Fuel 203 (2017) 244–252

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Fuel
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Full Length Article

Catalytic cracking of heavy fractions from the pyrolysis of waste HDPE

and PP
Peter Lovás, Pavol Hudec ⇑, Boris Jambor, Elena Hájeková, Michal Horňáček
Department of Petroleum Technology and Petrochemistry, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, Slovak Republic

h i g h l i g h t s

 Pyrolysis of automotive waste HDPE and PP plastics.

 Preparation of distillation ends from HDPE and PP pyro-oils.
 Catalytic cracking of HDPE-wax and PP-wax in MAT.
 Comparison of cracking products of linear and branched polymer-waxes.
 HDPE-wax increases gas-yield while PP-wax increases gasoline-yield.

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

Article history: In the present paper, automotive waste plastics were considered as a potential source of fuels and
Received 24 May 2016 chemicals. The feedstock in the experimental tests was represented by the heaviest fractions from the
Received in revised form 17 April 2017 distillation of pyro-oil from the pyrolysis of high-density polyethylene (HDPE-wax) and polypropylene
Accepted 27 April 2017
(PP-wax). Due to their very high viscosity both polymer-waxes were, prior to processing, diluted in atmo-
spheric gas oil (GO). Mixtures with hydrotreated vacuum gas oil (HVGO) were also prepared and pro-
cessed under simulated fluid catalytic cracking conditions via a MAT-test. The product distribution
Keywords:
was similar to the one shown by the commercial FCC process: light gases (C1, C2), LPG, gasoline fraction,
Catalytic cracking
HDPE
light and heavy cycle oil. To maintain optimal performance a commercial FCC equilibrium catalyst (FCC-
PP ECAT) was used. When processing HDPE and PP waxes, high yields of profiling products – propylene and
FCC gasoline were obtained. In the case of the PP-wax feed without HVGO, the yield of gasoline was even
Gasoline higher than in case of pure HVGO. When cracking HDPE-wax feed mixtures the product distribution
was oriented more towards the production of propylene. The composition of liquid products considering
all types of feedstock consisted mainly of iso-alkanes and aromatics. The calculated values of microactiv-
ity for the HDPE-wax and PP-wax feedstock, with or without HVGO, were significantly higher than in the
case of pure HVGO.
Ó 2017 Published by Elsevier Ltd.

1. Introduction with an energetic potential. Chemical recycling thus represents

Increased production by the automobile industry and increas-
ing demand for new cars every year naturally results in the gener-
ation of automotive waste, and this is predominantly polymer
waste. In relation to the high-energy prices and strict emission lim-
its, a great effort is being made to find suitable ways of improving
plastics recovery [1]. Several routes of waste plastics upgrading are
available: reuse, mechanical recycling and chemical recycling [2,3].
Chemical recycling can comprise either turning back to monomers
(in case of polyalkenes) or converting the plastics into substances
⇑ Corresponding author.
E-mail address: pavol.hudec@stuba.sk (P. Hudec).
all thermochemical processes, which deal with the conversion of
polyalkenes into low-molecular products and fractions that can
be used as alternative fuels. There are several thermochemical pro-
cesses that can be utilized for valorization of waste plastics: pyrol-
ysis, catalytic cracking, hydrocracking and gasification [4].
Pyrolysis is a convenient process for obtaining light products from
plastics with the aid of just heat. Liquid products of relatively high
quality, mainly in the range of gasoline and diesel, can be obtained
[5]. The problem is with the heaviest fractions (so-called waxes)
from the pyrolysis, which have not found a suitable use so far
[6]. The above-mentioned waxes represent the heaviest product
from the pyrolysis of automotive polymer waste. Their chemical
composition is dependent on the initial polymer (e.g. HDPE, PP)

http://dx.doi.org/10.1016/j.fuel.2017.04.128
0016-2361/Ó 2017 Published by Elsevier Ltd.
 P. Lovás et al. / Fuel 203 (2017) 244–252
and consists predominantly of long-chain hydrocarbons with dif-
ferences in the carbon chain length and structure, and in the
degree of saturation. Further thermochemical conversion of the
oil-waxes in the presence of a catalyst has many advantages,
including higher selectivity (shape-selectivity in case of zeolites)
and milder conditions in comparison with thermal cracking. Addi-
tion of a catalyst into the process can result in a decrease of hun-
dreds of degrees in the operating temperature [7–13]. Among all
the process available, fluid catalytic cracking is revealed as most
suitable as it is a source of gasoline and petrochemicals. This pro-
cess is very attractive because it is practically energetically inde-
pendent with no additional hydrogen needed during the process
[14]. Taking into account the relevancy of the polymer upgrading
is important, plus the chosen process, and also the feedstock selec-
tion. Catalytic testing of polymers in their virgin form is therefore
of little meaning in comparison to real mixtures from automotive
waste, as well as from agricultural sources [15].
The overall product distribution from catalytic cracking of poly-
mer waste is affected mainly by the chosen catalytic system.
Zeolite-based solid acid catalysts have been widely used in cat-
alytic cracking reactions for years, both in the laboratory and on
the industrial scale [16]. Besides the textural properties of the zeo-
lite catalyst, its overall acidity also plays a significant role in the
end-product distribution. Catalyst acidity should be at a certain
value, in order for the catalyst to provide sufficient feed conver-
sion. On the other hand, excessively high acidity values can result
in an over-cracking of the feed, with an extensive liquid fraction
loss in favor of gaseous products [17], which is undesirable when
liquid fuel production is the preferred output.
As for the heavy polymer oil-waxes another problem is their
high viscosity, which is the reason for diluting them in various sol-
vents. In many articles the middle distillate from FCC – light cycle
oil (LCO) was used [18,19] though LCO, as a product of cracking,
has a high content of aromatic hydrocarbons and as such its activ-
ity towards further cracking is very low. A more convenient option
would be the use of atmospheric gas oil, which could through pos-
sible intermolecular interactions with the polymer cracking inter-
mediates, contribute to higher yields of the light fractions.
When considering the utilization of polymer waxes on the
industrial scale, catalytic tests with the conventional FCC feed
hydrotreated vacuum gas oil are of importance [20,21].
In the present paper, catalytic cracking tests using different
mixtures of waxes obtained by pyrolysis of real polymers from
automotive waste were performed. In particular, mixtures of HDPE
and PP waxes with atmospheric gas oil as diluent were processed
without and then with the addition of HVGO. The effect of the feed
modification was investigated as the catalytic system was the
same in all cases (FCC equilibrium catalyst). The main parameters
monitored were: the yield of propylene and C4 hydrocarbons, the
yield of the gasoline fraction and the microactivity value.
2. Materials and methods
2.1. Feed specifications
The basic source of the feed used in the present research con-
sists of poly-alkene automotive plastic waste provided by a
waste-treatment center for end-of-life vehicles. After mechanical
separation, real samples of polypropylene (PP) and high density
polyethylene (HDPE) were crushed into small pieces and processed
via thermal cracking in a stainless-steel batch reactor at a the tem-
perature of 430–450 °C under a constant flow of nitrogen [22]. The
viscous liquid output of the thermal cracking process (depolymer-
izate) was then fractionated by atmospheric distillation, thus
obtaining a light fraction ( boiling range of gasoline) and subse-
245
quent vacuum distillation yielding a middle distillate fraction
(boiling range of diesel) and a distillation residue – wax – with
a boiling point >330 °C (a highly viscous heavy oil-like substance).
The amount of the distillation residue in case of PP thermal crack-
ing counted for ca. 17 wt.% and in case of HDPE thermal cracking
for ca. 47 wt.% [23].
Since the obtained distillation residue – wax – is not suitable for
direct use as automotive fuel component due to its high molecular
weight and viscosity, its valorization through catalytic cracking
was examined in the present research. The preparation of the feed
samples was subject to our laboratory feed delivery system, which
is not able to inject samples with high viscosity. Therefore the PP-
wax and HDPE-wax feed samples could not be injected directly
into the catalytic cracking reactor. Simple dilution in hydrotreated
vacuum gas oil (HVGO) also did not serve the purpose as the vis-
cosity was still too high for ensuring the continuous feed delivery
through the capillary of the linear dosing device of the micro-
activity test equipment even when heated up to 50 °C. Based on
the latter observation, respective mixtures of PP and HDPE waxes
with atmospheric gas oil (crude oil-based, b.p. 220-350 °C) were
prepared. The polymer wax was heated at  50 °C and diluted in
gas oil. In case of PP it was possible to prepare a mixture of gas
oil (GO) + 30 wt.% of PP-wax (GOPP) and in case of HDPE we were
able to prepare a mixture of GO + 40 wt.% HDPE-wax (GOHDPP)
reaching the feasible mixture viscosity.
To incorporate the conventional FCC feed – HVGO in the pro-
cess, prepared gas oil – polymer waxes mixtures were diluted in
HVGO with the amount of 50 wt.%. As the result it was possible
to prepare feed samples of HVGO + 50 wt.% of GOPP and HVGO
+ 50 wt.% of GOHDPE containing PP-wax and HDPE-wax, respec-
tively, due to the contribution of the gas oil to the overall reduction
in viscosity. The labeling of the individual prepared feed samples,
together with a more detailed description, is given in Table 1.
2.2. Experimental setup
Catalytic cracking of the polymer-based feed was performed
using the standard procedure of microactivity test (MAT). The
experimental apparatus was setup with respect to the ASTM
D3907 protocol [24], where the catalyst is deposited on the fixed
bed of a tubular reactor. The catalyst amount of 4.00 ± 0.05 g was
placed in the reactor in each one of the experiments. An inert
atmosphere in the reaction apparatus was maintained through
the constant flow of gaseous nitrogen of 30 cm3/min. Feed delivery
into the reactor was carried using a linear injector with the feed
being injected from a syringe, with a varying delivery time of 80,
60, 40 and 20 s (respective catalyst to oil ratio, C/O = 2, 4, 6, 12)
to examine the effect of the C/O on the overall product distribution.
The operational temperature of the catalytic cracking apparatus
was maintained at 525 ± 1 °C.
The products of the cracking were condensed immediately in a
series of wet-ice coolers placed at the reactor output, with the
liquid product quantification through weighing. Incondensable
gaseous products went on through the coolers into a glass water
Table 1
Feed samples labeling and description.
Sample Description
GO atmospheric gas oil
HVGO hydrotreated vacuum gas oil
GOHDPE atmospheric gas oil with 40 wt.% of HDPE-wax
GOPP atmospheric gas oil with 30 wt.% of PP-wax
HVGO + GOHDPE hydrotreated vacuum gas oil with 50 wt.% of the
GOHDPE
HVGO + GOPP hydrotreated vacuum gas oil with 50 wt.% of the GOPP
246 P. Lovás et al. / Fuel 203 (2017) 244–252
reservoir. In addition to the gaseous and liquid products there was
also a solid deposit – coke – formed on the catalyst causing its
deactivation after each experimental run. The coke was oxidized
in air at 590 °C after the experiment, with the amount coke deter-
mined from the material balance before and after oxidation.
The value of microactivity (MA) was calculated as the difference
between the mass of feed injected into reactor and the mass yield
of liquid products with a boiling point over 216 °C in wt.% with
respect to the mass of feed. Reproducibility of MA-values, based
on 10 experiments at standard conditions – 4 g of FCC-ECAT,
525 °C, C/O ratio of 12, HVGO as feed – was 83 ± 0.4.
2.3. Catalytic system
Considering the potential industrial application of the studied
polymer waste catalytic cracking, the standard equilibrium cata-
lyst (FCC-ECAT) was chosen to be tested in the catalytic cracking
experiments. From the structural point of view, FCC-ECAT consists
of an ultra-stable zeolite Y and of meso- and macroporous acidic
clays, although the exact composition is protected by the manufac-
turer. SEM pictures were taken using a TESLA BS 300 in connection
with a TESCAN digitalizing unit. The average particle size of FCC
catalyst is in the range of 80–120 lm, as can be seen from Fig. 1.
The textural properties determination was performed via physical
adsorption of nitrogen at the temperature of liquid N2 ( 196 °C)
using ASAP-2400 apparatus (Micromeritics). The measured cata-
lyst sample was evacuated overnight at 350 °C before adsorption
analysis. The individual textural specifications were determined
as follows: the specific surface area SBET was calculated using the
conventional BET isotherm (relative pressure range p/p0 = 0.05–
0.3). The external surface area comprising also the surface of meso-
pores St and the volume of micropores Vmicro were calculated from
the t-plot using the Harkins-Jura master isotherm. The value of the
total pore volume Vp was calculated from the adsorption data at
relative pressure p/p0 = 0.99. The overall catalyst acidity was quan-
tified using temperature programmed desorption of ammonia
(TPD) in the temperature range of 220 – 650 °C with a heating rate
of 12 °C/min. Brønsted and Lewis acidity was evaluated by room-
temperature FTIR-spectra of pyridine adsorbed at 150 °C on self-
Fig. 1. SEM-picture of FCC-ECAT.
supported wafers (8 mg/cm2) using Mattson-Unicam Genesis
equipment. Total acidity was divided into Brønsted (B) and Lewis
(L) types on the basis of integral FTIR intensities – Fig. 2 – corrected
by published extinction coefficients. Textural properties of the
equilibrium and regenerated catalysts as well as the acidity values
are presented in Table 2. It is seen that the greater part of acidity is
concentrated in Lewis acid sites, which is the result of the severe
conditions of industrial FCC catalyst stabilization (up to 800 °C
steam treatment) before use and conditions in repeated regenera-
tions (over 700 °C, in the presence of steam).
2.4. Analysis of the cracking products
Both gaseous and liquid products were qualified and quantified
using gas chromatography. In the case of the gaseous products, a
gas chromatograph HP 6890+ with a two parallel branch GC sys-
tem was used. The first branch consists of two chromatographic
columns HP PLOT Q (30 m  0.53 mm  40 mm) and HP PLOT 5A
(30 m  0.53 mm  50 mm) with the output on the TCD detector.
The second branch is built up by HP PLOT M (50 m 
0.53 mm  15 mm) chromatographic column with the output on
the FID detector. Analysis of the gaseous products comprised pri-
marily identification and quantification of C1 to C6 hydrocarbon
gases, with propylene and C4 alkenes being the most desirable.
Z-73Chromatographic analysis of the liquid products was
carried out via a simulated distillation according to ASTM D7169
[25]. Using this method, the liquid product was fractionated into
a gasoline fraction (C5-C12), with the b. p. range of 216–350 °C, into
a light cycle oil fraction LCO (C12-C20), with the b. p. range of
216–350 °C and into a heavy cycle oil fraction HCO (C20+), with
the b. p. > 350 °C.
In addition, the liquid product underwent analysis using gas
chromatography-mass spectrometry (GC–MS) in order to obtain
a more detailed composition of the liquid phase, particularly the
presence of unsaturated heterocyclic hydrocarbons (aromatics).
For GC–MS analysis, an Agilent Technologies GC 7890A gas chro-
matograph was used with the chromatographic column HP-5MS
(30 m  250 mm  0.25 mm) and with the ion source of an Agilent
Technologies model 5975C mass selective detector (MSD) operated
in electron impact ionization mode.
3. Results and discussion
3.1. Catalytic cracking of the HDPE-wax mixtures
In this section the results from the catalytic cracking of two dif-
ferent HDPE-wax feed mixtures are presented. The first one is the
mixture of 40 wt.% of HDPE-wax in atmospheric gas oil (GOHDPE)
Fig. 2. FTIR-spectra of Brønsted (1545 cm 1) and Lewis (1445 cm 1) acid sites by
pyridine adsorption on equilibrium (ECAT) and regenerated (REGENER) FCC-
catalysts.
 P. Lovás et al. / Fuel 203 (2017) 244–252 247

Table 2
Textural specifications and acidity of the standard equilibrium FCC catalyst and regenerated FCC catalyst.

Catalyst SBET (m2/g) St (m2/g) Vtot (cm3/g) Vmicro (cm3/g) Total acidity TPDA (mmol H+/g) B-acidity FTIR (mmol/g) L-acidity FTIR (mmol/g)
FCC ECAT 161 56.8 0.243 0.054 0.150 0.032 0.118
FCC REGENER 159 55.6 0.248 0.055 0.152 0.032 0.120

Table 3 The use of pure GO has not shown a significant effect on either
Product distribution (wt.%) from the catalytic cracking of GOHDPE feed over the FCC- of the HDPE-wax based mixtures, as it has more or less followed
ECAT catalyst. the propylene trend of the two feeds.
C/O ratio 2 4 6 12 Significantly higher was the yield of C4 hydrocarbons in case of
pure GO (Fig. 3b, blue dotted line). The latter can be related to the
Gaseous products 38.7 46.2 43.3 38.7
H2S 0.1 0.1 0.1 0.1
chemical composition of GO. Linear alkanes, which are predomi-
C1 0.7 0.9 0.9 0.8 nant in GO, can act as H-donors in hydrogen transfer reactions that
C2 1.7 2.0 2.0 1.7 leads to the decrease in the abundance of the C6-C12 hydrocarbons
Propylene 8.8 10.2 9.5 7.1 (gasoline fraction).
C4 20.2 23.2 21.5 21.3
As assumed, the yield of the gasoline fraction in the case of pure
Others 7.2 9.8 9.3 7.7
Liquid org. phase 53.9 48.9 49.1 50.4 GO was lower compared with the two HDPE-wax based feeds
Gasoline fraction 29.1 30.3 33.6 36.2 throughout almost the whole range of C/O ratios (Fig. 3c). Compar-
LCO fraction 19.7 14.9 12.5 10.2 ing GOHDPE and GOHDPE + HVGO mixtures, it can be seen that the
HCO fraction 5.1 3.7 3.0 4.0
gasoline yield was slightly higher when considering the feed mix-
Coke 7.4 4.9 7.6 10.9
ture without HVGO. The observed difference is not of great signif-
icance though, and it can be stated that the relatively high overall
yields of gasoline were obtained using HDPE-wax based feeds,
being very close to the gasoline yield from pure HVGO cracking
– Table 3, and the second one is the latter mixture with hydro- (Fig. 3, dashed line).
treated vacuum gas oil 1:1 (HVGO + GOHDPE) – Table 4. For com- The effect of pure GO addition is more significant in the forma-
parison we also performed catalytic cracking test with pure GO tion of coke. At the C/O ratio = 12, at which the catalyst activity is
(blue dotted line) to examine the effect of this diluent on the pro- at its highest, the coke yield in case of pure GO is relatively high
duct distribution – Fig. 3. Profiling products of the polymer feed (Fig. 3f, blue dotted line). This is also reflected in a higher coke
cracking are: propylene, C4 hydrocarbons, gasoline fraction and yield in the case of GOHDPE mixture at C/O = 12, compared to
coke. GOHDPE + HVGO. With a decreasing C/O ratio the coke yield also
As it can be seen in Fig. 3a, the yield of propylene in case of the decreases, which corresponds with the formation of more abun-
GOHDPE feed is only slightly higher compared to the one after the dant gaseous products at lower C/O ratios, considering all types
addition of HVGO. Rapid decrease in case of the GOHDPE mixture of tested feedstock. The contribution of secondary reactions in
at C/O ratio = 2 can be connected to the ongoing non-selective sec- the formation of coke in the case of GOHDPE is significant, as the
ondary reactions, which occur due to the further feed delivery to coke yield was higher than in case of pure HVGO cracking (Fig. 3f,
the surface of the partially deactivated catalyst. These reactions dashed line).
involve isomerization of the carbon chain, inter- and intra-
molecular hydrogen transfer (Fig. 4). The above mentioned reac-
tions lead to a reduction in the overall gaseous products yield 3.2. Catalytic cracking of the PP-wax mixtures
(including C4 gases) with the simultaneous increasing production
of iso-alkanes and aromatics in the carbon range of the gasoline Similarly, as in the case of HDPE, the PP-wax was diluted in
fraction or eventually of polyaromatics i.e. coke precursors [26]. atmospheric gas oil (GO) prior to cracking at the rate of 30 wt.%
In the case of the feed mixture with HVGO the opposite phe- of PP-wax, and results of cracking of this feed as well as its mixture
nomenon can be observed (Fig 3 a,b). The yields of propylene with HVGO are shown in Tables 5and 6. The tested waxes (HDPE
and C4 hydrocarbons have increased at C/O = 2 when looking at and PP) differ in their chemical composition as they were prepared
the GOHDPE + HVGO mixture. by the cracking of different polymer molecules. The complex com-
position is similar though, as they are both composed of alkanes
and alkenes with boiling points above 350 °C [27]. This fact is nat-
urally reflected in the different product distribution.
Table 4 The overall gaseous product formation is relatively low in com-
Product distribution (wt.%) from the catalytic cracking of HVGO + GOHDPE feed over parison with HDPE-wax. Considering the fact that the PP-wax is
the FCC-ECAT catalyst. predominantly composed of branched alkanes and alkenes [28],
C/O ratio 2 4 6 12 there is a natural decrease in the gas formation in favor of heavier
products. The yield of propylene and C4 hydrocarbons was higher
Gaseous products 45.3 41.5 42.0 38.2
H2S 0.1 0.0 0.0 0.0 in case of GOPP mixture in comparison with the feed with HVGO,
C1 1.1 1.0 0.9 1.0 as can be seen in Fig. 5a. There is deviation from the trend at the
C2 2.1 1.9 1.8 1.8 C/O ratio = 12 where the yield of propylene is lower than in case
Propylene 10.8 8.9 8.4 7.1
of HVGO mixture (Fig. 5a). This observation can be linked with
C4 23.2 22.3 22.8 20.5
Others 8.0 7.4 8.1 7.8
the stronger effect of the PP-wax component in the feed. In the first
Liquid org. phase 49.9 52.5 51.8 52.9 phase of the cracking reaction (higher C/O ratio) the catalyst active
Gasoline fraction 27.3 31.1 31.0 34.1 sites are available for the PP-wax feed molecules, as in this stage
LCO fraction 14.3 15.0 14.2 13.8 the deactivation of the catalyst through coke is low. Changed diffu-
HCO fraction 8.3 6.4 6.6 5.0
sivity inside the catalyst is therefore responsible for the lower for-
Coke 4.8 6.0 6.2 8.9
mation of gas and higher formation of heavier fractions.
248 P. Lovás et al. / Fuel 203 (2017) 244–252
Fig. 3. Effect of different feedstock on the product distribution from catalytic cracking of HDPE-wax mixtures at different C/O ratios, using FCC-ECAT as catalyst (527 °C,
WHSV = 15 h 1).
The yield of gaseous products in case of pure GO is higher when
compared to polymer-based feed (Fig. 5a,b, blue dotted line),
which corresponds with the higher tendency of GO to form hydro-
carbon gases as mentioned in the Section 3.1.
As for the yield of the gasoline fraction, high amounts of this
desired product were obtained when cracking both feeds contain-
ing PP-wax (Fig. 5c). A positive fact is that the gasoline yields of PP-
wax based feedstock are practically identical with the yield from
pure HVGO cracking (Fig. 5c, dashed line). At the ratio C/O = 12
the amount of gasoline produced is even higher compared with
pure HVGO. In case of the GOPP mixture there are two effects that
lead to a high gasoline yield: 1. acidic macro- and mesoporous
components of the FCC-ECAT catalyst (active clays), which increase
the diffusivity inside the catalyst structure 2. Highly active compo-
nents of the PP-wax based feed (mainly alkenes) which support the
formation of C6-C12 hydrocarbons, which is also enhanced through
the selectivity of the FCC-ECAT catalyst. The contribution of pure
GO in the feed mixture appears as insignificant as in case of pure
GO, as the gasoline yield is lower than either of the PP-wax based
feeds (Fig. 5c, blue dotted line).
The coke formation considering the GOPP feed mixture was rel-
atively low throughout the whole range of C/O ratios (Fig. 5f). Low
rates of formation of coke precursors in favor of gasoline range
hydrocarbons in case of the mentioned feed can be related to a
lower coke yield. Regarding the coke amount produced when
cracking GOPP + HVGO mixture, relatively high coke content was
obtained in the end-products. Here an interaction of reactive alke-
nes from the PP component with the saturated hydrocarbons from
the HVGO component, i.e. hydrogen transfer can be presumed.
These interactions increase the feed conversion on one hand, but
also increase the formation of polyaromtaic compounds (coke pre-
cursors) on the other. This effect is manifested mainly at the C/O
ratio = 12.
3.3. Catalytic cracking of HDPE-wax vs. PP-wax
A detailed GC–MS analysis of the liquid products from catalytic
cracking of the feed mixtures with HDPE-wax and PP-wax was per-
formed. Based on the analytical results it can be stated that, for all
kinds of feedstock, saturated hydrocarbons (mainly iso-alkanes)
and aromatic compounds (C6-C8) dominated in the liquid products
– Fig. 6.
Higher amounts of iso-alkanes and aromatics in the liquid prod-
ucts are associated with the following factors [7]:
 textural properties of the catalyst used (FCC-ECAT), whose pore
structure endorses formation of bigger structures, whereas its
shape selectivity supports the generation of gasoline-range
hydrocarbons
 P. Lovás et al. / Fuel 203 (2017) 244–252 249

Fig. 4. Secondary reactions of the polymer chain during catalytic cracking: a) isomerization of the carbon chain b) hydrogen-transfer reactions – intermolecular c) hydrogen-
transfer reactions – intramolecular.

Table 5 Table 6
Product distribution (wt.%) from the catalytic cracking of GOPP feed over the FCC- Product distribution (wt.%) from the catalytic cracking of HVGO + GOPP feed over the
ECAT catalyst. FCC-ECAT catalyst.

C/O ratio 2 4 6 12 C/O ratio 2 4 6 12

Gaseous products 45.2 43.3 43.5 26.7 Gaseous products 41.9 35.5 36.3 30.7
H2S 0.2 0.2 0.2 0.1 H2S 0.1 0.1 0.1 0.0
C1 1.0 0.9 0.9 0.6 C1 1.0 0.9 1.0 1.0
C2 2.1 1.9 1.9 1.2 C2 1.9 1.7 1.9 1.7
Propylene 9.5 8.7 8.4 4.3 Propylene 9.1 7.0 7.0 5.4
C4 24.9 23.4 24.1 15.2 C4 22.7 19.0 19.8 16.4
Others 7.5 8.3 8.0 5.3 Others 7.1 6.8 6.5 6.2
Liquid org. phase 50.9 51.6 50.7 67.6 Liquid org. phase 52.9 56.9 55.0 56.6
Gasoline fraction 30.9 32.5 34.5 48.3 Gasoline fraction 30.3 34.3 33.9 39.3
LCO fraction 16.2 15.0 14.0 13.6 LCO fraction 15.3 16.4 15.2 12.7
HCO fraction 3.9 4.1 2.2 5.7 HCO fraction 7.3 6.2 5.9 4.6
Coke 3.9 5.1 5.8 5.7 Coke 5.2 7.6 8.7 12.7

 preferential adsorption of alkene intermediates on the catalyst

surface, leading to enhanced hydrogen transfer reactions,
resulting in higher formation of saturated branched structures
as well as the unsaturated cyclic structures
The above-mentioned higher content of iso-alkanes and aro-
matics results in an octane number increase of the gasoline frac-
tion. This is clearly a positive when considering the use of the
gasoline obtained in the future blending process. Low alkene con-
tent in the liquid product positively affects the oxidation stability.
Comparing the product distribution from catalytic cracking
using different polymer-based feedstock (HDPE-wax, PP-wax), a
higher formation of gaseous products in case of HDPE-wax can
be observed. As for the PP-wax feedstock generally a higher forma-
tion of the gasoline fraction can be seen in Fig. 7.
The above-mentioned differences between HDPE-wax and PP-
wax are significant, whereas the presence of HVGO in the feed mix-
ture has virtually no effect on these differences. Preferential forma-
tion of gases in the case of HDPE-wax and of the gasoline fraction
in the case of PP-wax results from the differences in chemical com-
position of these two polymer feedstocks [28].
Based on the latter there is an option to choose flexibly between
the desired end-product (light gases or gasoline fraction) by using
either HDPE-wax or PP-wax as feedstock.
3.4. Microactivity results
Evaluation of the microactivity values of the respective polymer
mixtures was focused on the comparison of these values with the
250 P. Lovás et al. / Fuel 203 (2017) 244–252

Fig. 5. Effect of different feedstock on the product distribution from catalytic cracking of PP-wax mixtures at different C/O ratios, using FCC-ECAT as catalyst (527 °C,
WHSV = 15 h 1).

1
Fig. 6. Composition of the liquid fraction from catalytic cracking of polymer-based mixtures, using FCC-ECAT as catalyst (C/O = 12, 527 °C, WHSV = 15 h ).
 P. Lovás et al. / Fuel 203 (2017) 244–252 251

1
Fig. 7. Distribution of the product fractions from the catalytic cracking of polymer-based mixtures, using FCC-ECAT as catalyst (C/O = 12, 527 °C, WHSV = 15 h ).

conventional FCC feed HVGO (Fig. 8a,b). As it can be seen in all
cases of polymer mixtures, the values of microactivity were higher
compared to pure HVGO throughout the whole range of C/O ratios.
As mentioned in Section 2.2 the microactivity value represents
mainly the formation of gaseous products and gasoline. Since the
polymer feedstock gave higher yields of these product fractions
than HVGO, the higher microactivity values clearly correspond
with this phenomenon.
3.5. Regenerability of catalyst
Equilibrium FCC-catalyst – FCC-ECAT – represents equilibrium
mixture of particles of FCC-catalyst going out just from regenerator
in industrial FCC-technology. Each particle of catalyst (in commer-
cial technology ca. 100 tons) goes through the reactor (riser) for
several seconds, where it acts as catalyst and cracks the large mole-
cules of vacuum gas oil to much lighter fraction at the temperature
of about 525–545 °C, then the rest of the oil is stripped from the
catalyst by hot steam, and coked catalyst particles pass to the
regenerator where the coke burns off at a temperature of over
700 °C. The FCC-ECAT used in this paper thus represents a mixture
of catalyst particles that have passed many hundreds, may be
many thousands times through the technological loop reactor-
regenerator. Consequently, it is very little possible that one regen-
eration step after cracking of a lighter mixture than industrial feed
could decrease the surface area and acid properties, even though
we carried out an experiment with regenerated catalyst used in
cracking of HVGO + GOHDPE mixture, once again burned off the

Fig. 8. Microactivity values from the catalytic cracking of: a) HDPE- and b) PP-based mixtures compared with pure HVGO, using FCC-ECAT as catalyst (527 °C,
WHSV = 15 h 1).
252 P. Lovás et al. / Fuel 203 (2017) 244–252
coke and determined the specific surface area and acidity – results
are in Table 2. At the practically same composition of cracking
products it can be seen that the characteristics were practically
unchanged.
4. Conclusions
In the present paper, catalytic cracking tests of HDPE-wax and
PP-wax based feed mixtures were performed. Commercial equilib-
rium FCC catalyst FCC-ECAT was used. Polymer waxes were diluted
in atmospheric gas oil due to viscosity issues. Chosen feed mixtures
were then also processed with commercial hydrotreated vacuum
gas oil (HVGO).
Processing mixtures with HDPE-wax and GO resulted in high
yields of propylene and in the gasoline fraction yield very close
to that of pure HVGO cracking. It is also positive that the content
of undesired LCO and HCO fractions was relatively low. The addi-
tion of HVGO to the HDPE-wax mixture resulted in a slight
decrease in propylene and gasoline, with an increase in the forma-
tion of heavier liquid fractions. Using the PP-wax feed mixture
with GO followed a similar trend as HDPE-wax considering the
heavier liquid fractions, but resulted in a greaterer increase in
the yield of the gasoline fraction. Based on the detailed fractional
composition of the products with regards to all types of used feed-
stock, it can be concluded that the use of HDPE-wax results in an
increased formation of gases and the use of PP-wax results in an
increased formation of gasoline. Regarding the future potential
use of this feedstock industrially there is a possibility of switching
between the feedstock types depending on the desired product
distribution.
The calculated values of microactivity, which stands for a stan-
dard evaluation parameter for FCC catalysts, were in all cases of
HDPE and PP waxes higher when compared to a standard commer-
cial FCC feedstock HVGO.
Acknowledgements
The Slovak Research and Development Agency (Contract No.
APVV-15-0449) is gratefully acknowledged for the financial sup-
port of the research.
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