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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.
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
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
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
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.
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,
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).
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
HDPE/ LDPE/
PS
PS
PP/
PS
PVC/
PS
PET/
PS
310
340
230
290
420
130
3090
4810
3260
4590
na ) not available