45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic

Hydrocarbons obtained by pyrolysis of contaminated waste plastics

Nikolett Borsodi *(1), Norbert Miskolczi(1), András Angyal(1), László Bartha(1), József
Kohán(2), András Lengyel(2)
(1)
Universiy of Pannonia, Department of MOL Hydrocarbon and Coal Processing
8200 Veszprém, Egyetem u. 10.
Tel.: +36-88-624-000
Fax: +36-88-624-520
*e-mail: borsodinikolett@almos.uni-pannon.hu
(2)
MOL Hungarian Oil and Gas Plc.

Key words: pyrolysis, motor oil flask, effect of contamination

Abstract: In this work the pyrolysis of contaminated plastic waste was studied. The
pyrolysis of clear and contaminated waste plastics was carried out in a tubular reactor,
applying 500°C temperature. Y-zeolite catalyst was applied to reduce the contaminant
level in the products and the effect of pre-treatment of raw materials was also studied.
It was established that the catalyst could increase the yields of volatile products but its
effect was significant only in case of clear, non-contaminated raw materials. In the
absence of catalyst the pre-treating of raw materials had only moderate effect on the
quantity and quality of the products. The determined properties of the low contami-
nated products were advantageous with respect to their energetic utilization. However
it was also cleared that the pyrolysis of high contaminated raw materials could not
result in acceptable hydrocarbon fractions for refinery plants.

I. Introduction
The world’s plastic consumption has been significantly increased in the last decades.
Nowadays the disposal of the plastic wastes means a huge problem because their deg-
radation takes a very long time in the nature. One of the plastic waste recycling proc-
esses is the pyrolysis. Pyrolysis of plastic wastes is carried out in the temperature
range of 400-700°C in the absence of oxygen. Among these conditions the long po-
lymer chains are cracked into lower hydrocarbons. The energetic utilization is one of
the further utilization of pyrolysis products.
Plastic wastes from the packaging sector usually contain contaminants in their own
material or on their surface. Chemical recycling of contaminated plastics is possible
but the contaminants can appear in the products and the high heteroatom content of
the products reduces their quality.
The energy consumption of the pyrolysis process is quite high because of the endo-
thermic cracking reactions. In addition the products of thermal pyrolysis have a wide
carbon number distribution. [1-2]. Therefore there are several processes that apply
catalysts in order to decrease the activation energy of the reactions. By using catalysts
the reaction temperature can shifted to lower temperatures. Catalysts also change the
composition of the products, eg. liquid products obtained from thermo-catalytic deg-
radation have a lower average molecular weight therefore they are much more ade-
quate to used as blending components of fuels [1-12]. The most often applied hetero-
geneous catalysts are different types of zeolites and acid solids like alumina, silica-
alumina, aluminium pillared clays and mesostructured materials (Al-MCM-41and Al-
SBA-15) [7].
 45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic 2

However, the direct catalytic pyrolysis has a number of disadvantages. The activity of
catalyst can rapidly decrease because of the contaminants (sulphur, metal and other
contaminants) that are present in the plastics. The coke formation on the surface of the
catalyst is another reason for the deactivation. Furthermore catalysts presents addi-
tional costs in the technology, therefore its regeneration is crucial. Nevertheless, re-
generation process could be difficult because already the first step, the separation of
the catalyst from the heavy oil is complicated [7].
A number of workers have investigated the thermo-catalytic pyrolysis of polymers on
different zeolite catalysts. Most of these researches have applied pure plastic material
or mixed plastic as raw material. Only a few investigations with real plastic wastes
were presented in the literature [12-13]. In some cases the effect of catalysts on the
decomposition of heteroatom containing plastics was also investigated [14-16].

II. Experimental

Raw materials
Two raw materials were applied in the experiments: original off-grade granulated
HDPE (high density polyethylene) and motor oil contaminated HDPE derived from
waste motor oil flasks collection system. The former was obtained from TVK Plc. and
the latter from Design Ltd. The composition of the motor oil flasks is shown in Fig. 1.
According to Fig.1. the raw material contained a significant amount of motor oil
which could contain various heteroatoms. Therefore in some cases the raw material
was washed with light naphtha for 30 minutes and was dried for 180 minutes in vac-
uum. In the washing process 2.5 l solvent was added to 1 kg grinded motor oil flask in
a mixer. In case of catalytic cracking experiments the applied catalyst was Y-zeolite
type catalyst (with Si/Al ratio 23, BET surface area 192.2 m2/g and the surface area of
micropores 94.2 m2/g). Chlorine content of raw material was 720 ppm.

(a) (b)

Figure 1 - The composition of the raw material (a) Motor oil flasks (b) Washed motor oil flasks

Pyrolysis procedure
Pyrolysis of raw materials was carried out in a laboratory scale continuous tubular
reactor. The layout of the process is shown in Fig. 2. The plastic waste was first
grinded up to particles with 3 mm diameter. Then it was fed into an extruder (feeding
rate was 0.5 kg raw material/hr). The plastic was melted in the extruder and driven
into the reactor the experiments occurred in the absence of oxygen. The extruder and
the reactor was electrically heated, the temperature was measured by thermocouples.
In every experiment the temperature of the pyrolysis was 500°C. The reactor was
built from three parts which temperature could be controlled separately. Hydrocar-
 45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic 3

bons obtained by the cracking reactions were separated in a distillation column. Three
products were separated: gas, liquid and heavy oil. In every experiments gases were
get into a trap containing 0.1N NaOH solution to trap HCl. After that the alkali solu-
tion was titrated with hydrochloric acid to quantify the HCl in the gases.

Fig. 2 – Layout of the process: 1. electric motor, 2. extruder, 3. parts of the reactor, 4. distillation unit,
5. gas-liquid separator, 6. water trap 7. temperature controller

Analysis of pyrolysis products

The gas and liquid products were characterized using DANI GC fitted with a 30 m x
0.32 mm Restek-Q column and a 30 m x 0.53 mm Rtx-1 column.
The composition of the raw material was analyzed by a TENSOR 27 type Fourier
Transformed Infrared (FTIR) spectrometer in the range of 4000–400 cm-1.
The chlorine content of raw material and pyrolysis products was determined by a Mit-
subishi TOX-100 type instrument. Samples were burned in an Argon/Oxygen atmos-
phere at 900°C. The resulting chloride was lead into a titration cell where it was au-
tomatically titrated by silver ions generated coulometrically.
Determination of density, heating value, melting point, nitrogen and sulphur content
corrosion properties, flashpoint open cup (Marcusson), flashpoint closed cup (Pensky-
Martens) of liquid products were performed by using standardized test methods: MSZ
EN ISO 12185:1996, MSZ 19954:1971, MSZ 11721:1964, ASTMD 6428 99 and
ASTMD 6366 99, MSZ EN ISO 2160, MSZ 15967:1979, MSZ EN ISO 2719:2000
respectively.

III. Results and discussion

Product yields
According to Fig.3. it can be stated that the applied catalyst increased the yields of the
volatile products. However the cracking activity of the catalyst was significantly
lower in the case of the pyrolysis of contaminated raw material. It was established that
the inorganic (S, N, Cl) content of the raw material caused the deactivation of the
catalyst. Moreover it was also established that the pre-treatment of the contaminated
raw material could increase the volatile yields with 10%. The thermal degradation of
contaminated raw materials resulted in higher yields of volatile hydrocarbons com-
pared with the yields of original HDPE pyrolysis.
 45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic 4

100

80
Gas
Composition, % 60 Liquid
Heavy oil
40

20

0
Thermal Y-zeolite Thermal Y-zeolite Thermal Y-zeolite
Original Motor oil flasks Washed motor oil
flasks

Fig. 3 – Product yields

Composition of gas and liquid products

Composition of gases was analyzed by a gas-chromatograph. All of the gaseous prod-
ucts were in the carbon number range C1-C5. In every case two dominant components
could be observed: C2 and C4. This could be explained with the structure and degrada-
tion mechanism of polyethylene because it is built up from C2 monomers. In thermal
cases saturated and unsaturated linear hydrocarbons were dominant. The gases
evolved during thermo-catalytic pyrolysis contained i-C4 and i-C5 molecules.

100

80
Aromatic
Composition, %

Branched
60
n-Alkenes

40 n-Alkanes

20

0
Thermal Y-zeolite Thermal Y-zeolite Thermal Y-zeolite
Original Motor oil flasks Washed motor oil
flasks

Fig. 4 – Composition of liquid products

Composition of liquid products is shown in Fig. 3. According to Fig.3 it can be seen

that the n-alkanes and n-alkenes were the major components of the liquid fractions.
Moreover branched and aromatic hydrocarbons could be also detected. The use of
catalyst did not affect significantly the composition of liquid products obtained by the
pyrolysis of motor oil flask. However in the case of the pyrolysis of original HDPE
the catalyst increased the concentration of the branched and aromatic hydrocarbons in
the liquid product. Thus it can be stated that the isomerisation effect of the catalyst
 45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic 5

was not realized at the pyrolysis of the contaminated raw materials, because contami-
nants deactivated the applied catalyst.

(a)
25

20
Composition, %

15 Thermal
Y-zeolite
10

0
5 6 7 8 9 10 11 12 13 14 15 16 17 18
Carbon number

(b)
18
16
14
Composition, %

12
10 Thermal
8 Y-zeolite
6
4
2
0
5 6 7 8 9 10 11 12 13 14 15 16 17 18
Carbon number

(c) 20
18
16
Composition, %

14
12 Thermal
10 Y-zeolite
8
6
4
2
0
5 6 7 8 9 10 11 12 13 14 15 16 17 18
Carbon number

Fig. 4 – Composition of liquid products: (a) Original raw material (b) Motor oil flasks (c) Washed mo-
tor oil flasks
 45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic 6

Carbon number distribution of liquid products is shown in Fig. 4 a-c. All of the liquid
products were consisted of hydrocarbons from C5 to C18. In Fig. 4a the carbon number
distribution of liquid products obtained from thermal and thermo-catalytic pyrolysis
of original HDPE are shown. In the thermo-catalytic case the liquid product contained
lighter hydrocarbons compared to the thermal product. In other words the average
molecular weight of the liquid product became lower. This phenomenon could not be
observed on the carbon number distribution of liquid products derived from the pyro-
lysis of motor oil flasks (Fig 4b and c). The two maximums of the carbon number dis-
tribution curve could be explained with the heterogeneity of the raw material. The col-
lected motor oil flasks were composed of polymers with different average molecular
weight.

Contaminant level of pyrolysis products

Chlorine, sulphur and nitrogen content of pyrolysis products were analyzed. Contami-
nants of the gas products (eg. HCl, HCN, H2S, NH3) can be derived from the heteroa-
tom content of the raw material. The chlorine concentration of gases was determined
and it was between 726 and 1003 ppm. The pre-treatment of the motor oil flask could
decrease the chlorine content of the gas products by 10-20%.
The concentration of contaminants in liquid products is shown in Fig. 5a-c. According
to Fig. 5 it can be observed that the degradation products of original HDPE contained
sulphur, chlorine and nitrogen in negligible concentrations. Liquid products derived
from the pyrolysis of motor oil flasks contained chlorine between 591 and 862 ppm,
sulphur between 273 and 428 ppm and nitrogen between 161 and 327 ppm. The pre-
treatment of the raw material could decrease the contaminant level. The chlorine con-
tent decreased approximately by 27%, while sulphur and nitrogen content by 31% and
45%, respectively.
The concentration of contaminants in the heavy oil was lower than in the liquid prod-
ucts. The effect of the raw material pre-treatment on the contaminant concentration of
the heavy oil could be also observed. The application of catalyst did not affect signifi-
cantly the contaminant level of products.

(a)
450
400
Sulphur content, ppm

350
300
250
200
150
100
50
0
Thermal Y-zeolite Thermal Y-zeolite
Motor oil flasks Washed motor oil flasks
 45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic 7

(b) 1000
900

Chlorine content, ppm

800
700
600
500
400
300
200
100
0
Thermal Y-zeolite Thermal Y-zeolite
Motor oil flasks Washed motor oil flasks

(c) 350
Nitrogen content, ppm

300
250
200
150
100
50
0
Thermal Y-zeolite Thermal Y-zeolite
Motor oil flasks Washed motor oil flasks

Fig. 5 – Contaminant level of liquid products: (a) Sulphur content (b) Chlorine content (c) Nitrogen
content

Properties of the pyrolysis products

The properties of the products were determined which are important with respect to
further utilization. According to Table 1 it can established that the density of liquid
products decreased when Y-zeolite was applied. The density of the liquid products
derived from the pyrolysis of motor oil flask was higher than the sample derived from
the HDPE pyrolysis. Corrosion tests of liquids from motor oil flasks shows that they
are in the 1/b class because of the heteroatom containing substances in the pyrolysis
oils. All of the liquid products had a flashpoint below 22°C.
The flashpoint, melting point and heating value of heavy oil were also determined
(Table 2). Flashpoint and melting point of the samples derived from the pyrolysis of
original HDPE decreased by the application of catalyst, which shows the cracking ac-
tivity of the Y-zeoilte. The properties of the samples derived from the pyrolysis of
motor oil flasks did not show significant differences.
 45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic 8

Table 1 – Properties of liquid products

Washed motor oil
Original Motor oil flasks
flasks
Thermal Y-zeolite Thermal Y-zeolite Thermal Y-zeolite
Density (20 °C), g/cm3 0.752 0.719 0.797 0.774 0.792 0.791
Corrosion test 1/a 1/a 1/b 1/b 1/b 1/b
Flashpoint (Pensky-
< 22 < 22 < 22 < 22 < 22 < 22
Martens), °C

Table 2 – Properties of heavy oil

Washed motor oil
Original Motor oil flasks flasks
Thermal Y-zeolite Thermal Y-zeolite Thermal Y-zeolite
Flashpoint
(Marcusson), °C 207 189 215 223 217 214
Melting point, °C 73.1 62.2 74.2 72.1 71.4 70.8
Heating value,
39.4 39.9 38.7 39.1 38.9 39.2
MJ/kg

Conclusion
In this work thermal and thermo-catalytic pyrolysis of contaminated plastic wastes
was studied. The effect of pre-treatment of raw material on the product yields and
quality, especially on the contaminant level was also investigated. It was found that
thermal degradation of contaminated plastic wastes resulted in higher yields of vola-
tile products than the pyrolysis of pre-treated or original raw material. Moreover it
could be stated that the applied catalyst did not have significant cracking and isomeri-
sation effect in case of the pyrolysis of contaminated raw material. The decreased ac-
tivity of the catalyst could be explained with the heteroatom content of raw materials.
The pre-treatment of the contaminated plastic wastes had not significant effect on the
composition and properties of the liquid products. However the contaminant level of
products could be decreased with the pre-treatment of the motor oil flasks.

Acknowledgements
We gratefully acknowledge the financial support from Chemical Engineering Insti-
tute’s Cooperative Research Centre, MOL Hungarian Oil and Gas PLC and Hungar-
ian Academy of Sciences János Bolyai Researching Foundation.

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