used
was similar to that of HPLC. The columns were two
46 ] 150 mm 5 km RPSEC 100 type in series. This
method diers from HPLC in that the elution order is
in reverse molecular size, i.e. the largest molecule is
eluted rst. Two detectors were used in series, these
being a refractive index detector and an ultra-violet
detector, enabling the extent of sample aromaticity to
be determined. The analytical equipment was linked to
a chart recorder in addition to a computer with data
processing facilities. A small amount of the oils and
waxes were dissolved in 10 cm3 of tetrahydrofuran
(THF). This solvent was also the eluent through the
system.
RESULTS
Mass balances
The product yields for each individual plastic and the
plastic mixture are shown in Table 3. All polymers produced a hydrocarbon gas and an oil or waxy fraction.
Some polymers produced a small amount of char. Polyvinyl chloride also produced HCl gas upon heating.
Polypropylene gave the largest amount of pyrolytic oil

and PVC the smallest with the respective yields being

85% and 3169%. Oil was the major product formed
from the pyrolysis of all polymers with the exception of
PVC where HCl gas was the dominant product.
The appearance of the liquid products was varied.
HDPE, LDPE and PP all gave a light coloured waxy
product. PS produced a red/brown liquid, whereas both
PVC and PET gave a dark almost black heavy liquid.
The gases produced were a comparatively minor
component when compared with the oil yield. However,
in the main, all gases were deemed potentially useful
due to their hydrocarbon nature. HDPE, LDPE and
PP yielded similar quantities of gas. PS and PVC produced only very small amounts. PET made the largest
volume of gas. However, due to the oxygen present in
its structure (see Fig. 2), upon depolymerisation the
major part was carbon dioxide, with this representing
more than 66% of the gas yield.
PET and PVC gave a large amount of char, the yields
being 155% and 1692% respectively. Wenning16 noted
that PVC showed a coke formation of approximately
20% by weight.
A theoretical product yield for the plastic mixture
was calculated from the experimental yields obtained
for each individual polymer. The theoretical and experimental results were comparable. The liquid fraction collected was a dark waxy substance, though less viscous
than the waxes from HDPE, LDPE or PP pyrolysis.
The gas yield of 964% was lower than the theoretical
value of 13%. The reason for this may simply be due to
a smaller number of secondary reactions. The HCl collected from the mixture was almost one-third of that
expected. This may be due to the occurrence of organochloride compounds in the oil fraction. Comparisons of
the product yields between plastics and products are
more clearly presented in Figs 3a and 3b.
The mass balances obtained by other researchers
dier widely depending on the reaction conditions used.
Kaminsky11 found that using polyethylene as a feed, up
to 50% of the input material can be retrieved in the
liquid form. Here the wax yield for polyethylene was
more than 80% at 700C. Using mixed plastic waste in
a rotary kiln pyrolysis unit Wenning16 obtained a
product composition of gas 3050%, oil 4050% and
coke 515% at pyrolysis temperatures between 650 and

TABLE 3
Comparison of Product Yields from the Pyrolysis of Polymers in a Fixed Bed
Reactor (%)

Gases
Oil
Char
HCl
Total

HDPE

L DPE

PS

PP

PET

PV C

Mixture

1677
7972
000
000
9648

1502
8425
000
000
9927

341
8377
350
000
9067

1363
8444
015
000
9823

3399
4130
1555
000
9084

247
3169
1378
5293
10087

963
7512
287
231
8993

Pyrolysis of plastics in a xed bed reactor

13

Fig. 3b. Comparison of products from the pyrolysis of six

thermoplastics and a plastic mixture in a xed bed reactor.

Fig. 2. Structures of repeating units of the thermoplastics

used.

850C. The aim of the work presented here is oil production. More than 75% of the yield from the pyrolysis
of a mixture was a liquid fraction.
Gas analysis
The gases identied were hydrocarbons up to C
4
including methane, ethane, ethene, propane, propene,
butane, butene, plus carbon dioxide, carbon monoxide
and hydrogen.

The evolution of gases from HDPE, LDPE, PP and

PVC were similar. This is due to their comparable
structures (Fig. 2). Each polymer contains the monovalent group of atoms CH CHwX with their dier2
ences being introduced with a change in the X-group.
All thermally degrade through random scission17,18 to
give a wide product size distribution. The temperature
at which degradation begins is between 300C and
450C. The thermal behaviour of polyvinyl chloride
diverges slightly from the other similarly structured
polymers. The CwCl bond in PVC has a lower bond
energy than other bonds in its structure,19 as Table 4
shows, and upon heating it is this bond which is primarily broken. Therefore, PVC degradation begins
around 150C which is a much lower temperature
than for the other polymers. The intermolecular chain
transfer
reaction
which
follows
leads
to
dehydrochlorination20 and HCl gas is evolved. This
contains until 90% of the Cl present in the structure has
been given o. The empirical formula of PVC is such
that, upon heating, the chlorine yield is 56% of the original sample. Once dehydrochlorination is complete
PVC yields hydrocarbon gases consistent with a vinyl
polymer.
The results of the gas evolution from the pyrolysis of
all polymers are given in Table 5. The gures are represented in terms of weight/weight percentage, i.e. as a
percentage of the original sample. It is evident that the
percentage of alkenes, less than or equal to C , is much
4
greater than alkanes. In some cases the ratio is 3 : 1.
Hydrogen is the smallest contributor to the gas stream.
TABLE 4
Bond Energies Found in the Polymers Used

Fig. 3a. Comparison of product yields with the pyrolysis of

six thermoplastics and a plastic mixture in a xed bed reactor.

Bond

Dissociation energy
(kcal mol~1)

CwC
CxC
CwH
CwO
CwCl

83
146
99
86
81

E. A. W illiams, P. T . W illiams

14

TABLE 5
Total Gases Evolved from the Pyrolysis of Polymers and a Polymer Mixture (Wt/Wt%)

HDPE
LDPE
PS
PP
PET
PVC
Mixture

Hydrogen

Methane

Ethane

Ethene

Propane

Propene

Butane

Butene

CO
2

HCl

012
005
004
005
031
012
008

190
114
053
093
071
077
097

221
167
008
145
003
047
101

608
400
026
352
141
015
167

131
133
002
100
013
024
070

456
400
005
353
009
019
083

022
032
000
023
000
011
014

036
200
006
129
000
015
220

126
059
116
331
2271
026
206

000
000
000
000
000
5293
231

Kaminsky and Sinn,21 in their research of PE and PP

pyrolysis, found much higher percentages of gaseous
hydrocarbons at temperatures of 740C and 830C.21
However, the trend of more alkenes than alkanes with
negligible amounts of hydrogen was the same as found
here. Thereafter, there is a tendency for the smaller
alkenes to dominate the mixture, with the trend being
ethene [ propene [ butene. This is particularly apparent with HDPE, LDPE and PP pyrolysis. Taylor22
found this trend with both alkanes and alkenes for
polyethylene, polypropylene and tyre pyrolysis. PVC
evolved a larger proportion of small compounds than
large compounds. However, methane evolution dominated the hydrocarbon product mixture. Polystyrene
and polyethylene terephthalate both yielded negligible
amounts of hydrocarbon gases although methane and
ethene were the major contributors in each case. The
gas trends are more clearly seen in Fig. 4.
Since the gaseous fraction is a signicant portion of
the products it is important to determine whether the
resultant gas has any value. Many researchers have sug-

gested that the gas generated from the pyrolysis reaction could be reburnt so as to increase the energy
balance of the process.12 The caloric value of the gas is
therefore considered to be important. North Sea gas has
a gross caloric value of 386 MJ kg~1.23 The hydrocarbon gases produced here all have a gross caloric
value greater than 45 MJ kg~1 23 and so it is clear that
the gases produced could provide energy to the process.

Elemental analysis (CHN)

Table 6 shows the elemental analysis of the chars produced. The majority element is carbon in all cases. This
is to be expected, since during depolymerisation the
weakest points of the structure break rst resulting in
the production of a more thermally stable product.
Carbon to carbon triple and double bonds are among
the hardest to break (see Table 4) and so it follows that
mainly carbon will remain in the char. Little hydrogen
was present and there was a negligible amount of nitro-

Fig. 4. Comparison of hydrocarbon gas yields from the pyrolysis of each individual plastic and a plastic mixture in a xed bed
reactor.

Pyrolysis of plastics in a xed bed reactor

15

TABLE 6
Elemental Analysis of Chars from the Pyrolysis of Polymers
and Polymer Mixture in a Fixed Bed (%)

Carbon
Hydrogen
Nitrogen
Ash

Pet

PV C

Mixture

8493
248
000
586

9015
255
015
291

8773
199
013
423

gen, indicating no interaction between the sample and

the carrier gas.
If the percentage of oxygen in the chars is taken as
being the dierence between the whole char and the
results presented in Table 6 then it is evident that the
char from PET pyrolysis has a signicant amount of
oxygen, that is 673%. This may be due to the presence
of oxygen within the original polymer structure. The
amount of ash in the PET char is also quite high, especially when compared with that of PVC.
A theoretical elemental composition for the char
obtained from the mixture can be made from the data
gained from the individual polymer chars. It was
observed that the theoretical and experimental results
were similar. However, the experimental results show
less carbon and hydrogen and a notable increase in the
amount of char.
Oil analysisFourier Transform infra-red spectrometry
The FTIR spectra obtained for the pyrolysis oils from
HDPE, LDPE, PP, PS and PVC are similar due to

their similar structure. Figure 5a shows the spectra of

HDPE, LDPE and PP pyrolysis oils, Fig. 5b shows the
spectra of PS, PVC and PET pyrolysis oils and Fig. 5c
shows the spectrum obtained for the polymer mixture
pyrolysis oil.
HDPE, L DPE and PP pyrolysis oils
The area of the spectrum between 3000 cm~1 and
2800 cm~1 shows the presence of wCH , wCH and
3
2
CwH groups. The peak preceding these at 3050 cm~1
is an indication of the presence of alkenes. HDPE,
LDPE and PP all have sharp peaks in these regions
which dominate their spectra. This illustrates the highly
aliphatic nature of the oils produced. More evidence of
saturated alkane groups and substituted alkenes appear
between 1500 and 1400 cm~1. Peaks found at approximately 1380 cm~1 and 1320 cm~1 reinforce the identication of molecules with CwCH and CwH bonds
3
respectively.
PV C pyrolysis oil
Polyvinyl chloride, as expected, has strong absorption
peaks in aliphatic regions of the spectra. It also has
peaks which are between 3500 and 3000 cm~1 showing
the presence of xCwH stretches and, consequently,
aromatic compounds, though the intensity of the
absorption is only small. As mentioned earlier almost
90% of the chlorine content of PVC is evolved as HCl.
So, the presence of absorption bands representative of
Cl bonded groups was negligible within the oil. The
pyrolytic oil from PVC is therefore very similar to that

Fig. 5a. FTIR spectra of HDPE, LDPE and PP pyrolysis oils.

E. A. W illiams, P. T . W illiams

16

Fig. 5b. FTIR spectra of PVC, PS and PET pyrolysis oils.

produced from the pyrolysis of polyethylene and polypropylene. There does, however, seem to be an increase
in the amount of aromatic compounds here.
PS pyrolysis oil
Polystyrene diers slightly from the other vinyl polymers. Again CH and CH groups are identied
3
2

between 2950 and 2850 cm~1 showing the presence of

short and long chains of both alkanes and alkenes. The
peaks between 1420 cm~1 and 1400 cm~1 show the
presence of alkenes and those at 1460 cm~1 and
1380 cm~1 again relate to an alkane structure. In addition three peaks just above 3000 cm~1 are very intense,
illustrating the highly aromatic character of the oil orig-

Fig. 5c. FTIR spectra of the pyrolysis oil derived from the plastic mixture.

Pyrolysis of plastics in a xed bed reactor

inating from the benzene ring present in the polymer
structure. Benzene ring substitution patterns also occur
in the region between 1950 and 1650 cm~1. Mono-, diand tri-substituted benzene rings could attribute for the
absorption peaks in the region 780750 cm~1.
PET pyrolysis oil
The presence of oxygen within the PET structure leads
to the identication of many dierent functional groups.
There is a very broad stretching around 3400 and
3200 cm~1. This could be due to intramolecular OH or
hydrogen-bonded OH groups. Thus, there is a likelihood that this pyrolytic oil contains some alcohols and
possibly some carboxylic acids. Some aldehyde structures have been noted primarily around the 950
900 cm~1 region. There is also an indication of
aromatic CwH around 3040 cm~1 and 3020 cm~1 in
the polyethylene terephthalate spectra. Again, peaks are
indicative of some alkenes being present. The pyrolytic
oil from polyethylene terephthalate pyrolysis has the
functional groups which correspond to the presence of
aldehydes, ketones, carboxylic acids, alcohols and aromatic compounds possibly substituted with one of these
functional groups.
Polymer mixture pyrolysis oil
The polymer dominating this simulated plastic fraction
of municipal solid waste is polyethylene. It follows that
the spectrum of the mixture is extremely similar in its
outline to that of polyethylene. However, on closer
examination the spectrum is much more complex.
The peak between 3100 and 3000 cm~1 could be due
to the presence of xCwH stretch associated with aromatic homocyclic compounds. Aromatic compounds
could be expected with the inclusion of polystyrene in
the mixture. Aromatic absorption bands also feature
elsewhere in the spectrum. A small peak at 1500 cm~1
shows in-plane deformation of CxC. The much larger
peak at between 1460 and 1440 cm~1, which is possibly
an overlap of two peaks, could also infer CxC in-plane
deformation. The peaks between approximately 950 and
680 cm~1 show aromatic groups. Those, particularly at
900, 890 and 780 cm~1 represent CwH out-of-plane
deformations which are characteristic of aromatic
groups.
Groups with an oxygen atom are also reasonably distinct. There is broad stretching around 3400 and
3200 cm~1 due to intramolecular OH or hydrogenbonded OH groups. A strong absorption peak at
1380 cm~1 can be attributed to CwO stretching and
OwH in-plane deformations in tertiary alcohols and
phenols. A smaller peak around 1320 cm~1 could be
due to primary and secondary alcohols. CxO stretching vibrations observed at between 1680 cm~1 and
1650 cm~1 suggest, therefore, the presence of carboxylic
acids in addition to alcohols. Aldehydes and ketones
also contribute to the oil matrix. Peaks at around

17
975 cm~1 and 1280 cm~1 show the presence of these
groups.
In summary, the FTIR spectrum of the polymer
mixture shows the presence of many of the groups mentioned in the matrix of each individual polymer pyrolysis oil. However, the aromatic groups and some
oxygenated groups in particular seem to account for a
much larger amount than can be attributed simply to
the accumulation of the single polymer degradation
reactions. It is possible, therefore, that the primary products formed initially from each polymer react with different products than if only a single polymer were being
pyrolysed. This results in dierent secondary products
being formed. This is not necessarily true for all collisions but there is some evidence that interaction
between primary degradation products do occur.

Oil analysissize exclusion chromatography

It has been suggested that one possible use of the liquid
products from plastic pyrolysis is as a chemical feedstock.12,24,25 If this is to become a reality then the oil
must have sufficient properties to be substituted into
existing petrochemical processes.
BP Chemicals found that the wax produced from the
pyrolysis of plastics can be mixed with naphtha at up to
20%.8 This can then be fed to a steam cracker without
signicantly altering the process. Naphtha is a cut of
crude oil and has a boiling range between 120C and
180C. It consists of a complex mixture of hydrocarbons
and could have a similar composition to the waxes produced in this research. One important characteristic of
feedstocks used in petrochemical processes, such as
steam cracking and catalytic cracking, is the molecular
weight distribution and the boiling point range. It was
therefore thought important to look at the molecular
weight characteristics of the pyrolysis oils to see
whether they are comparable with existing petrochemical feedstocks.
Size exclusion chromatography was used to determine the molecular weight distribution of each pyrolysis
oil and wax sample. The results of SEC are presented
both as RI and UV. n-Alkanes are not absorbed in UV
light and so the use of the two detectors can yield values
for both aliphatics and aromatics in the oil. Analysis of
the oils and waxes produced from both the individual
polymers and the polymer mixture gave a weight distribution between a molecular weight value of 64 and
2000 daltons (Da). However the vinyl polymers had the
largest range due to the random nature of the depolymerisation reaction.
Table 7 shows the size exclusion data for the pyrolysis oils. The polydispersity gives an indication of the
number of diering sized components in the sample. So,
if the sample was a pure compound then its polydispersity is equal to one. The polydispersity values for PS
and PET are 121 and 109 respectively, whereas for the

E. A. W illiams, P. T . W illiams

18

TABLE 7
SEC Data for Pyrolysis Oils from Polymers and a Polymer Mixture in the Fixed Bed Reactor
Polymer
HDPE

L DPE

PS

PP

PET

PV C

Mixture

UV detector
Number average MW
Weight average MW
Polydispersity

178
281
158

208
250
121

116
147
127

280
439
157

210
276
132

230
384
167

136
209
153

RI detector
Number average MW
Weight average MW
Polydispersity

240
360
150

209
306
146

145
176
121

241
403
167

195
212
109

251
334
128

125
165
132

other pyrolysis oils the gure is much larger, ranging

between 167 and 128.
The size exclusion chromatography graphs have been
plotted with weight percentage against a log molecular
weight. A log scale enables examination of the data for
low molecular weight compounds which would otherwise be restricted on a linear scale.22 Figures 6a, 6b and
6c show the molecular weight of pyrolysis oils from
polystyrene, polyethylene and the plastic mixture
respectively. For most of the polymers there were two
regions of diering molecular weights within each
sample. The gures from the refractive index detector,
illustrating the oil/wax as a whole, show a peak between
a log molecular weight value of 18 and 27 and then a
second peak in the range 2734 for all polymers except
PVC and PET. Here only one molecular weight range
was observed.
For LDPE, HDPE, PP and PS the rst peak representing smaller molecular weight compounds is larger

than that showing heavier molecules. The amount of the

LDPE wax with a molecular weight less than log 27 or
500 Da is 87%. For HDPE, PP and PS this gure is
75%, 70% and 62% respectively. Although only 62% of
the polystyrene pyrolysis oil had a molecular weight of
500 Da or less the maximum molecular weight of a
component was found to be only 907 Da. Polystyrene is
known to degrade with an unzipping reaction to form
mainly its monomer.26 So a small gure for the molecular weight range is expected. When presented as boiling
points, (Figs 6a, 6b and 6c) the results indicate that at
least 70% of the waxes and 62% of the polystyrene oil
have a boiling range between approximately 46C and
379C. The modal boiling point for LDPE, HDPE and
PP is 270C. For PS this is greatly reduced to only
126C.
The results for the pyrolysis oils from PVC and PET
are very similar to the others in that their log molecular
weight is between 18 and approximately 34. However,

Fig. 6a. Molecular weight and boiling point distribution of

LDPE pyrolysis oils.

Fig. 6b. Molecular weight and boiling point distribution of

PS pyrolysis oils.

Pyrolysis of plastics in a xed bed reactor

Fig. 6c. Molecular weight and boiling point distribution of

pyrolysis oils derived from a plastic mixture.

only one range is observed. Again the modal boiling

point for the oils is 270C.
The pyrolysis oil from the plastic mixture has a
molecular weight range similar to the wax from polyethylene pyrolysis. There are two molecular weight
ranges, with 73% of the oil having a molecular weight
less than log 24 or 250C. The modal boiling point (see
Fig. 6c) is much less than that found for either high or
low density polyethylene, but is more in agreement with
that found for a polystyrene oil. Therefore, even though
polyethylene was the major component of the original
sample mixture, the characteristics of the oil do not
match so that the presence of several polymers together
results in smaller products being formed upon heating.
The resultant oil from the mixture seems at rst
glance to be better placed than either HDPE, LDPE or
PP to be used as a feed for a steam cracker. The boiling
range is quite low, around that of naphtha itself.
Analysis of the oil has shown that a signicant proportion of the oil product has an aromatic nature. If it is to
be used alongside naphtha, then more detailed investigations of its performance in such processes will have to
be carried out. Work done so far shows promising
results.

CONCLUSIONS
The quantity of the oil fraction produced from four of
the six thermoplastics and the polymer mixture is
approximately equal to, or greater than, 80%. This high
yield is clearly benecial to any process utilising the oil
fraction. In addition, the gaseous fraction consists of
high heating value hydrocarbons which have the potential to be used as a fuel.

19
Analysis of the pyrolysis oils has shown that the composition of those from HDPE, LDPE, PP, PVC and the
polymer mixture is mainly aliphatic. PS has a more
complex composition with mainly aromatic components and PET yields mainly oxygenated and aromatic compounds. All have the potential for chemical
feedstock production.
The molecular weight of each pyrolysis oil is between
64 and 2000 Da. For the majority of the samples each
has a modal boiling point of 270C. When mixed
together the boiling point range was reduced giving a
peak at only 126C. This is within the boiling point
range of the naphtha feed used in a steam cracker for
ethylene production and so pyrolysis oil from mixed
plastic could possibly be substituted into this chemical
process.
The pyrolysis of individual polymers and their
mixture give three products which all have the potential
to be used as fuels or chemical feedstocks. More
research into optimum reaction conditions for the formation of the most useful products will prove invaluable for future waste utilisation eorts.

ACKNOWLEDGEMENTS
The authors would like to thank the Department of
Trade and Industry via the Energy Technology Support
Unit, Harwell, Oxfordshire for support for this work
(Grant number B/T1/00397/00/00) and also, BP Chemicals for the supply of polymer samples.
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