Journal of Analytical and Applied Pyrolysis 117 (2016) 273–281

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Journal of Analytical and Applied Pyrolysis

journal homepage: www.elsevier.com/locate/jaap

Thermo-catalytic co-pyrolysis of recovered heavy oil and municipal

plastic wastes
Norbert Miskolczi a,∗ , Funda Ateş b
a
MOL Department of Hydrocarbon and Coal Processing, University of Pannonia, 10 Egyetem u., 8200 Veszprém, Hungary
b
Department of Chemical Engineering, Faculty of Engineering, Iki Eylul Campus, Anadolu University, 26555 Eskişehir, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: In this work municipal plastic wastes were co-pyrolyzed together with waste plastic derived heavy oil at
Received 7 July 2015 500 ◦ C in a stirred batch reactor using ␤-zeolite, y-zeolite and m-Ni-Mo-catalysts. The effect of the heavy
Received in revised form 24 October 2015 oil/municipal plastic waste ratio to the product properties was basically investigated. Higher pyrolysis
Accepted 12 November 2015
oil and gas yields were observed by the using of catalyst and by the re-using of heavy oils. Catalysts could
Available online 25 November 2015
be affecting especially the concentration of hydrogen, isobutene and isopentane in gases. Both pyrolysis
oil and heavy oil contained paraffin, olefins, aromatics and cyclic compounds, while the heavy oil had
Keywords:
hydrocarbons with higher molecular weight. Based on GC–MS and EDXRFS results the composition of
Waste
Catalyst
pyrolysis oil and their contaminants were significantly affected by both the waste plastic/heavy oil ratio
Co-pyrolysis and catalyst presence. Lower waste plastic/heavy oil ratio and selected catalyst could efficiently decrease
Contaminant the concentration of contaminants and increase the valuable hydrocarbon content.
GC–MS © 2015 Elsevier B.V. All rights reserved.

1. Introduction polymers is widely investigated and has much attention in the last
decade. Especially the co-pyrolysis of plastics with biomass [4,5]
Pyrolysis should be an advanced route for waste utilization. As and vacuum gas oil [6] or even with petroleum based heavy oil [7]
a matter of fact, there are different processes for waste pyrolysis, is well published. However, less information is available about the
but only numerous are operates; because the economical prod- waste derived heavy oil and waste polymer co-pyrolysis.
uct utilization is a great challenge [1,2]. Especially, the improving Besides the advantageous of the waste pyrolysis (e.g., reduction
of product composition is still opened questions, which must be of the disposed waste amount, recovery of chemicals, fuels, valu-
solved. Generally synthetic zeolites are applied to obtain higher able products or fossil fuel replacement, etc.), the main benefit of
yields of volatiles together with favorable properties: y-zeolite, the waste co-pyrolysis should be the products upgrading. Marcilla
ZSM-5, ␤-zeolite, MCM-41, etc. [3]. et al. have investigated the pyrolysis properties of the vacuum gas
Industrial scale pyrolysis processes converse wastes into gases, oil and polyethylene blends. They have concluded, that the mix-
pyrolysis oil, heavy oil, tar or even char. Waste derived heavy oil tures of vacuum gas oil and polyethylene is decomposed in two
fraction should be also utilized for energetic purpose, but their have reaction steps; the product yields and properties were significantly
lower price. It is known, that heavy oil obtained by waste pyroly- affected by not only the presence of FCC, ZSM-5, y-zeolite, ␤-zeolite
sis contain similar hydrocarbons than pyrolysis oils, but the length and Al-MCM-41 catalysts, but also by the ratio of vacuum gas oil
of carbon frame and the molecule weight are significantly higher and polyethylene [6,8]. Recently, among others Joppert et al. have
regarding heavy oils. Another difference between the two fractions given a brief summary about the main features of waste polymer co-
is that the pyrolysis oil is more expensive than heavy oil. That is pyrolysis [9]. It was found, that optimized reaction conditions are
why to maximizing the yield of pyrolysis oil is a key question in needed for advanced product properties and the Fractional Design
case of waste polymer pyrolysis. One possible way for heavy oil Methodology should be successfully used to reach favorable prod-
utilization is their re-using as blending into raw materials of pyrol- uct distribution.
ysis and their consequent co-pyrolysis. The co-pyrolysis of different In this work real municipal plastic wastes (MPW) were
pyrolyzed, and then the heavy oil (HO) product was re-used for
their co-pyrolysis together with MPW using different ratios of raw
materials. The product yields and properties have been modified
∗ Corresponding author. by different catalysts: ␤-zeolite, y-zeolite and m-Ni-Mo-catalyst.
E-mail address: mnorbert@almos.uni-pannon.hu (N. Miskolczi).

http://dx.doi.org/10.1016/j.jaap.2015.11.005
0165-2370/© 2015 Elsevier B.V. All rights reserved.
274 N. Miskolczi, F. Ateş / Journal of Analytical and Applied Pyrolysis 117 (2016) 273–281

sured by thermocouple and the wall temperature was controlled

Gases by PID controller. At the end of 1 h pyrolysis three products were
PT
2 4 obtain: gases, pyrolysis oil and heavy oil. Gases from the reactor
top section were driven through a water cooler (T = 20 ◦ C), where
pyrolysis oil was condensed. Then the pyrolysis oil and gas prod-
Nitrogen
ucts were separated in a phase separator and collected for further
TT
3 analysis. The amount of gases was measured by a gas flow meter
and collected in a gas bag. Finally, pyrolysis oil was measured by
laboratory scale and yields were calculated. Based on three inde-
1 TC

TZ pendent parallel measurements, the precision of the pyrolysis was

SD = 1.5%, SD = 1.8% and SD = 1.3% regarding the gases, pyrolysis oil
Pyrolysis oil and heavy oil, respectively.

Char
5
2.3. Product analysis
Heavy oil
Gases were analyzed using gas chromatograph (DANI Mas-
Fig. 1. Process for pyrolysis (1: reactor; 2: water cooler; 3: separator; 4: gas meter; ter Gas Chromatograph, DANI Instruments S.p.A.) provided with
5: filter). PTV/FID, and a 50 m × 0.32 mm silica column (fused with Al2 O3 /KCl
coating), at 40 ◦ C. The calibration was taken based on known com-
Especially the effect of the MPW/re-used, waste derived HO ratio position of gaseous hydrocarbon mixtures based on their retention
to the product structure were investigated. time and peak areas.
The pyrolytic oils were dissolved in dichloromethane (CH2 Cl2 )
2. Experimental and analyzed by gas chromatography/mass spectrometer using a
Hewlett-Packard HP 7890 gas chromatograph coupled to a HP 5975
2.1. Raw materials quadrupole detector. The gas chromatograph was equipped with a
HP-5MS capillary column (phenyl methyl siloxane, 30 m × 0.25 mm
MPW raw material was obtained from urban collection with i.d., Agilent technologies). Helium was selected as the carrier gas
86.7%, 4.2% and 5.7% volatile fraction, fixed carbon and ash content, with the flow rate of 1.2 ml/min. The oven was programmed to
respectively. Owing to the waste source of raw material, it contains hold at 45 ◦ C for 2 min, then rumped at a rate of 5 ◦ C/min to 290 ◦ C
3.4% moisture. Originally, the used MPW was as the mixtures of and held for 10 min. The mass spectrometer was acquired in EI
larger object; therefore they were shredded and then grinded into mode (70 eV) in a mass range of 33–533 m/z. Identification of the
particles with dimension up to 1 cm before pyrolysis. Before the components was based on a comparison of their mass spectra with
pyrolysis, representative amount of raw material was analyzed by Willey library. A detailed description of this method can be found
FTIR method to identify the kinds of polymers and weighted each elsewhere [12].
particle by laboratory scale. Unknown particles were identified by The average molecular weight of heavy oils was measured by a
infrared spectra comparison. Based on results, MPW contains 51.7% Waters type size exclusion chromatography system (Waters 1515
HDPE, 28.9% LDPE, 11.2% PP, 2.5% PVC and 5.5% others. type pump, Waters 717 plus Autosampler unit and Waters 2414
Zeolite type catalysts are widely used to affect the pyrolysis differential refractometer, Ultrastyragel columns (7.8 × 300 mm)).
and modify the product properties [10,11]. In our earlier work Polystyrene standards were used for GPC calibration. Samples had
different zeolites – y-zeolite, ␤-zeolite and Ni-Mo-zeolite – were been dissolved and were filtered on a 0.2 ␮m Millipore (Millex
tested both to promote the increasing in volatile hydrocarbon yields filter) membrane. Impurities in both pyrolysis oils and heavy
and modify their composition [12]. In our current work similar oils were determined by an energy dispersive X-ray fluorescence
catalysts but with different properties were used. Both ␤- and spectrometer in helium medium (Phillips PW 4025/02 MiniPal,
y-zeolites built up by 12 member rings, while the pore size and rhodium-side window tube anode (power of 9W) and Si-PIN detec-
the three dimensional structure complexities are different. Fur- tor). The fluorescent x-ray was detected by a Si-PIN detector with
thermore, each catalyst had grained before pyrolysis to obtain a beryllium window.
similar grain diameter, which was 41 mm (y-zeolite), 39 ␮m (␤- Pyrolysis oils were also analyzed by the following standard-
zeolite) and 45 ␮m (m-Ni-Mo-zeolite), while the micropore surface ized methods: determination of distillation curve (ASTM-D 1078),
areas were 115 m2 /g (y-zeolite), 158 m2 /g (␤-zeolite) and 124 m2 /g determination of flash point (ISO 2719:2002) and determination
(m-Ni-Mo-zeolite). The acidity measurement has resulted that y- liquid density (ISO 12,185:1996).
zeolite has 0.29 mequiv of NH3 /g, ␤-zeolite has 0.40 mequiv of Regarding heavy oils density, flash point, melting point and
NH3 /g and m-Ni-Mo-zeolite has 0.19 mequiv of NH3 /g values. caloric values were measured by ISO 12185:1996, MSZ 15967:1979
and MSZ 24000-5:1978 methods, respectively. The hydrocarbon
2.2. Procedure composition of heavy oil was followed by infrared technique
(TENSOR 27 type Fourier transformed infrared spectrometer,
This work focused to the co-pyrolysis of MPW and MPW derived resolution: 2 cm−1 , illumination: SiC Globar light, monocroma-
HO mixtures (MPW/HO: 100/0, 70/30 and 30/70) in the presence of tor: Littrow prism, detector: RT-DLaTGS (Deutero l-␣-Alanine
different catalysts. The pyrolysis process is shown in Fig. 1. Firstly a Triglycin-Sulphate) type detector with KBr window) in the
larger amount of HO was obtained for further co-pyrolysis using 400–4000 cm−1 wave number range.
500 ◦ C without catalyst. 750 g of raw materials were placed in A Brookefield Cone&Plate viscometer was used to measure the
the stirred reactor in each experiment, and then the reactor wall viscosity of oils. CPA-52Z spindle was used. Viscosities were mea-
temperature was elevated to 500 ◦ C under nitrogen blanket and sured at temperatures of 40 ◦ C and 50 ◦ C and shear rate of 100 s−1 .
atmospheric pressure. In case of thermo-catalytic pyrolyses 5% of Viscosities of oils were determined at temperatures of 40 ◦ C and
catalysts were used. The temperature of the reactor vessel was mea- 50 ◦ C. Because these temperatures are required for adequate flow
 N. Miskolczi, F. Ateş / Journal of Analytical and Applied Pyrolysis 117 (2016) 273–281 275

25 of the heavy oil re-using, that owing to the “dilution” effect, slower
a catalyst deactivation was found.
20
3.2. Composition of gaseous products
Product yield, %

15 The compositions of gaseous products are summarized in Fig. 3,

No-catalyst
which contained hydrogen and C1 –C5 hydrocarbons. However, the
y-zeolite
C2 , C3 and C4 hydrocarbons had the highest portion. It is clear, that
10 m-Ni-Mo
the raw material composition had a slight effect to the gaseous
b-zeolite
product composition, but the presence of catalysts notably affected
5 that. Especially the concentration of hydrogen and branched hydro-
carbons changed significantly. Without catalyst, the hydrogen,
isobutane and isopentane concentration were 3.5–3.8, 4.5–6.0% and
0
5.6–7.8, respectively, which could be increased to 18.5–23.2% and
100/0 70/30 30/70
Waste polymer/Heavy oil rao
13.0–19.8% in thermo-catalytic pyrolysis, respectively. On the other
hand the hydrogen concentration significantly increased by the
80 using of Ni-Mo-catalyst (8.1–9.5%), what was nearly three times
b higher, than that of obtained by thermal pyrolysis, without cata-
70
lysts. It is important to remark, that the concentrations of branched
60 hydrocarbons also increased in the order of 100/0, 70/30 and 30/70
MPW/HO ratio. That refers to both the higher and longer catalysts
Product yield, %

50 activity in case of higher heavy oil containing raw materials. As it

No-catalyst was above discussed, heavy oil should be as “diluting” media of raw
40
y-zeolite materials, because the MPW had higher viscosity and longer car-
30 m-Ni-Mo bon chains than the heavy oils. In general the active sites belong
b-zeolite to microporous surfaces are responsible to gaseous hydrocarbon
20
formation, which should be the cause for the phenomenon that ele-
10 vated gaseous product yields and more significant catalyst activity
(especially isomerisation) was found using 30% MPW diluted in 70%
0 MPW derived heavy oil (30/70 MPW/HO).
100/0 70/30 30/70
Waste polymer/Heavy oil rao
3.3. Pyrolysis oil properties
Fig. 2. Yields of gaseous (a) and pyrolysis oil (b) products from co-pyrolysis of MPW
and HO, using different catalysts and MPW/heavy oils feed ratios. 3.3.1. Characterization of oils by GC–MS
Oil compositions have been evaluated by GC–MS. The distri-
bution of compounds in the oils was determined using a semi
ability and atomization quality and oils at these temperatures quantitative study by means of the percentage area of chromato-
behave in a Newtonian manner [13]. graphic peaks. As can be seen in Table 1, the components in
pyrolysis oil can be grouped into five categories: paraffin, olefins,
aromatics, cyclic, and oxygenated compounds. The percentages of
3. Results and discussion these five main groups of oils have also been given in Table 2.
Pyrolysis oil obtained by non-catalytic treatment of waste plas-
3.1. Product yield tics contains more olefins (49.5%), than that of paraffin (32.8%),
while a small amount of cyclic compounds (4.0%) and oxygenated
The yields of gases and pyrolysis oil are summarized in Fig. 2. compounds (4.0%) were also found. Carbon distribution of the non-
The thermal pyrolysis of 100% MPW has resulted 21.5% pyrolysis catalytic pyrolysis oils was in C9 –C34 range, however wider carbon
oil and 2.5% gas fractions. Contrary, both pyrolysis oil and gas yields range of pyrolysis oil constituents has been found (up to C57 ) in
were higher by the using of catalyst; especially ␤-zeolite catalyst other experimental works [15]. In non-catalytic procedure of plas-
showed high efficiency in increasing of volatile yields (34.2% pyrol- tic waste and MPW/HO, the linear chain hydrocarbons (paraffin and
ysis oil and 8.1% gases). Moreover the yields of volatiles could be olefins) were the main products of oils (82–91%), furthermore the
also increased by the co-pyrolysis of MPW and HO. E.g., the pyrol- olefins were produced with high concentration. When waste plas-
ysis oil yield was 67.9% and 56.2% using 70/30 and 30/70 MPW/HO tics are mixed with heavy oil, the carbon distribution has expanded
ratios. It is also clear that the tendency of increasing was more to the C9 –C36 range. Adding of HO to MPW was able to increase
significant using catalysts, which refers to the advantage of heavy the concentration of paraffin and olefins. Maximum increase in the
oil presence in MPW/HO pyrolysis. Heavy oil has lower viscosity concentration of paraffin and olefins were obtained with mixture of
and average molecular weight than the solid polymer particles. 70/30 MPW/HO, because the paraffin and olefins could be increased
It means that heavy oil was able to “dilute” the MPW particles, by 16.7% and 7.5%, respectively. In the mixture of 30/70 MPW/HO,
which resulted more significant volatile yield increasing efficiency the increase in concentrations was less (6.1% and 5.1%). Olefin to
of catalysts. As it was concluded earlier both the macropores and paraffin ratio of MPW oil was 1.5, while this ratio was 1.4 and
micropores perform key role regarding the polymer decomposition 1.5 for oils obtained with mixture of 70/30 and 30/70 MPW/HO,
reactions, catalyst acidity or even their deactivation [14]. In general respectively.
the scission reaction is started on the macropores of catalyst and As a result of plastics decomposition, the formation of olefins is
then continued both on its macropores and micropores. The great- carried out above 500 ◦ C. The main pyrolysis product below pyrol-
est problem is the catalyst deactivation during the pyrolysis, which ysis temperature of 500 ◦ C is paraffin [16,17]. However, in this
should be occurred by the formation of carbon and polyaromatic study, despite pyrolysis occurs at a pyrolysis temperature of 500 ◦ C,
depositions on the catalyst surface. One of the favorable properties the concentration of olefins is higher than that of the paraffin. It
276 N. Miskolczi, F. Ateş / Journal of Analytical and Applied Pyrolysis 117 (2016) 273–281

Table 1
Main compounds and their relative proportions (area%) in the oils obtained from%100 waste plastic and co-pyrolysis of waste plastic with heavy oil in the catalytic or
non-catalytic procedure.

Retention time Compound name No-catalyst Y-zeolite Ni-Mo-catalyst ␤-zeolite

100/0 70/30 30/70 100/0 70/30 30/70 100/0 70/30 30/70 100/0 70/30 30/70

3.66 Toluene x x x 0.2 1.0 0.6 0.2 0.6 0.4 x 0.8 0.2
4.02 1-Octene x x 0.2 0.5 0.5 0.5 0.3 0.3 0.3 0.2 x 0.3
4.16 3-Octene x x 0.2 x 0.3 0.8 0.2 0.5 0.3 0.3 x 0.5
4.23 Heptane, 2,4-dimethyl- x x x 0.6 x x x x x x x x
4.93 2,4-Dimethyl-1-heptene 0.3 1.3 1.1 1.8 1.8 1.5 1.9 1.1 2.1 1.2 1.9 1.5
5.41 1,2,3-Trimethylcyclohexane x x 0.2 0.6 0.5 0.4 0.2 0.5 0.4 0.2 x x
5.62 Ethyl benzene x x x x 3.2 1.8 0.1 1.2 0.9 0.4 2.1 1.0
5.85 p-Xylene x x x 0.2 x x 0.1 0.8 0.5 0.6 1.6 0.8
6.32 1-Nonene x 1.1 1.0 1.2 x x x x x 0.6 x x
6.5 Nonane 0.3 0.5 0.5 0.8 x x 0.4 x x 0.5 x x
6.61 Styrene x x x x 6.4 5.4 1.0 3.5 3.2 1.0 5.9 4.5
7.31 Benzene, (1-methyl-ethyl)- x x x x 0.3 0.2 0.1 0.1 0.2 0.5 2.1 1.6
8.01 Benzene, propyl- x x x x 0.3 x x x x x 0.5 0.2
8.85 Alpha-methylstyrene x x x x 2.1 1.6 x 1.4 1.2 x x x
8.95 1,9-Decadiene x x 0.4 0.3 x x x x x 0.3 x x
9.21 1-Decene 0.6 2.1 2.0 2.0 2.6 1.9 2.5 2.3 2.6 2.2 0.9 2.2
9.45 4-Decene x x x 0.2 0.5 0.5 x x x x 0.8 0.3
9.72 Decane 1.6 0.6 0.8 1.2 1.0 0.9 0.9 1.0 1.0 1.0 0.5 0.9
9.82 Nonane, 2,6-dimethyl x x x 0.3 x x 0.4 0.3 x 0.3 x 0.3
10.02 Decane, 4-methyl- 0.4 x x 0.4 0.3 x x 0.5 x x x
10.24 Benzene, 1-propenyl x x x x 0.2 0.1 x 0.1 x x x x
11.82 Cyclopentane, propl- 0.9 0.6 0.9 0.6 1.2 1.1 0.8 1.3 0.9 0.8 0.7 0.4
12 Cyclooctane, methyl- 1.0 x x 0.6 x x x x x 0.8 x x
12.29 1-Undecene 2.7 2.1 1.7 2.1 2.2 2.0 2.9 2.1 2.6 1.9 1.3 2.0
12.51 Undecane 1.2 1.0 0.9 1.1 1.2 0.9 1.1 1.1 0.9 1.1 0.8 0.9
12.63 5-Undecene 0.2 x 0.1 0.2 0.3 0.2 0.4 0.2 x 0.3 x 0.3
12.9 Benzene, 4-ethyl-1,2-diimethyl- x x x x x x x x x 0.1 0.4 0.1
13.06 Benzene, 1,2,4,5-tetramethyl- x x x x x x x x x 0.2 0.6 x
13.24 Ethanone, 1-cyclohexyl- 0.3 x 0.1 0.1 x x x x x 0.2 x x
13.91 2,2-Dimethyl-3-heptene trans 0.3 x 0.1 0.5 0.3 0.2 0.2 x 0.2 0.1 x x
14.82 1,11-Dodecadiene 0.8 0.5 0.6 0.2 0.7 0.6 0.8 0.5 0.5 0.6 0.2 0.6
15.12 1-Dodecene 2.5 1.9 1.9 2.3 2.0 1.8 2.0 1.9 1.9 1.9 1.1 1.9
15.34 Dodecane 1.6 1.1 0.9 1.1 1.2 1.1 1.3 1.0 1.2 1.0 0.9 1.2
17.46 Cylohexane, eicosyl- x x x x x x 0.2 x x 0.5 0.3 0.3
17.55 Cyclopentane, decy- x x x x x x 0.3 0.6 0.5 0.2 x x
17.66 1,12-Tridecadiene 1.1 0.9 0.7 x 0.9 0.7 0.7 0.4 0.6 0.7 x 0.7
17.83 1-Tridecene 3.0 2.2 1.9 2.3 2.1 2.1 2.7 2.4 2.0 2.0 1.5 2.1
18.12 Tridecane 1.7 1.2 1.2 1.4 1.4 1.2 1.6 1.4 1.5 1.3 1.2 1.2
18.28 Cyclohexane, 1,2,4-terimethyl- 2.0 1.0 0.7 1.1 0.9 0.9 1.1 1.2 1.3 0.8 0.5 0.8
18.47 Naphthalene, 2-methyl 0.8 0.4 0.3 0.5 0.5 0.5 0.4 0.7 0.5 0.4 0.2 0.5
18.71 4-Isopropyl-1,3-cyclohexanedione 1.5 0.7 0.6 0.9 0.8 0.8 0.9 1.3 1.0 0.7 0.5 0.8
19.50 Cyclohexane, (3-methylpentyl)- x x x 0.3 x 0.2 0.2 x x 0.2 x x
20.31 1,13-Tetradecadiene 0.8 0.8 0.6 0.4 0.8 0.5 1.5 x 0.4 0.6 0.3 x
20.41 Cyclotetradecane x x x 0.8 x x x x x x x x
20.56 1-Tetradecene 3.0 2.5 2.0 1.7 2.1 2.0 2.9 2.8 1.8 2.2 1.3 2.2
20.65 Tetradecane 1.5 1.1 0.9 0.8 1.1 0.9 0.7 1.2 0.9 1.0 1.0 1.1
22.83 E-10-Pentadecenol 0.7 1.0 0.6 1.0 0.5 0.5 0.4 0.6 0.3 0.6 0.2 x
22.98 1-Pentadecene 3.2 2.6 2.3 2.0 2.1 2.3 2.2 3.0 2.0 2.5 1.7 2.8
23.17 Pentadecane 1.8 1.5 1.1 1.3 1.2 1.1 1.0 1.2 1.1 1.1 1.1 1.0
23.77 Trans-7-pentadecene 0.5 0.4 0.3 0.4 0.6 0.3 0.5 0.3 0.5 0.5 0.4 0.2
24.82 Bicyclo[3.2.1] oct-2-ene x x x x x x 0.7 x x x x x
25.21 1,15-Hexadecadiene x 0.8 x 0.8 0.3 x 0.6 x 0.5 x 0.5 x
25.45 1-Hexadecene 2.8 2.3 2.9 2.0 1.9 2.6 2.9 2.6 1.7 2.9 1.2 2.8
25.55 Hexadecane 1.8 1.5 1.2 1.0 1.2 1.1 0.9 1.2 0.9 1.2 1.3 0.9
26.88 Benzene, 1,1 -(1,3-propaneddyl) bis x x x x 1.0 0.7 0.2 1.0 0.8 x 1.1 0.6
27.48 E-2-Octadecadecen-1-ol x x x x 0.3 x x 0.4 0.3 0.5 x x
27.60 1-Heptadecene 2.6 3.0 2.8 3.0 1.8 2.6 2.9 2.6 1.8 2.2 1.3 2.8
27.85 Heptadecane 1.5 1.3 1.1 0.9 1.2 1.1 1.1 1.3 1.3 1.1 1.1 0.9
28.22 5-(Aminooxy) pent-1-enylbenzene x x x x 0.7 0.1 0.1 0.3 0.4 0.2 0.4 0.2
28.63 1-Hexadecanol, 2-methyl- 0.6 0.5 0.4 0.5 0.4 0.7 0.3 0.4 0.2 0.3 0.2 0.4
29.38 Naphthalene, 1,2,3,4-tetrahydro-1-phenyl x x x 0.5 0.2 0.4 0.1 0.2 0.5 0.2 0.9 0.1
29.74 1-Octadecene 3.0 2.8 2.8 2.3 1.7 2.0 2.2 2.3 1.8 2.2 1.2 1.9
29.96 Octadecane 1.3 1.1 1.2 0.8 1.1 1.1 1.1 1.2 1.5 1.1 1.1 1.0
31.15 Naphthalene, 1-phenyl- x x x x 0.2 x x 0.3 0.3 x x x
31.69 18-Nonadecen-1-ol 1.0 0.7 x x 0.3 x x x 0.2 x x x
31.85 1-Nonadecene 2.3 2.0 2.9 3.0 1.6 2.6 2.9 2.8 1.7 2.3 2.3 2.4
31.98 Nonadecane 1.8 1.1 1.1 1.2 1.2 1.0 1.2 1.3 1.6 1.1 1.1 1.0
33.08 2-(3-thienyl)-butanal x x x x x x 0.2 x 0.2 0.3 0.3 x
33.42 Naphthalene, 2-phenyl- x x x x 0.1 x x 0.1 x x 0.4 0.1
33.68 1-Octadecanol x x 0.4 0.5 0.3 0.4 0.2 0.3 0.1 0.2 0.5 0.4
33.80 1-Eicosene 2.3 2.5 2.8 2.8 1.7 2.1 1.7 1.8 1.7 2.2 2.0 2.0
33.92 Eicosane 1.6 1.1 1.1 0.9 1.1 1.2 1.2 1.0 1.4 1.1 1.2 1.0
34.14 5-Eicosene x x x 0.7 0.2 0.1 0.2 x 0.6 0.5 0.3 0.2
 N. Miskolczi, F. Ateş / Journal of Analytical and Applied Pyrolysis 117 (2016) 273–281 277

Table 1 (Continued)

Retention time Compound name No-catalyst Y-zeolite Ni-Mo-catalyst ␤-zeolite

100/0 70/30 30/70 100/0 70/30 30/70 100/0 70/30 30/70 100/0 70/30 30/70

35.46 2-Octadecyl-propane-1,3-diol x x x x x x 0.1 x x 0.3 0.5 0.2

35.58 1-Heneicosene 2.5 2.7 2.7 2.6 1.6 2.2 2.7 2.1 2.9 2.1 2.0 2.2
35.76 Heneicosane 1.1 1.4 1.2 1.0 1.0 1.1 0.9 1.3 1.3 1.0 1.2 0.9
36.26 10-Heneicosene x x x 0.6 x 0.1 0.2 0.2 0.2 0.5 0.3 0.3
37.33 1-Docosene 2.3 2.6 2.4 2.6 1.7 2.0 2.6 2.0 2.4 2.4 2.0 2.0
37.54 Docosane 1.1 1.4 1.1 1.1 0.9 1.1 0.9 1.2 0.9 1.0 1.2 0.9
37.81 Bicyclo[3.1.1]heptan-3-one, 6,6-dimethyl- x x x x x x 0.6 x 0.1 x 0.7 x
38.33 Cyclohexane, 2,4-diethyl-1-methyl- x x x x x x 0.5 x 0.4 0.2 0.6 0.3
38.98 1-Tricosene 2.0 2.4 2.4 2.4 1.3 1.9 2.5 2.0 2.0 2.0 2.1 2.0
39.23 Tricosane 1.0 1.3 1.0 0.9 0.9 1.0 0.5 1.0 1.0 0.9 1.0 0.7
39.53 Cyclotetracosane x x x 0.6 x 0.1 0.3 x 0.1 0.6 0.5 0.3
40.68 Tetracosene 1.8 2.4 2.2 2.4 1.5 1.7 2.3 1.8 2.3 2.1 1.7 2.0
40.89 Tetracosane 0.9 1.4 0.9 0.7 0.9 0.9 1.0 1.0 1.1 0.9 0.9 0.6
42.3 Pentacosene 1.7 2.2 2.3 1.9 1.5 1.6 2.0 1.4 2.2 1.9 1.8 1.7
42.42 Pentacosane 0.8 1.3 0.9 0.7 0.8 0.8 0.8 1.0 1.0 0.7 1.0 0.7
43.14 1H-indole, 2-methyl-3-phenyl x x x 1.8 x x 0.4 x x x 0.5 x
43.74 Hexacosene 2.3 2.3 2.2 2.0 1.5 1.6 2.0 1.5 2.1 1.9 1.8 1.8
43.94 Hexacosane 1.3 1.3 0.8 0.5 0.7 0.7 1.2 0.8 1.2 0.8 1.1 0.7
44.57 2-Hepten-4-one, 6-hydroxy-2-methyl-6- x x x x x x 0.8 x 0.1 x 0.1 x
45.31 1-Heptacosene 1.8 2.1 2.1 1.7 1.4 1.4 x 1.5 2.1 1.6 1.6 1.5
45.38 Heptacosane 1.1 1.2 0.7 0.6 0.7 0.7 0.9 0.8 0.9 0.8 0.9 0.6
46.64 1-Octacosene 1.1 1.8 2.0 0.3 1.3 1.4 x 1.6 2.0 1.7 1.6 1.4
46.79 Octacosane 0.8 1.1 0.9 2.2 0.7 0.7 1.4 0.7 1.6 0.9 0.8 0.6
48 1-Nonacosene 1.0 0.2 0.3 x x 1.4 x x 1.0 x 1.8 1.4
48.14 Nonacosane 0.8 1.9 2.6 1.7 1.9 0.5 1.5 2.2 1.9 1.2 1.3 0.6
49.4 1-Triacontene 1.1 0.1 2.2 x x x x x x 1.6 1.4 0.1
49.45 Triacontane 0.9 1.0 0.7 1.9 1.8 1.8 1.7 2.2 1.9 0.6 1.6 2.1
50.45 1-Hentriacontene 0.2 2.9 x x x 1.1 x x x x x 1.4
50.7 Hentriacontane 1.8 2.6 2.3 1.6 1.7 0.6 1.9 2.1 1.8 1.8 1.7 0.5
52 Dotriacontane 1.3 0.3 2.1 1.4 1.5 1.5 1.4 1.8 1.4 1.7 1.7 1.4
52.74 Cyclohexyleicosane x x x x x x 0.9 0.2 0.4 x x x
53.51 Tritriacontane 1.1 2.4 2.0 1.2 1.4 1.4 1.3 1.6 1.2 1.7 1.3 1.7
55.3 Tetratriacontane 0.9 2.4 2.0 1.2 1.3 1.3 0.9 1.7 1.1 1.8 1.0 1.7
57.57 Pentatriacontane x 2.2 2.1 0.9 1.6 1.6 1.0 2.0 1.5 1.6 0.9 1.7
60.19 Hexatriacontane x 1.9 1.9 0.7 1.0 1.1 1.0 1.4 1.1 1.5 0.9 1.5

Table 2
Main properties of pyrolysis oils using different catalysts and MPW/heavy oils feed ratios.

No-catalyst Y-zeolite m-Ni-Mo ␤-zeolite

MPW/HO 100/0 70/30 30/70 100/0 70/30 30/70 100/0 70/30 30/70 100/0 70/30 30/70

Density, g/cm3 (at 20 ◦ C) 0.848 0.841 0.832 0.822 0.805 0.787 0.828 0.801 0.792 0.814 0.795 0.782
Viscosity at 40 ◦ C, mPas 133 188 216 119 147 181 126 161 202 113 133 168
Viscosity at 50 ◦ C, mPas 94 129 143 84 107 122 89 114 138 71 95 108
Boiling point, ◦ C
IBP 30 29 32 28 29 26 28 30 29 29 30 30
10% 117 106 101 96 92 85 97 94 88 90 86 79
50% 190 186 182 173 162 156 179 166 159 171 160 152
90% 291 288 285 279 270 263 278 275 268 274 268 261
FBP 324 319 322 316 317 315 319 317 316 316 318 315

Paraffin 32.8 38.3 34.9 32.0 31.6 30.1 31.4 36.1 34.6 31.8 29.6 27.2
Olefins 49.5 53.3 52.1 49.1 41.0 46.7 49.0 43.8 46.2 47.3 38.2 47.4
Aromatic compounds - - - 3.1 16.4 11.5 2.8 10.2 9.0 3.5 17.5 9.8
Cyclic compounds 4.0 1.6 1.8 4.5 2.6 2.7 5.8 3.8 4.0 4.3 3.7 4.1
Oxygenated compounds 4.0 2.9 2.1 3.0 2.7 2.3 2.8 2.4 2.4 3.1 2.6 2.0
n(Olefin)/n(Paraffin) 1.5 1.4 1.5 1.5 1.3 1.6 1.6 1.2 1.3 1.5 1.3 1.8

Cl, mg/kg 1285 731 173 1322 639 214 1135 631 195 1273 683 210
Br, mg/kg 1533 937 264 1407 1140 326 1522 1053 279 1563 1099 385
P, mg/kg 498 307 115 663 315 94 582 357 102 574 298 117
S, mg/kg 71 33 16 57 29 15 65 36 9 51 24 14
Sb, mg/kg 189 111 47 173 104 37 164 117 51 179 96 43

refers that thermal cracking favored the formation of olefins in this Aromatic compounds were not determined in the non-catalytic
study. Thermal degradation process of plastic wastes (mainly con- procedure, while oxygenated and cyclic compounds were detected
sist of polyethylene) has been carried out via random chain scission only small amounts. Cyclic compounds in co-pyrolysis experi-
to form primary radicals. These primary radicals can undergo ␤- ments decreased slightly compared to pyrolysis of waste plastics
scission, which reactions of secondary radicals have promoted the alone (Table 2). Oxygenated products are undesirable in oils. They
formation of olefins [18]. In this respect, pyrolysis temperature of decrease heating value and stability of oils, while increases vis-
500 ◦ C is considered to be sufficient to formation of olefins in this cosity, and also they make oils corrosive. Because of the structure
study. of raw material, oxygenated compounds were detected only small
278 N. Miskolczi, F. Ateş / Journal of Analytical and Applied Pyrolysis 117 (2016) 273–281

amounts (between 2 and 4 %) in non-catalytic procedure. This

means, the obtained products have high boiling point and low valu-
able products. The addition of the catalyst to the process at this
stage would be more beneficial regarding the quality of the product
[19]. Zeolites are identified as one of the most effective catalyst for
cracking of plastics in the literature [19], because they can influ-
ence the product distribution. When the olefins and paraffin are
considered in 100% MPW pyrolysis experiments, it is seen that
the contribution of all catalysts was less (Table 2), but the effect
of the catalysts has been more significant in co-pyrolysis exper-
iments. The concentration of paraffin and olefins was reduced in
the co-pyrolysis experiments. Paraffin and olefins showed a min-
imum decrease, when MPW was pyrolyzed alone in the catalytic
experiments. But the concentrations of these two components have
significantly decreased using y-zeolite and ␤-zeolite in the co-
pyrolysis. The maximum decrease in concentrations of paraffin and
olefin are provided with mixture of 70/30 MPW/HO and a ␤-zeolite,
when compared to non-catalytic procedure. The concentration of
paraffin and olefins decreased of 22.7 % and 28.3%, respectively.
When the results with y-zeolite are evaluated, the decrease was
slightly less than that of the obtained with ␤-zeolite. In the mixture
of 30/70 MPW/HO, the decrease in concentrations was 21.9% and
9% with ␤-zeolite. During the catalytic reactions, produced paraffin
and olefins first were decomposed to lighter ones. Then, the olefins
were absorbed on the acid sites and undergo further reactions to
produce mainly gas compounds and aromatics [20]. When con-
sidered to the percentage of the paraffin and olefins, least change
was obtained with the Ni-Mo-zeolite catalyst among other cata-
lysts. For instance, in the mixture of 70/30 MPW/HO, paraffin and
olefins were decreased of 5.9% and 17.7%, respectively. Cyclic com-
pounds and oxygenated components in co-pyrolysis experiments,
decreased slightly compared to pyrolysis of waste plastics alone as
well as non-catalytic procedure.
Catalytic procedure has faster reaction rate and lead to some
reactions such as isomerization, aromatization, as well as cracking
[19]. All three types of catalysts produced aromatic compounds,
whereas aromatization reactions are not favored during non-
catalytic procedure. In this study, aromatics are mainly composed
of toluene, p-xylene, styrene, alkyl-benzene and naphthalene sub-
stitutes (Table 1). When MPW is pyrolyzed alone, the concentration
of aromatic components was observed close to each other (∼3%).
But, in the co-pyrolysis experiments, maximum yield of this com-
ponent (17.5%) was obtained with the ␤-zeolite and in the mixture
of 70/30 MPW/HO. In the same mixture, the yield of aromatics
obtained with y-zeolite (16.4%) was slightly lower than that of the
␤-zeolite. It is seen that the concentration of paraffin and olefins
significantly reduced in the catalytic co-pyrolysis experiments and
aromatic compounds displaced of paraffin and olefins.
Plastic wastes can be converted to fuel components by conven-
tional methods. When assessing the oil products, these methods
can be divided into three distinction groups: thermal cracking
(pyrolysis), catalytic cracking or hydrocracking. Catalytic cracking
reactions take place on the catalyst surface, while thermal crack-
ing reactions occur both on the catalyst surface and the spaces
between the particles of the catalyst. So, both pyrolysis mechanisms
also work effectively during the catalytic pyrolysis [21]. Catalytic
cracking is an alternative and more selective process compared
to pyrolysis. Generally, catalytic cracking contributes to the for-
Fig. 3. Composition of gaseous products (in v/v%) from co-pyrolysis of MPW and HO, mation of valuable products. In the catalytic degradation of the
using different MPW/HO ratio (without catalyst (a), y-zeolite (b), m-Ni-Mo-catalyst
polymer chain, the molecular weight of polymer chain could be
(c) and ␤-zeolite (d)).
rapidly reduced and then carbonium ion intermediates would be
rearranged by hydrogen and carbon atoms shifts with producing
the high quality isomers. In the reactions that proceed by the car-
bonium ion mechanism, the reaction rate is accelerated by strong
acid sites [19,22]. Polymers with long chain are broken by the effect
of rising temperatures and paraffin forms first, then olefins dur-
 N. Miskolczi, F. Ateş / Journal of Analytical and Applied Pyrolysis 117 (2016) 273–281 279

Table 3
Some other properties of heavy oil using different catalysts and MPW/heavy oils feed ratios.

No-catalyst Y-zeolite m-Ni-Mo ␤-zeolite

MPW/Heavy oil 100/0 70/30 30/70 100/0 70/30 30/70 100/0 70/30 30/70 100/0 70/30 30/70

Density, g/cm3 (at 100 ◦ C) 0.889 0.885 0.978 0.877 0.869 0.861 0.875 0.870 0.864 0.876 0.868 0.859
Flash point, ◦ C 218 217 215 206 201 194 207 204 199 202 198 193
Melting point, ◦ C 101 98 97 96 93 90 95 91 86 96 92 87
Mw , g/mol 1960 1880 1805 1685 1560 1430 1670 1540 1415 1665 1535 1420
Caloric value MJ/kg 40.8 40.9 41.0 41.1 41.2 41.1 40.9 41.2 41.1 41.2 41.0 40.9
Aliphatic paraffin content, % 58.5 60.6 59.8 49.7 36.2 36.6 53.9 44.6 48 45.7 36.7 35
Aliphatic olefin content, % 38.2 35.5 37.3 38.4 29.7 29.9 28.5 23.6 20.5 41.9 30.3 33.2
Aromatic content, % 1.1 2 1.4 5.2 27.8 26.3 6.3 16.7 17.1 7.1 28.3 27.6
Naphthen content, % 2.2 1.9 1.5 6.7 6.3 7.2 11.3 15.1 14.4 5.3 4.7 4.2
Cl, mg/kg 284 239 244 295 273 256 248 239 251 264 271 258
Br, mg/kg 331 320 317 334 315 347 329 312 306 313 325 317
P, mg/kg 82 75 71 88 89 73 74 85 81 84 79 78
S, mg/kg 17 15 17 19 18 16 20 18 16 15 17 18
Ca, mg/kg 14 11 12 14 16 12 15 18 17 18 15 14
Sb, mg/kg 44 41 46 42 49 42 44 47 41 43 48 42

The stability of pyrolysis oils is important, because it affects the

handling or storage of products. Viscosity indicates the stability
of oil product [25]. Depending on raw material, viscosity of pyrol-
ysis oil (40–100 mPas at 50 ◦ C) is less than that of the heavy oil
(180 mPas) [26]. Viscosity, , of oils generated from 100% waste
plastic or co-pyrolysis of MPW/HO with (y-zeolite, ␤-zeolite, Ni-
Mo), or without catalyst were determined. Obtained data were
presented in Table 2. In general, the viscosity of oils decreases with
an increase in temperature. The viscosity of oils at 40 ◦ C was higher
than that of 50 ◦ C independent of with or without catalyst. Viscos-
ity obtained from 100% waste plastics without catalyst was 133
and 94 mPas for 40 ◦ C and 50 ◦ C, respectively. Heavy oil has a ten-
dency of increase in viscosity. In fact, the higher the percentage
Fig. 4. Olefin/paraffin ratio of heavy oils obtained from MPW/HO co-pyrolysis, using of added heavy oil the higher viscosity obtained. Heteroatoms S,
different catalysts and MPW/heavy oils feed ratios. N, O in the heavy oil can interact with other groups by hydrogen
bonding or weak van der Waals forces, and polymerize to form
larger molecules, thus leading to the increasing of viscosity [27].
ing thermal cracking. Catalysts are used in pyrolysis to break long An increase was observed in viscosity of oil products obtained
straight chain carbons. Breaking of the CC bonds and conversion of by adding heavy oil to waste plastics compared to pyrolysis of
primary products to more valuable secondary products are carried 100% waste plastics. Therefore, it is important to evaluate heavy
out by Brondsted acidic sites in the catalytic cracking. Olefins are the oil together with other products instead use alone. The results
primary products and aromatics are produced by olefin cyclization showed that the viscosity of oils produced without catalyst was
in the catalytic procedure. However, the formation and selectiv- high. But pyrolysis with catalyst improved the viscosity of oils.
ity of these products are mainly depend on the type of catalyst The viscosities by using different catalysts, y-zeolite, ␤-zeolite and
used [17,19]. Zeolites have strongly acid features. Pore sizes and Ni-Mo, were reduced compared to non-catalytic procedure. The
acidity of catalysts are also important and contributes to cracking viscosity of all oil samples, as reported in Table 2, was reduced
and isomerization of hydrocarbons [23,24]. Y-zeolite and ␤-zeolite 15–24.5% comparing to non-catalytic procedure. Viscosity of the
which have high acidity promote the secondary reactions such as 30/70 MPW/HO at 50 ◦ C was determined as 122, 108 and 138 mPas
isomersation and aromatization. using y-zeolite, ␤-zeolite and Ni-Mo respectively, which is smaller
In this study, acidic catalysts contributed to the elimination of than the viscosity of heavy oil. So, the use of appropriate catalyst is
paraffin and olefins and generation of aromatics. ␤-zeolite cat- the key factor to improved oil viscosity. An appropriate catalyst
alyst has been determined as superior, while mixture of 70/30 reacts with the heteroatom-containing groups, and the viscosi-
MPW/HO was the optimum ratio regarding production of aromatic ties of oils reduce. ␤-zeolite was determined as the most effective
compounds. catalyst for producing low-viscosity pyrolysis oils. Oils that were
catalyzed with ␤-zeolite had a lower viscosity than that of the
3.3.2. Other properties of pyrolysis oils oils catalyzed with other catalysts. Oils that have highest viscos-
Table 2 summarizes the other properties of heavy oils. Their ity are those obtained with Ni-Mo catalyst. The viscosities of the
boiling point ranges were between 26 and 324 ◦ C, while their den- oils generated using ␤-zeolite catalyst at 50 ◦ C were 71, 95 and
sity was changed in the range of 0.782–0.848 g/cm3 . Both boiling 108 mPa s for oils generated from 100% MPW, 70/30 MPW/HO
point ranges and densities of pyrolysis oils well demonstrated that and 30/70 MPW/HO, respectively. The higher the larger molecule
higher portion of components with lower molecular weights was products content, the higher the viscosity of the oils. Viscosities
in pyrolysis oil not only with decreasing MPW/HO ratios, but also have been decreased by break down larger molecules. Oils pro-
in the presence of any catalysts. E.g., the density of pyrolysis oil duced with catalyst suggested that they are more stable because
was 0.848, 0.845 and 0.841 g/cm3 using 100/0, 70/30 and 30/70 viscosities are lower than that of the oils produced without catalyst.
MPW/HO ratios without catalyst, respectively. Furthermore the Regarding contaminants chlorine, bromine, phosphorous, sulphur
densities of thermo-catalytic derived pyrolysis oils were in the and antimony was measured in pyrolysis oils. The most benefit of
range of 0.782–0.828 g/cm3 . the MPW/HO co-pyrolysis is that the concentrations of contam-
280 N. Miskolczi, F. Ateş / Journal of Analytical and Applied Pyrolysis 117 (2016) 273–281

inant have significantly decreased, what is important advantage m-Ni-Mo-catalyst. Owing to the “dilution” effect of the heavy oil,
for further fuel-like utilization of pyrolysis oils. E.g., the concentra- higher yields of gaseous product and pyrolysis oil were found
tion of chlorinated compounds was 1285, 731 and 173 mg/kg using using lower MPW/HO ratio, especially in the presence of ␤-
raw materials with 100/0, 70/30 and 30/70 MPW/HO oil ratios, zeolite catalyst. Each catalyst modified the main carbon frame of
respectively. A similar trend was found regarding the other ele- both gaseous and pyrolysis oil products, resulting vast amount of
ments (Br, P, S and Sb) and the lowest Br, P, S and Sb content was branched hydrocarbon. Pyrolysis oils contain olefins, paraffin, small
measured in case of 30/70 MPW/heavy oil ratios with 264 mg/kg, amount of cyclic compounds and oxygenated compounds in carbon
94 mg/kg, 9 mg/kg and 37 mg/kg, respectively. It is also clear, that range of C9 –C34 . Acidic ␤-zeolite catalyst showed high activity in
the catalysts could not significantly affect the contaminant amount elimination of paraffin and olefins and increasing of the aromat-
in pyrolysis oils. MPW destruction experiments resulted pyrolysis ics concentration, while 70/30 MPW/HO was the optimum ratio
oils with 1285 mg/kg Cl, 1533 mg/kg Br, 498 mg/kg S and 189 mg/kg regarding production of aromatics. Owing to the real waste source
Sb containing without catalysts, while the Cl, Br, P, S and Sb concen- of the raw material, chlorine, bromine, phosphorous, sulphur and
tration were in the range of 1273–1322 mg/kg, 1407–1563 mg/kg, antimony as contaminants were detected in pyrolysis oil and heavy
574–663 mg/kg, 51–65 mg/kg and 164–179 mg/kg using catalyst, oil. The most benefit of the MPW/HO co-pyrolysis was that the
respectively. concentrations of contaminant could significantly decreased using
higher concentration of heavy oil. Regarding hydrocarbons, heavy
oils contained aliphatic paraffin and olefins, aromatics and cyclic
3.4. Heavy oil properties
compounds. ␤-zeolite and y-zeolite catalysts increased a bit the
olefin concentration, while Ni-Mo-catalyst promoted especially the
The selected properties of the heavy oils are summarized in
production of cyclic hydrocarbons.
Table 3. Heavy oils have higher density, than pyrolysis oils. It was
changed in the range of 0.859–0.889 g/cm3 . Similarly as it was
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