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Polymer Degradation and Stability 70 (2000) 373385

www.elsevier.nl/locate/polydegstab

Pyrolysis of mixed polyolens in a uidised-bed reactor and on a


pyro-GC/MS to yield aliphatic waxes
M. Predel, W. Kaminsky *
Institute of Technical and Macromolecular Chemistry, University of Hamburg, Bundesstrasse 45, D-20146 Hamburg, Germany
Received 19 April 2000; accepted 18 May 2000

Abstract
Polyolens (PE, PP and PS) were pyrolysed in a uidised-bed reactor on kilogram scale at 510 C. Pyrolysis products were analysed with GC, GC/MS and other methods. It was shown that valuable products, mostly aliphatic waxes, are received from polyolens. It was also investigated if mixtures of dierent polyolens (PE, PP, PS) interact with each other in uidised bed pyrolysis
yielding dierent pyrolysis products than received from the pure, individual polyolens. The same polymer mixtures were also
analysed using a pyro-GC/MS-device. # 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Pyrolysis; Polyolens; Polyethylene; Polypropylene; Polystyrene; Fluidised bed reactor; Pyro-GC/MS

1. Introduction
In 1997 the total consumption of plastics was
27,281,000 t in the European Union. More than 10 million t were polyethylenes (HDPE/LDPE/LLDPE) and
nearly 6 million t were polypropylene (PP). Polyvinyl
chloride (PVC) and polystyrenes (PS/EPS) followed
with a consumption of 4.6 million or 2.7 million t
respectively. Forty-two per cent of all plastics were used
for packaging [1].
A huge amount of plastic waste is collected from german households every year by the DSD (Duales System
Deutschland). After sorting out the PVC by specic
weight in a water bath a polyolen mixture remains
(polyolen light fraction). This mixture consists mostly
of polyethylene (PE), polypropylene (PP) and polystyrene (PS). A possible way to recycle these plastics is
to pyrolyse them in a uidised bed reactor (Hamburg
Pyrolysis Process). This well established and optimised
technical pyrolysis process was developed in the 1970s [2].
At 700 C aromatics and olenic gases are the main
products from polyolen feedstock [3]. When the uidising gas is replaced by steam, olens are the main
products [4,5].

* Corresponding author. Tel.: +49-40-428383162; fax: +49-40-428386008.


E-mail address: kaminsky@chemie.uni-hamburg.de (W. Kaminsky).

At temperatures of only about 500 C aliphatic waxes


are the main products from polyolen input material. A
pyrolysis temperature of 510 C was found to be an
optimised temperature for feedstock recycling of mixed
polyolens. The products with a boiling point below
500 C were planned to be used as (co-)feed in a steamcracker to yield back monomers for polymer production. The waxes with a boiling range above 500 C were
planned to be used in a catalytic cracker (FCC-process)
to yield petrochemical products. In previous investigations it remained unclear if the pyrolysis products from
mixed plastics pyrolysis in a uidised bed dier from a
simple addition of the decomposition products from the
individual plastics [6,7].
The Hamburg pyrolysis process was also applied successfully to pure polystyrene. More than 60% monomer
and 25% of other aromatics were received at a pyrolysis
temperature of 515 C [8].
It was reported that the addition of some PS to polyolen feedstock (PE, PP) accelerates the pyrolysis and
leads to decomposition products with a shorter chain
length, e.g. more volatile products.
When 2040 g of a PE/PS mixture were heated in a
quartz retort at 48 K min1 up to 500, 600 or 700 C the
formation of low boiling products was favoured. More
oil was obtained than expected from addition of both
individual polymers [9].
The xed bed pyrolysis of a mixture (3 g) of PE/PS as
well as PP/PS at a heating rate of 25 K min1 up to

0141-3910/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.
PII: S0141-3910(00)00131-2

374

M. Predel, W. Kaminsky / Polymer Degradation and Stability 70 (2000) 373385

700 C resulted in dierent pyrolysis products than


expected from the pure polymers, too. The amount of
gases evolved was tripled (PE/PS-mixtures) or doubled
(PP/PS-mixture) in comparison to the pure polymers
[10,11].
Using a cascade of three circulated-spheres-reactors
(330/380/440 C, feed max. 3 kg h1) for stepwise pyrolysis of mixed, molten plastics, an interaction of PS and
PE was discovered. An enhanced amount of ethylbenzene was found in the pyrolysis products of PS. The
formation of ethylbenzene is accompanied by the formation of more olenic compounds during PE pyrolysis. This was explained by a hydrogen transfer from
PE to PS. To investigate these interactions further
experiments were made under isothermal conditions
with on-line mass spectrometry of blends of PE and PS
(30 mg samples). The apparent activation energy for the
thermal degradation of PE was found to be decreased in
presence of PS at temperatures from 410 to 480 C. The
production of volatile products from PE was accelerated, especially during the initial phase of the decomposition. More unsaturated pyrolysis products from PE
were received [12].
It was not reported if this accelerating eect of mixed
plastics could also be found in uidised bed pyrolysis, in
which the material to be pyrolysed as well as the degradation products are only exposed to cracking temperature for a short time period. The following experiments
have been performed to investigate if this eect can also
be found in uidised bed pyrolysis.

It was also examined how the same samples of mixed


polyolens behave in pyrolysis in a Pyro-GC/MS-analyser and if an eect on the pyrolysis products by mixing
the polymers can be observed there.
2. Experimental
2.1. Input materials
The polyolens used were pellets of about 24 mm in
diameter. Their labellings were: PE: Ladene high density
polyethylene, Sabic Marketing Ltd, PP: polypropylene
4L609, Shell Chemicals, PS: polystyrene 143 E, AlbisPlastic, Hamburg.
2.2. Pyrolysis plant and experiments
2.2.1. The uidised bed reactor
The pyrolysis experiments were carried out on the
LWS 4 pyrolysis plant at our institute. A general ow
scheme is shown in Fig. 1.
The LWS 4 was designed for a throughput of 13
kg h1 of organic material. The reactor consisted of a
steel tube (length 1220 mm, 130 mm inner diameter).
The gas distributor was a steel plate with 150 tubes
(2.50.75 mm) which were formed into hooks, thus
ensuring that no uidising quartz sand (8 kg, 0.30.5
mm diameter) could fall through the plate. The uidising plate (gas distributor) divided the tube in the gas

Fig. 1. Fluidised bed pyrolysis plant.

M. Predel, W. Kaminsky / Polymer Degradation and Stability 70 (2000) 373385

375

Table 1
Process parameters of uidised bed pyrolysis experiments
Experiment

#01

#02

#03

#04

#05

#06

#07

#08

#09

100

100

60
40

40
60

90

10

100

90
10

54
36
10

100

Temperature in uidised bed (botton),  C


Temperature in uidised bed (top),  C
Freeboard temperature,  C
Duration of input, h:min
Troughput of polymer, g/h
Gas residence time in the reactor, s
Gas stream (cold, before compressor), m3/h

5133
5163
4656
4:20
826.2
5.6
3.70

5121
5161
4474
5:15
952.4
4.6
4.40

5102
5132
4773
3:45
1066.7
4.3
4.80

5101
5161
4681
3:55
1021.3
4.1
4.9

5122
5172
4451
3:42
973.0
4.1
4.90

5103
5143
4582
3:48
1052.6
4.2
4.85

512 1
5141
4711
3:55
1020.4
4.0
5.00

5131
5151
4701
3:50
1043.5
4.1
4.95

5142
5152
4701
3:52
967.7
3.9
5.10

Product fractions before work-up Gases, g


Oils, g
Waxes, g
Soot, g
Total products, g
Polymer input, g
Loss (), gain(+), g
Recovery rate,%

246.1
1054.5
2208.3
9.1
3518
3500
18
100.5

127.2
523.4
4331.8
8.5
4991
5000
9
99.8

169.5
682.1
3123.8
4.5
3980
4000
20
99.5

167.7
708.8
3079.5
7.1
3933
4000
37
99.1

72.7
550.3
2959.0
1.3
3583
3600
17
99.5

222.0
1224.7
2506.2
3.1
3956
4000
44
98.9

177.2
1378.0
2434.8
3.0
3993
4000
7
99.8

103.2
892.5
2939.0
5.6
3940
4000
60
98.5

83.6
270.2
3135.8
6.2
3496
3500
4
99.9

Input material

% PE
% PP
% PS

preheating zone and the uidised bed reactor zone.


Above the uidised bed zone another tube (length 500
mm, 158 mm inside diameter) was added to reduce the
vertical gas velocity inside the reactor. Because only
very little carbon black was found on the sand (0.050.1
wt%) after the experiments, the same sand was used for
the next experiments again.
The polymers were mixed in an extruder device (type
Arburg Allrounder 100 UR) connected to the reactor to
ensure a perfect, homogeneous mixture of the polymer
molecules. This way the polymer feed entered the reactor at a temperature of about 250 C. The very continuous feed rate enabled constant process conditions.
The uidised bed was heated indirectly by electricity.
Before reaching the uidised bed, the uidising gas was

preheated up to 340 C. Prior to the experiments all air


was replaced with inert nitrogen. During the experiments it was slowly displaced by pyrolysis gases then
acting as uidising medium. During the whole experiment there was a slight pressure above athmospheric
pressure so that no oxygen could get into the plant.
The product gases left the reactor and passed a combined cooling and separation unit. Carbon black and
ne sand were precipitated in a cyclone. Waxes and
liquids were collected in an impact precipitator, coolers
and electrostatic precipitators.

Table 2
Pyro-GC/MS-experiment parameters
Device

Shimadzu QP 5000 GC/MS


and Pyrolyser PYR-4A

Pyrolyser oven temperature


Column

510 C
Macherey & Nagel, Optima-1-TG
25 m length, 0.32 mm diameter,
0.1 mm lm
Helium 5.0, 60 kPa
1:5
80 C (5 min),
3 C/min>360 C (30 min)
About 50 mg
Ionisation method: electron
impact ionisation (EI)
Ionisation voltage: 70 eV
Detector voltage: 1.4 V
Mass range: 30-700 m/z
Scan interval: 1 s
Scanspeed: 1000 amu/sa

Carrier gas
Split ratio
Temperature program
Input
MS-parameters

Fig. 2. Part of the gas chromatograms of the light wax fraction


nding groups to compare.

amu: atomar mass unit.

376

M. Predel, W. Kaminsky / Polymer Degradation and Stability 70 (2000) 373385

The pressure was controlled manually using the compressor valves. The compressor pumped the gas, which
was nearly free of higher hydrocarbons after passing the
separation unit, into the uidised bed again. The excess
gas was burned in a are after its volume, pressure and
temperature was measured. Gas samples were taken in
regular intervals. Process parameters are shown in Table 1.

2.2.2. Analysis of pyrolysis products:


In all experiments gases, yellow oils and solid, yellowgreen waxes, as well as some soot were obtained as
pyrolysis products.
Pyrolysis gas samples were analysed on dierent
capillary GC-columns and quantied with TCD- and
FID-detectors.

Table 3
Mass balances of experiments at 510 C on PE/PP mixtures (in wt%)
Experiment
Input%

Sum Gases

PE
PP
Hydrogen
Methane
Ethane
Ethene
Propane
Propene
n-Butane
i-Butane
n-Butenes
i-Butene
Butadiene

#02

#09

#03

#04

#01

#06

100
0

100
0

60
40

40
60

0
100

0
100

0.026
0.19
0.34
0.46
0.44
0.53
0.22
0.0039
0.35
0.032
0.035
2.6

0.022
0.19
0.31
0.44
0.36
0.53
0.17
0.0029
0.32
0.028
0.033
2.4

0.011
0.33
0.58
0.54
0.41
1.8
0.12
0.025
0.26
0.42
0.037
4.5

0.029
0.34
0.67
0.39
0.45
2.3
0.060
0.064
0.53
0.26
0.018
5.1

0.015
0.42
0.90
0.31
0.45
3.5
0.023
0.059
0.16
1.0
0.0081
6.8

0.0081
0.34
0.96
0.26
0.43
3.8
0.021
0.053
0.10
1.0
0.0064
6.9

i-, n-C5
i-, n-C6
i-, n-C7
i-, n-C8
i-, n-C9
==>2,4-Dimethylheptene
i-, n-C10
i-, n-C11
i-, n-C12
i-, n-C13
n-C14,15+i-C14,15,16,17
n-C16,17+i-C18,19,20
Sum aliphatics
==>Naphtenes
==>Alkanes
==>Alkenes
==>Dienes
Aromatics
Not identied or detected
Sum Oils (bp< 300 C)

0.65
1.2
1.0
0.67
0.65

0.84
0.77
0.68
0.63
1.5
1.8
10.4
0.47
3.0
6.6
0.78
0.0071
2.7
13.2

0.57
1.2
1.1
0.66
0.70

0.84
0.82
0.71
0.73
1.5
1.9
10.6
0.50
3.1
6.8
0.76
0.033
3.0
13.7

1.7
1.9
1.0
0.88
3.8
2.6
1.0
0.73
0.94
0.69
2.6
1.7
16.8
0.65
3.5
11.8
1.5
0.018
2.6
19.4

2.3
2.0
0.86
0.77
5.1
3.3
0.91
0.63
0.98
0.71
2.6
1.6
18.5
0.57
3.9
13.0
1.6
0.0042
4.8
23.2

3.5
3.0
1.1
0.99
10.0
7.1
1.0
0.63
1.5
0.80
4.2
1.4
28.2
0.73
4.6
22.0
1.6
0.021
8.5
36.7

3.2
3.0
1.1
0.86
10.7
8.9
1.1
0.64
1.6
0.78
4.3
1.4
28.6
0.72
4.3
22.7
1.6
0.031
6.8
35.4

Not identied or detected


n-C18,19+i-C21,22,23
n-C20,21+i-C24,25,26
n-C22,23+i-C27,28,29
n-C24,25+i-C30,31,32
n-C26,27+i-C33,34,35
n-C28,29+i-C36,37,38
n-C30,31+i-C39,40,41
n-C32,33+i-C42,43,44
n-C34,35+i-C45,46,47
n-C36,37+i-C48,49,50
Light Waxes (300 C< bp <500 C)

0.63
2.1
2.3
2.3
2.4
2.5
2.4
2.4
2.4
2.4
2.4
24.0

0.59
2.5
2.7
2.6
2.8
2.9
2.9
2.9
2.8
2.9
2.9
28.5

0.73
2.1
2.2
2.2
2.2
2.3
2.3
2.3
2.3
2.3
2.3
23.2

0.72
2.1
2.0
2.3
2.2
2.2
2.2
2.1
2.2
2.2
2.2
22.4

1.7
2.2
1.7
2.0
1.9
2.1
2.0
2.0
2.0
2.0
2.0
21.6

1.1
2.5
1.9
2.0
1.9
2.0
1.8
1.5
1.8
1.8
1.8
20.2

60.0
0.17
100.0

55.2
0.18
100.0

52.8
0.11
100.0

49.1
0.18
100.0

34.6
0.26
100.0

37.3
0.078
100.0

Heavy Waxes (bp > 500C )


Soot
Total

M. Predel, W. Kaminsky / Polymer Degradation and Stability 70 (2000) 373385

All waxy products received from an experiment were


combined and a homogeneous sample was taken. This
sample was mixed with the oil in the ratio the fractions
had been recovered. This mixture was distilled at
reduced pressure to yield an oil fraction, a light wax
fraction and a heavy wax fraction.
The oils were investigated by GC- and GC/MS-analysis with a capillary column (Macherey & Nagel, SE 52,
50 m, 0.32 mm, 0.5 mm) using internal standards
cumene and 1-phenylnaphthalene.
The light wax fraction was analysed with a hightemperature GC-column (Macherey & Nagel, Optima1-TG, 25 m, 0.32 mm, 0.1 mm) in solution of about 2
wt.% in decalin. Every triple of hydrocarbons from
PP with the same carbon number (i-hydrocarbons)
enclosed a pair of hydrocarbons from PE-decomposition (n-hydrocarbons). This observation enabled nding sensible compound-groups for presenting results
(Fig. 2).
Samples of the sand in the reactor and the precipitates
from the cyclone were combusted in a furnace at 815 C
to constant weight. The loss in weight was balanced as
carbon-black/soot.
All fractions were combined to obtain the total mass
balance. Losses or gains could be attributed to uncertainties in the calculation of the gas fraction from the
discontinuous analysis results. Therefore, the dierence
up to 100% was calculated to the gas fraction.
The total mass balances consists of the following
product fractions:
. Gases (up to C4)
. Oils (bp. <300 C, n-C5-17, i-C5-20)
. Light waxes (bp between 300500 C, n-C18-37 and
i-C21-50)
. Heavy waxes (bp > 500 C, >n-C37 and >i-C50)
. Soot, carbon black

377

2.2.3. The pyro-GC/MS-analyser


The pyro-GC/MS-technique is a fast method to perform pyrolysis experiments. The machine used was a
pyrolyser-device type PYR-4A combined with a QP5000 GC/MS made by Shimadzu.
The polymer sample (about 40 mg) was placed into a
tiny bucket of inert platinum, which was dropped into
an infrared laser heated oven. The pyrolysis products
passed a split of the GC, were separated on the GCcolumn and nally identied and quantied by MS.
Process parameters are shown in Table 2.
As it is dicult to mix such tiny amounts of polyolens,
the samples had been prepared using the extruder that
was also used as feeder/mixer in the uidised bed pyrolysis experiments. From these samples small lms were
pressed that were nally analysed in the pyro-GC/MS.
Due to the wide range of pyrolysis products the gases
and oils could not be separated and thus were detected
together. Therefore, gases and oils are balanced in only one
product fraction.
The pyrolysis products were directly analysed and
their quantity was given in TIC% (total ion current),
which must not be compared to wt.% (weight%).
3. Results and discussion
3.1. Experiments in the uidised bed reactor
3.1.1. Experiments on PE/PP-mixtures
The mass balances are shown in Table 3. Two experiments (#01, #06 and #02, #09) have been completely
repeated in order to check reproducibility.
Gas and oil production of pure PE-feed is only about
one third of that evolved by PP-feed. It is remarkable
that the trimer of propene (2,4-dimethylheptene) is
formed in very high amounts from PP (one quarter of

Fig. 3. Product fractions of PE/PP-pyrolysis in the uidised bed reactor.

378

M. Predel, W. Kaminsky / Polymer Degradation and Stability 70 (2000) 373385

Table 4
Mass balances of experiments at 510 C on PE/PS mixtures (in wt%)
Experiment
Input%

Sum Gases

Sum Oils (bp<300 C)

PE
PS
Hydrogen
Methane
Ethane
Ethene
Propane
Propene
n-Butane
i-Butane
n-Butenes
i-Butene
Butadiene
n-C5
n-C6
n-C7
n-C7
n-C9
n-C10
n-C11
n-C12
n-C13
n-C14
n-C15
n-C16
n-C17
Sum Aliphatics
==>Naphtenes
==>Alkanes
==>Alkenes
==>Dienes
Benzene
Toluene
Styrene
Ethylbenzene
a-Methylstyrene
Other Aromatics
Sum Aromatics
Not identied or detected

Not identied or detected


n-C18,19
n-C20,21
n-C22,23
n-C24,25
n-C26,27
n-C28,29
n-C30,31
n-C32,33
n-C34,35
n-C36,37
Light Waxes (300 C<bp<500 C)
Heavy Waxes (bp>500C )
Soot
Total
a

#02

#09

#05a

#05

100
0

100
0

100*
0

90
10

0.026
0.19
0.34
0.46
0.44
0.53
0.22
0.0039
0.35
0.032
0.035
2.6

0.022
0.19
0.31
0.44
0.36
0.53
0.17
0.0029
0.32
0.028
0.033
2.4

0.65
1.2
1.0
0.67
0.65
0.84
0.77
0.68
0.63
0.70
0.80
0.86
0.92
10.4
0.47
3.0
6.6
0.78
0.0071

0.0071
2.7
13.2

0.57
1.2
1.1
0.66
0.70
0.84
0.82
0.71
0.73
0.77
0.73
0.90
0.97
10.6
0.50
3.1
6.8
0.76
0.0093
0.024

0.033
3.0
13.7

0.81
1.4
1.2
0.80
0.84
0.95
0.91
0.81
0.81
0.87
1.0
1.3
1.4
13.2
0.65
3.9
8.3
1.0

13.2

0.73
1.3
1.1
0.72
0.76
0.86
0.82
0.73
0.73
0.78
0.91
1.2
1.3
11.9
0.58
3.5
7.5
0.90
0.017
1.1
5.2
0.36
0.34
0.47
7.5
2.4
21.8

0.63
2.1
2.3
2.3
2.4
2.5
2.4
2.4
2.4
2.4
2.4
24.0

0.59
2.5
2.7
2.6
2.8
2.9
2.9
2.9
2.8
2.9
2.9
28.5

0.47
3.1
3.2
3.4
3.3
3.4
3.3
3.3
3.3
3.3
3.3
33.6

0.43
2.8
2.9
3.1
3.0
3.0
3.0
3.0
3.0
3.0
3.0
30.2

60.0
0.17
100.0

55.2
0.18
100.0

50.4
0.041
100.0

45.3
0.037
100.0

05*: Results from experiment #05 without PS-pyrolysis products.

0.027
0.22
0.37
0.54
0.40
0.65
0.21
0.0027
0.41
0.046
0.039
2.9

0.025
0.20
0.33
0.49
0.36
0.59
0.19
0.0024
0.37
0.042
0.035
2.6

M. Predel, W. Kaminsky / Polymer Degradation and Stability 70 (2000) 373385

the oil, 79 wt.% total). Branched aliphatic compounds


like that are known to have very high octane numbers
[13]. In the oil fraction of the PE-experiments the ratio
alkane/alkene/diene is 1 : 2.2 : 0.25. PP-polymer gives
much more unsaturated products. The ratio is 1:5:0.37.
The amount of light waxes decreases slightly when
changing from PE to PP. The amount of heavy waxes is
nearly cut down to half.
The amount of the dierent fractions is shown vs.
ratio of both polymers (Fig. 3). Lines are received which
indicate that there is no interaction between the two
polymers PE and PP in uidised bed pyrolysis.
3.1.2. Experiments on PE/PS-mixtures
The mass balances are shown in Table 4. The gures
in column #05* were not received experimentally but
calculated from experiment #05 by leaving all PS-pyrolysis products out.
So the experiments #02 and #09 show experiments on
pure PE and the column #05* shows PE-pyrolysis products inuenced by the presence of PS.
A slight shift in the product distribution from the
heavy waxes to the light wax fraction might be assumed,
but taking in account the accuracy from the experiment
performed twice, it cannot be proved that there is any
mixing eect by PS on the PE-pyrolysis products.
The ratio alkane/alkene/diene of pyrolysis products
from PE-pyrolysis does not change in the presence of
PS. The peak distribution of the light wax fraction does
not dier, whether there was PS present or not (GCs
shown in Fig. 4).

379

3.1.3. Experiments on PP/PS-mixtures


Two pyrolysis experiments on pure PP are compared
to an experiment with a PP/PS-mixture (Table 5). In the
column of experiment #07* all pyrolysis products
resulting from PS of experiment #07 are neglected,
according to the procedure in column #05*. A small
dierence in the amount of pyrolysis products can be
observed, but again it is in the range of inaccuracy of
the repeated experiment. So an eect of PS on PPpyrolysis cannot be proved with certainty.
The ratio alkane/alkene/diene in the oil fraction does
not dier signicantly in the presence of PS. But when
comparing the gas-chromatograms of the distilled light
wax fraction a hint for an interaction was discovered.
The peak distribution of the PP-waxes received from
PP/PS-pyrolysis is much simpler than that received from
pure PP-pyrolysis. The GCs of the light wax fractions
from pure PP and PP with 10% PS are shown in Fig.
5(a) and (b). When comparing the intensities of the
compounds in one oligomer-group (especially at > iC30), it was discovered that the formation of dienes
(especially the last isomer) is strongly enhanced when
PS was present during pyrolysis.
3.1.4. Experiments on PE/PP/PS-mixtures
Finally a mixture of PE/PP is compared to a mixture
of PE/PP/PS (Table 6).
Again the column in the middle (#08*) shows the
pyrolysis products, neglecting PS-decomposition products
from experiment #08. Products received from a mixture
with PS are very much the same as without, apart from

Fig. 4. Gas-chromatograms of light wax fractions from PE/PS-experiments (uidised bed).

380

M. Predel, W. Kaminsky / Polymer Degradation and Stability 70 (2000) 373385

Table 5
Mass balances of experiments at 510 C on PP/PS mixtures (in wt%)
Experiment
Input%

Sum Gases

Sum Oils (bp<300 C)

PP
PS

#01

#06

#07a

#07

100

100

100*

90
10

Hydrogen
Methane
Ethane
Ethene
Propane
Propene
n-Butane
i-Butane
n-Butenes
i-Butene
Butadiene

0.015
0.42
0.90
0.31
0.45
3.5
0.023
0.059
0.16
1.0
0.0081
6.8

i-C5
i-C6
i-C7
i-C8
i-C9
==>2,4-Dimethylheptene
i-C10
i-C11
i-C12
i-C13
i-C14
i-C15,16,17
i-C18,19,20
Sum Aliphatics
==>Naphtenes
==>Alkanes
==> Alkenes
==>Dienes
Benzene
Toluene
Styrene
Ethylbenzene
a-Methylstyrene
Other Aromatics
Sum Aromatics
Not identied or detected

0.0038
0.31
0.77
0.25
0.31
3.1
0.019
0.044
0.11
0.88
0.0059
5.8

0.0034
0.28
0.69
0.23
0.28
2.8
0.017
0.040
0.10
0.79
0.0053
5.2

3.5
3.0
1.1
0.99
10.0
7.1
1.0
0.63
1.5
0.80
0.18
4.0
1.4
28.2
0.73
4.6
22.0
1.6

0.021
0.021
8.5
36.7

3.2
3.0
1.1
0.86
10.7
8.9
1.1
0.64
1.6
0.78
0.19
4.1
1.4
28.6
0.72
4.3
22.7
1.6

0.031
0.031
6.8
35.4

3.1
2.8
1.0
0.86
10.5
9.3
1.0
0.61
1.5
0.81
0.20
4.1
1.5
28.1
0.60
4.1
22.4
1.6

3.8
31.8

2.8
2.5
0.92
0.77
9.4
8.4
0.90
0.55
1.3
0.73
0.18
3.7
1.4
25.3
0.54
3.7
20.2
1.4
0.0074
0.38
7.1
0.11
0.29
0.41
8.3
5.1
38.7

1.7
2.2
1.7
2.0
1.9
2.1
2.0
2.0
2.0
2.0
2.0
21.6

1.1
2.5
1.9
2.0
1.9
2.0
1.8
1.5
1.8
1.8
1.8
20.2

1.3
2.7
1.9
2.0
2.3
1.9
1.8
1.9
2.0
2.0
2.0
21.8

1.1
2.4
1.7
1.8
2.1
1.7
1.7
1.7
1.8
1.8
1.8
19.6

34.6
0.26
100.0

37.3
0.078
100.0

40.5
0.084
100.0

36.4
0.075
100.0

Not identied or detected


i-C21,22,23
i-C24,25,26
i-C27,28,29
i-C30,31,32
i-C33,34,35
i-C36,37,38
i-C39,40,41
i-C42,43,44
i-C45,46,47
i-C48,49,50
Light Waxes (300 C<bp<500 C)
Heavy Waxes (bp>500C )
Soot
Total

0.0081
0.34
0.96
0.26
0.43
3.8
0.021
0.053
0.10
0.99
0.0064
6.9

07*: results from experiment #07 without PS-pyrolysis products.

M. Predel, W. Kaminsky / Polymer Degradation and Stability 70 (2000) 373385

additional polystyrene degradation products, leading to


the conclusion that the additional PS does not change
product spectra of PE/PP-mixtures.
3.2. Experiments on the Pyro-GC/MS-device
3.2.1. Experiments on PE/PP-mixtures
The experiments have been done with dierent ratios
of PE and PP. Experiments were repeated to check

381

reproducibility. The results are shown in Table 7 and


Fig. 6.
By comparing the amounts of the product fractions
no product-changing interaction between PE and PP
was found. The graphically displayed results show the
same trends observed in the uidised bed pyrolysis (ref.
Fig. 3), although the results from Pyro-GC/MS are
given in TIC% (total ion current). PP-pyrolysis yields
more gases and oils compared to PE-decomposition.

Fig. 5. (a) Gas-chromatograms of light wax fractions from PP/PS-experiments (uidised bed); (b) GCs of light wax fractions from PP/PS-experiments (uidised bed) ne structure.

382

M. Predel, W. Kaminsky / Polymer Degradation and Stability 70 (2000) 373385

Table 6
Mass balances of experiments at 510 C on PE/PP/PS mixtures (in wt%)
Experiment
Input%

Sum Gases

PE
PP
PS
Hydrogen
Methane
Ethane
Ethene
Propane
Propene
n-Butane
i-Butane
n-Butenes
i-Butene
Butadiene
i-, n-C5
i-, n-C6
i-, n-C7
i-, n-C8
i-, n-C9
==>2,4-Dimethylheptene
i-, n-C10
i-, n-C11
i-, n-C12
i-, n-C13
n-C14,15+i-C14,15,16,17
n-C16,17+i-C18,19,20
Sum Aliphatics
==>Naphtenes
==>Alkanes
==>Alkenes
==>Dienes
Benzene
Toluene
Styrene
Ethylbenzene
a-Methylstyrene
other aromatics
Sum Aromatics
Not identied or detected

#03

#08a

#08

60
40

60*
40*

54
36
10

0.011
0.33
0.58
0.54
0.41
1.8
0.12
0.025
0.26
0.42
0.037
4.5

0.012
0.32
0.59
0.50
0.46
1.8
0.13
0.027
0.26
0.38
0.028
4.5

0.011
0.29
0.53
0.45
0.41
1.7
0.11
0.024
0.23
0.34
0.025
4.1

1.7
1.9
1.0
0.88
3.8
2.6
1.0
0.73
0.94
0.69
2.6
1.7
16.8
0.65
3.5
11.8
1.5
0.012

0.0065
0.018
2.6
19.4

1.7
1.8
0.91
0.75
4.0
2.7
0.94
0.65
1.0
0.69
2.5
1.8
16.7
0.54
3.7
11.6
1.4

1.5
18.3

1.5
1.6
0.82
0.67
3.6
2.4
0.85
0.59
0.90
0.62
2.3
1.6
15.1
0.49
3.3
10.5
1.2
0.014
0.50
6.3
0.15
0.29
0.47
7.7
3.6
26.4

Not identied or detected


n-C18,19+i-C21,22,23
n-C20,21+i-C24,25,26
n-C22,23+i-C27,28,29
n-C24,25+i-C30,31,32
n-C26,27+i-C33,34,35
n-C28,29+i-C36,37,38
n-C30,31+i-C39,40,41
n-C32,33+i-C42,43,44
n-C34,35+i-C45,46,47
n-C36,37+i-C48,49,50
Light Waxes (300 C< bp <500 C)

0.73
2.1
2.2
2.2
2.2
2.3
2.3
2.3
2.3
2.3
2.3
23.2

1.1
2.4
2.3
2.3
2.4
2.4
2.3
2.3
2.3
2.3
2.3
24.4

0.96
2.2
2.0
2.1
2.1
2.1
2.1
2.1
2.1
2.1
2.1
22.0

Heavy Waxes (bp > 500 C)


Soot
Total

52.8
0.11
100.0

52.7
0.16
100.0

47.4
0.14
100.0

Sum Oils (bp< 300 C)

08*: results from experiment #08 without PS-pyrolysis products.

M. Predel, W. Kaminsky / Polymer Degradation and Stability 70 (2000) 373385

3.2.2. Experiments on PE/PS-mixtures


PS was added to the PE in shares of 10% and 50%.
The results are shown in Table 8.
The right part of the table shows only products from
PE-decomposition after all PS-decomposition products
were neglected. Neglecting all PS-degradation products
the amount of gas/oils increases with a rising PS-content
in the input mixture, whereas the amount of heavy
waxes decreases. The amount of the light wax fraction
remains constant. Pyrograms are shown in Fig. 7. No
dierence indicating an enhanced formation of unsatu-

383

rated products was detected in the peak distribution


when PS was present.
3.2.3. Experiments on PP/PS-mixtures
The same trend found in PE/PS-pyrolysis is observed
here: The amount of gases/oils increases on expense of
the heavy waxes. The amount of light waxes remains
constant (Table 9).
But there is also a change in the peak distribution of
the PP-waxes (Fig. 8) comparable to uidised bed
pyrolysis (compare to Fig. 5b). The formation of more

Table 7
PE/PP mixtures pyrolysed at 510 C on a pyro-GC/MS (in TIC%)a
Pyro-GC/MS-Experiment

#3

#17

#21

#10

#18

#9

#19

#8

#11

#7

#12

#15

#1

#2

Input ratio PP:PE


Input [mg]

100:0
46

100:0
41

100:0
63

80:20
26

80:20
48

60:40
31

60:40
45

40:60
38

40:60
33

20:80
35

20:80
30

20:80
48

0:100
106

0:100
59

29.1
2.3
31.4
3.1
2.2
2.4
2.3
2.2
2.5
2.9
3.0
3.6
3.4
55.6

32.0
2.3
34.3
3.2
2.0
2.1
2.0
2.9
2.3
2.6
2.6
2.8
3.2
56.9

30.4
2.4
32.8
3.1
2.2
2.5
2.7
3.4
3.1
2.9
3.6
3.4
3.7
59.7

29.9
2.2
32.1
2.5
2.1
2.2
2.3
2.7
2.7
2.8
3.4
4.2
3.7
57.0

25.8
1.8
27.6
2.4
2.0
2.1
2.3
3.2
2.8
3.3
3.7
4.5
4.7
53.9

23.3
2.4
25.6
3.7
2.7
3.1
2.9
3.2
3.2
3.4
3.5
3.7
4.0
55.0

25.8
1.8
27.6
2.6
2.1
2.5
2.4
2.7
3.1
3.6
3.7
4.4
4.5
54.7

19.3
3.4
22.7
3.0
3.2
2.5
3.0
2.7
3.1
3.6
3.6
3.5
3.6
50.9

20.3
2.9
23.2
2.6
2.5
2.8
2.8
3.5
3.2
3.4
3.8
4.5
4.6
52.2

16.4
3.7
20.1
2.8
2.9
2.9
3.2
3.7
4.0
4.3
4.4
4.9
5.0
53.1

13.8
3.8
17.6
3.1
3.1
3.6
3.5
3.6
3.9
4.2
4.6
4.7
4.8
51.8

12.8
3.1
15.9
2.9
2.9
3.4
3.6
4.2
4.2
4.3
4.8
5.2
5.6
51.5

11.2
2.2
13.4
2.7
2.8
3.2
3.4
3.7
3.8
4.1
4.4
4.4
4.7
45.8

8.8
1.8
10.7
2.6
2.8
3.1
3.6
3.7
4.3
4.3
4.7
4.7
4.8
44.5

40.9

39.9

36.7

39.3

41.4

41.1

40.8

45.6

43.2

42.0

43.4

42.9

49.5

50.6

H2, n-C1-15, i-C4-17


n-C16-17, i-C18-20
Oils, Gases (b.p < 300 C)
n-C18-19, i-C21-23
n-C20-21, i-C24-26
n-C22-23, i-C27-29
n-C24-25, i-C30-32
n-C26-27, i-C33-35
n-C28-29, i-C36-38
n-C30-31, i-C39-41
n-C32-33, i-C42-44
n-C34-35, i-C45-47
n-C36-37, i-C48-50
Light Waxes
(300 C < b.p. < 500 C)
Heavy Waxes
(bp > 500 C, >n-C37, i-C50)
Total
a

100

100

100

100

100

100

100

100

100

100

100

TIC=total ion current.

Fig. 6. Pyro-GC/MS experiments on PE/PP-mixtures (product fractions vs. input ratio).

100

100

100

384

M. Predel, W. Kaminsky / Polymer Degradation and Stability 70 (2000) 373385

Table 8
Pyro GC/MS-experiments at 510 C on PE/PS-mixtures (results in TIC%)a
Pyro-GC/MS-Experiment #1
Input ratio PE:PS
Input [mg]

#2

#6

#20

#13

#22

#24

100:0 100:0 90:10 90:10 50:50 50:50 50:50


106 59
42
40
40
74
30

R PS-Pyrolysis Products

1.9
2.0 16.9 13.1 15.8
H2, n-C1-15 11.2
8.8 11.5 14.9 24.3 23.4 24.8
n-C16-17
2.2
1.8
2.2
1.9
2.0
1.5
1.8
Oils, Gases (bp < 300 C) 13.4 10.7 13.7 16.9 26.3 25.0 26.6
2.7
2.6
2.6
2.2
2.0
1.9
1.6
n-C18-19
n-C20-21
2.8
2.8
2.9
2.6
1.9
1.9
2.1
n-C22-23
3.2
3.1
3.2
2.7
2.3
2.2
2.1
n-C24-25
3.4
3.6
3.6
3.1
2.6
3.1
2.5
3.7
3.7
3.8
3.7
2.7
3.7
2.7
n-C26-27
n-C28-29
3.8
4.3
4.2
4.1
3.0
3.5
2.8
n-C30-31
4.1
4.3
4.5
4.0
3.2
3.7
3.3
n-C32-33
4.4
4.7
4.8
4.4
3.3
4.1
3.3
4.4
4.7
5.1
4.8
3.7
4.0
3.7
n-C34-35
n-C36-37
4.7
4.8
5.4
4.9
3.7
4.3
4.1
Light Waxes
37.1 38.7 40.1 36.4 28.4 32.4 28.3
(300 C < bp < 500 C)
Heavy Waxes
49.5 50.6 44.3 44.7 28.4 29.6 29.4
(bp > 500 C, > n-C37)
Total
100 100 100 100 100 100 100
a

#1

#2

#6

#20

#13

#22

#24

100:0
100:0
90:10*
90:10*
50:50*
50:50*
50:50*
106
59
42
40
40
74
30
polystyrene decomposition products not considered
only products due to PE-pyrolysis shown

11.2
2.2
13.4
2.7
2.8
3.2
3.4
3.7
3.8
4.1
4.4
4.4
4.7
37.1

8.8
1.8
10.7
2.6
2.8
3.1
3.6
3.7
4.3
4.3
4.7
4.7
4.8
38.7

11.7
2.3
14.0
2.6
2.9
3.3
3.7
3.9
4.3
4.6
4.9
5.2
5.5
40.9

15.2
2.0
17.2
2.3
2.6
2.8
3.2
3.7
4.2
4.1
4.5
4.9
5.0
37.2

29.3
2.4
31.7
2.4
2.3
2.7
3.1
3.3
3.6
3.8
4.0
4.4
4.5
34.1

27.0
1.7
28.7
2.1
2.1
2.5
3.6
4.3
4.1
4.2
4.7
4.6
5.0
37.2

29.4
2.1
31.5
2.0
2.5
2.5
2.9
3.3
3.4
3.9
4.0
4.4
4.8
33.6

49.5

50.6

45.2

45.6

34.2

34.1

34.9

100

100

TIC=total ion current.

Fig. 7. Pyrograms of PE- and PE/PS-pyrolysis.

Fig. 8. Pyrograms of PP- and PP/PS-pyrolysis.

100

100

100

100

100

M. Predel, W. Kaminsky / Polymer Degradation and Stability 70 (2000) 373385

385

Table 9
Pyro GC/MS-experiments at 510 C on PP/PS-mixtures (results in TIC%)a
Pyro-GC/MS-Experiment #3
#17 #21 #4
#5
#14 #16 #21
Input ratio PP:PS
100:0 100:0 100:0 90:10 90:10 50:50 50:50 50:50
Input [mg]
46
41
63
30
62
43
43
34

R PS-pyrolysis products
H2, C1-17
i-C18-20
Oils, Gases (b.p < 300 C)
i-C21-23
i-C24-26
i-C27-29
i-C30-32
i-C33-35
i-C36-38
i-C39-41
i-C42-44
i-C45-47
i-C48-50
Light Waxes
(300 C < bp < 500 C)
Heavy Waxes
(bp > 500 C, >i-C50)
Total
a

1.7 2.1 26.3 24.8


29.1 32.0 30.4 30.2 28.8 28.5 30.8
2.3 2.3 2.4 1.7 2.1 2.0 2.1
31.4 34.3 32.8 32.0 30.9 30.5 32.9
3.1 3.2 3.1 2.7 2.8 2.4 3.1
2.2 2.0 2.2 2.0 2.0 2.2 1.8
2.4 2.1 2.5 2.5 2.5 1.9 1.9
2.3 2.0 2.7 2.2 2.1 2.7 1.9
2.2 2.9 3.4 2.3 2.2 2.4 2.0
2.5 2.3 3.1 2.7 2.1 1.7 1.5
2.9 2.6 2.9 3.2 2.3 2.5 1.7
3.0 2.6 3.6 3.2 3.1 2.4 1.9
3.6 2.8 3.4 3.0 2.7 2.2 2.3
3.4 3.2 3.7 3.0 3.4 2.4 2.4
27.7 25.8 30.6 26.9 25.1 22.8 20.4

#3
#17
#21
#4
#5
#14
#16
#21
100:0 100:0 100:0 90:10* 90:10* 50:50* 50:50* 50:50*
46
41
63
30
62
43
43
34
polystyrene decomposition products not considered
only products due to PE-pyrolysis shown

27.0
33.4
1.5
34.9
3.0
1.6
1.9
2.2
2.2
1.9
2.2
2.0
2.3
2.1
21.4

29.1
2.3
31.4
3.1
2.2
2.4
2.3
2.2
2.5
2.9
3.0
3.6
3.4
27.7

32.0
2.3
34.3
3.2
2.0
2.1
2.0
2.9
2.3
2.6
2.6
2.8
3.2
25.8

30.4
2.4
32.8
3.1
2.2
2.5
2.7
3.4
3.1
2.9
3.6
3.4
3.7
30.6

30.8
1.8
32.5
2.8
2.1
2.5
2.2
2.4
2.7
3.2
3.3
3.1
3.1
27.4

29.4
2.1
31.5
2.8
2.0
2.5
2.2
2.2
2.1
2.4
3.1
2.8
3.5
25.7

38.6
2.7
41.3
3.3
3.0
2.5
3.7
3.2
2.4
3.4
3.2
3.0
3.2
30.9

40.9
2.8
43.7
4.2
2.3
2.6
2.5
2.6
2.0
2.2
2.5
3.0
3.2
27.1

45.8
2.1
47.9
4.1
2.2
2.7
3.0
3.0
2.6
3.0
2.7
3.2
2.9
29.3

40.9 39.9 36.7 39.4 41.9 20.4 21.9 16.7

40.9

39.9

36.7

40.1

42.8

27.7

29.1

22.9

100

100

100

100

100

100

100

100

100

100

100

100

100

100

100

100

TIC=Total ion current.

unsaturated products waxes at >i-C30 (especially one


diene monomer) is strongly enhanced with PS present in
the feed material.

olens leading to more products with shorter chain


lengths, as reported using other pyrolysis methods. The
formation of more unsaturated waxes from PP is also
favoured when PP was blended with PS.

4. Conclusions
Mixed polyolens can be converted by uidised bed
pyrolysis at 510 C into valuable oils and waxes, which
can be used as feedstock in petrochemical processes.
The amount usable in a steam cracker (<500 C boiling
point) is 50 wt.% when using PE-feed and 70 wt.% when
using PP-feed. The amount usable from PE/PP-mixture
can be calculated on basis of these gures, because their
pyrolysis products can be calculated additionally.
When adding 10% PS to either PE or PP or a PE/PPmixture the distribution of products fractions does not
change signicantly apart from additional PS degradation products. This observation is contradictory to
other pyrolysis methods [912].
But when adding PS to PP the peak distribution of
the waxes changes signicantly, although its amount
remains constant: The formation of diene-waxes is
favoured at i-C30 and higher. But this fact will surely
have little eect when this product fraction is fed into a
steam cracker.
By using a pyro-GC/MS-analyser it was shown that
there is a mixing inuence of PS on the other two poly-

References
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leaet, Bruxelles, 1999.
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[4] Kaminsky W, Simon CM, Schlesselmann B. J Anal Appl Pyrolysis 1996;38:7587.
[5] Kaminsky W, Schlesselmann B, Simon CM. Polym Degrad Stab
1996;53:18997.
[6] Kaminsky W, Kastner H. Hydrocarbon Process 1995;May: 109
12.
[7] Kastner H. PhD thesis, University of Hamburg, 1998.
[8] Mertinkat J, Kirsten A, Predel M, Kaminsky W. J Anal Appl
Pyrolysis 1999;49:8795.
[9] Koo JK, Kim SW, Seo YH. Resour Conserv Recycl 1991;5:365
82.
[10] Williams PT, Williams EA. Energy & Fuel 1999;13(1):18896.
[11] Williams PT, Williams EA. In: Proceedings of the First International Symposium on Feedstock Recycling of Plastics (ISFR),
Sendai, Japan, 1999. p.1137.
[12] Bockhorn H, Hentschel J, Hornung A, Hornung U. Chem Eng
Sci 1999;54(15-16):304352.
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