The objective of this paper is the upgrading of chlorinated oils coming from the pyrolysis of mixed

plastic waste, in order to use them as fuel or feedstock for refineries. Two different samples of
pyrolysis oils have been thermally and catalytically cracked in a 300 mL autoclave at 325 °C and the
auto-generated pressure. Thermal cracking converts the plastic pyrolysis heavy oils into light liquid
fraThe pyrolysis oils used for the experiments were two samples obtained by the authors in previous
experiments of pyrolysis of municipal plastic waste, carried out in an installation consisting on a 3.5 L
semibatch reactor and a condensing system equipped with three condensers and an activated
carbon column, and purged with a 1 L min−1 N2 flow [6,18]. More specifically, two pyrolysis oils
samples have been used; (1) pyrolysis oils coming from several thermal pyrolysis of a mixture of 40
wt.% PE/35 wt.% PP/18 wt.% PS/4 wt.% PET/3 wt.% PVC carried out at 500 °C, atmospheric pressure,
and dwell times from 0 to 120 min, and (2) pyrolysis oils coming from catalytic pyrolysis runs of the
sameThere is some discussion within scientific community at this point. On the one hand, some
publications do not attribute any catalytic effect to Red Mud in terms of cracking enhancement
[28,29]. On the other hand, the authors [17,18], as well as other researchers [36,37], have
demonstrated that Red Mud possesses catalytic effect. The lack of agreement concerning the
catalytic effect of Red Mud can be attributed to the variation of the composition of this product
depending on its origin, due to the fact that it is a by-product coming from an industrial process
which uses mineral ore as raw material. For instance, Na2O is known to act as a catalytic poison in
the decomposition of some hydrocarbons and it has been reported that its proportion in Red Mud
can be up to 6 wt.% [38]. On the contrary, Table 1 shows that the Na2O content of the Red Mud
used for these experiments is much lower (1.8 wt.%). Looking at the results obtained in the catalytic
run of PO2 and comparing them to the results of the thermal run, it can be seen that the catalytic
effect of Red Mud is similar to that observed with PO1: the cracking ratio of PO2 in presence of Red
Mud is higher than in the case of the thermal run (from 67.5 to 86.5 wt.%), which means that the
yield of the heavy fraction decreases (13.5 wt.%).

This paper aims to examine the effect of different plastic waste types such as polystyrene (PS),
polyethylene (PE), polypropylene (PP) and polyethylene terephthalate (PET) on the yield and quality
of produced liquid oil from the pyrolysis process. A small pilot scale pyrolysis reactor was
commissioned for this purpose, and operated at optimum temperature and retention time of 450 C
and 75 min respectively. PS plastic waste showed maximum production of liquid oil (80.8%) along
with least production of gases (13%) and char (6.2%) in comparison to other plastic types. Liquid oils
from all plastic types contained mostly aromatic compounds with some alkanes and alkenes. Liquid
oil from PS pyrolysis contained styrene (48.3%), ethylbenzene (21.2%) and toluene (25.6%). Pyrolysis
liquid oils found to have ranges of dynamic viscosity (1.77e1.90 mPa s), kinematic viscosity
(1.92e2.09 cSt), density (0.91e0.92 g/ cm3 ), pour point (11(-60 C)), freezing point (15-(-65 C)), flash
point (28.1e30.2 C) and high heating value (HHV) (41.4e41.8 MJ/kg) similar to conventional diesel,
thus have potential as an alternative energy source for electricity generation. Upgrading of liquid oil
using different post-treatment methods such as distillation, refining and blending with conventional
diesel is required to make it suitable as a transport fuel due to presence of high aromatic
compounds. The recovery of aromatic compounds especially styrene from pyrolysis oil can be a
potential source of precursor chemic

Therefore cracking has been enhanced by Red Mud. At the same time, the light fraction and gases
yields significantly increase (66.1 and 20.4 wt.% respectively). At first sight, the increase of the liquid
fraction in the catalytic experiment of PO2 (compared to the thermal one) could seem to be contrary
to the behavior of PO1 sample, which showed a decrease in the liquid fraction under catalytic
conditions. However, this is also a consequence of the higher cracking obtained with Red Mud and it
can explained at follows: when PO2 is cracked in presence of Red Mud, the cracked molecules seem
not to be small enough to be part of the gas fraction, and most of them condense to be part of the
liquid fraction. The overall result, compared to the thermal experiment, is that the liquid fraction
increases, but this also means more cracking, as in the case of the PO1. This is probably due to the
different chemical nature of the oils, since PO2 is an almost completely aromatic sample and, as it
has been mentioned before, the aromatic chemicals have in general higher thermal stability than the
aliphatics.