Journal of Analytical and Applied Pyrolysis xxx (xxxx) xxx–xxx

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Journal of Analytical and Applied Pyrolysis

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Experimental study of catalytic pyrolysis of polyethylene and polypropylene

over USY zeolite and separation to gasoline and diesel-like fuels
⁎
Chantal Kassargya,b, Sary Awada, , Gaetan Burnensa, Khalil Kahineb, Mohand Tazerouta
a
GEPEA, UMR 6144, DSEE, IMT-Atlantique, Nantes 44307, France
b
Modeling Centre, Lebanese University, Beirut, Lebanon

A R T I C L E I N F O A B S T R A C T

Keywords: Thermal catalytic and non catalytic degradation of polyethylene (PE) and polypropylene (PP) were carried out in
Pyrolysis a batch reactor at 450 °C. The major product obtained from the non-catalytic pyrolysis of PE was 80 wt% of wax,
Polyethylene while the degradation of PP without any catalyst produced 85.5% of liquid. In catalytic degradation, ultra-stable
Polypropylene Y (USY) zeolite was used in a ratio of 1:10, with respect to PE and PP. In both cases, polymers were converted to
Catalytic cracking
liquid products with high yields (71 and 82 wt% respectively) and a low amount of coke deposit has appeared.
USY-Zeolite
The liquid fraction derived from the catalytic pyrolysis of PE was a mixture of C5-C39 compounds and that of PP
Alternative fuels
was a mixture of C5-C30. This wide range of components suggests the separation of liquids into two phases in
order to use them as diesel-like and gasoline-like fuels. Three temperatures of separation (130, 150, 170 °C) were
tested and the physical properties were compared. Among the tested temperatures, 170 °C was the optimal
temperature of separation where the distillation curves and physical properties of the light and heavy phases
fitted completely those of gasoline and diesel fuels, respectively. After separation, the gasoline-like fuel which
represents 60.6% of the total oil of PP and 57% of that of PE had high octane numbers (RON = 96 and
RON = 97, respectively), while the diesel-like fuel which accounts for 36.5% of the total oil of PP and 35.3% of
that of PE have high calculated cetane numbers (52 and 53, respectively).

1. Introduction reduce environmental charge, recycling and recovering methods should

be employed. Pyrolysis is a recovery method that consists on upgrading
Due to rapid urbanization and economic development, the world’s plastic wastes into fuel oil and valuable chemicals by heating at tem-
annual production of plastic materials has increased from around 1.7 perature range of 400–600 °C in the absence of oxygen [4].
million tons in the 1950s to nearly 311 million tons, of which 59 million Thermal and catalytic degradation of waste plastics are two kinds of
tons are accounted for by Europe alone [1]. Due to the increase in chemical valorization processes. The presence of catalysts in pyrolysis
generation, waste plastics are becoming a major stream in solid wastes, reduces reaction temperature and residence time, decreases energy
generating heavy environmental problems. consumption, promotes decomposition reaction and improves se-
There are six main plastic components in European municipal solid lectivity and the quality of the products [5].
waste which are high-density polyethylene (HDPE), low density poly- Pyrolysis of waste polyethylene has been investigated by many re-
ethylene (LDPE), polypropylene (PP), polystyrene (PS), poly- searchers who found that waxes are the main products in thermal
vinylchloride (PVC) and polyethyleneterephthalate (PET). Polyolefin cracking. Waxes derived from thermal cracking of PE are long chain
materials (PE and PP) constitute the majority of plastic wastes and re- made up of linear hydrocarbons having a carbon number heavier than
present around 68% of the municipal solid wastes [2]. C20 and which solidify at room temperature [6]. Kiran et al. [7] studied
A major part of post consumer plastic wastes are currently landfilled the pyrolysis of waste polyethylene in a fixed bed reactor, at a low
or incinerated. Since these wastes are non biodegradable and the areas heating rate and reaching 600 °C. Gas and wax were the two main
for landfill sites are limited, landfilling is not a suitable option for products obtained during the pyrolysis experiments. The wax formed
disposing plastic wastes. In addition, the use of incinerator have high caused an operating problem by plugging the product lines and con-
cost consumption, and generates some pollutants to the air like nitrous denser tubes.
and sulfur oxides, dusts, dioxins and furan [3]. Therefore, in order to In order to improve the quality of the liquid fuel produced from the

⁎
Corresponding author.
E-mail address: sary.awad@gmail.com (S. Awad).

http://dx.doi.org/10.1016/j.jaap.2017.09.005
Received 31 January 2017; Received in revised form 3 August 2017; Accepted 6 September 2017
0165-2370/ © 2017 Elsevier B.V. All rights reserved.

Please cite this article as: KASSARGY, C., Journal of Analytical and Applied Pyrolysis (2017), http://dx.doi.org/10.1016/j.jaap.2017.09.005
C. Kassargy et al. Journal of Analytical and Applied Pyrolysis xxx (xxxx) xxx–xxx

degradation of plastics, a range of catalysts have been utilized in the Table 1

catalytic degradation of polymers. The most commonly used catalysts Textural and acid properties of the USY zeolite.
are solid acid ones such as zeolites and silica–alumina [8]. Lerici et al.
SiO2/Al2O3 (mol/mol) 15
[9] studied thermocatalytic degradation of polyethylene, poly-
propylene (PP) and polyestyrene (PS) using the H-Y zeolite in a batch BET surface area (m2 g−1) 550
reactor at 500 °C. They reported that thermal cracking of polyolefins Na2O (wt%) 0.05
Micropore volume (MPV) (cm3 g−1) 0.1
produced waxes and the use of catalyst yielded higher percentages of
Crystal size (μm) 0.7–1.0
gaseous products which ranged between 42 wt% and 45 wt%, while PS Total acidity (mmol NH3 g−1) 0.1
yielded a greater amount of liquids (∼72 wt%).
A number of authors have reported promising results on the
cracking of polyolefins over several catalysts. Onu et al. [10] compared of each fraction meet the gasoline and diesel fuels standards.
the degradation of polyethylene and polypropylene over HZSM-5 zeo-
lite catalyst and a catalyst modified with orthophosphoric acid (PZSM- 2. Experimental
5) in a fixed bed reactor at 460–480 °C. According to their study, the
quantities of liquid products with PZSM-5 are smaller than those ob- 2.1. Materials and methods
tained over HZSM-5 for both PP (43.3%) and PE (34.6%), and all of the
liquids had high proportions of aromatic hydrocarbons. The feedstock samples for the present study were virgin plastic
The cracking ability of a catalyst is related to the acidity strength mainly made of PE and PP plastic types respectively thus the material
and the pore size which represent its main characteristics [11]. Strong variability can be eliminated. All of these plastics were granular with a
acid catalysts enhance the cracking of heavier hydrocarbons into more particle size of, approximately, 1.8 mm–4.5 mm.
lighter or gaseous hydrocarbons comparing to the weak acid catalysts. The catalyst used for the pyrolysis experiments was a commercial
This was reported by Sakata et al. [12] who studied the catalytic de- USY zeolite provided by TOSOH Corporation. Their main character-
gradation of HDPE into fuel oil over mesoporous silica (KFS-16) catalyst istics are presented in table 1. This zeolite has been selected for its
at 430 °C. The Product yields and composition were compared with medium Si/Al ratio (7.5). Indeed, for low Si/Al ratios, the number of
those obtained over solid acid catalyst (silica–alumina and ZSM-5). acid sites will increase, but their strength remains relatively less pro-
According to their study, ZSM-5 possessing strong acid sites produced nounced. However, a higher Si/Al ratio induces a drastic decrease of
less liquid products and more gaseous products than the silica-alumina the number of acid sites. In this case, “isolated” acide sites will be more
catalysts. On the other hand, KFS-16, having no acid sites, produced reactive. Hence, the selected Si/Al ratio seems to be a good compromise
liquid hydrocarbons with a high yield as 71 wt%. in order to enhance liquid production at the expense of gases [19].
Sakata et al. [13] also investigated the effects of various types of The catalyst was dried in an oven to remove moisture, and then
solid acid catalysts such as silica–alumina, zeolite and non-acidic me- was sieved in order to have a particle size between 200 and 800 μm. In
soporous silica catalysts on the degradation of polyethylene and poly- the catalytic pyrolysis experiments the plastic/catalyst mass ratio was
propylene at 430 and 380 °C respectively in batch operation. The de- 10/1.
gradation of PP and PE into gases was accelerated when using catalysts
with strong acid sites such as zeolite ZSM-5.
A number of authors have investigated the use of USY zeolite in the 2.2. Laboratory scale pyrolysis plant
catalytic degradation of polyethylene and polypropylene [2,14,15].
They reported that large-pore USY zeolite produced the highest amount Pyrolysis reactions were led in a laboratory scale batch reactor,
of liquid fraction compared to other tested catalysts like ZSM-5 zeolite developed by Pyrum Innovations (Fig. 1). The reactor is 200 mm height
which favored gas production. Moreover, the hydrocarbons formed with 90 mm diameter made of steel and heated by an electric coil with a
over USY zeolite were heavier than those formed with medium-pore power of 1100 W, which is connected to a programmable temperature
zeolites and the main products were alkanes with less alkenes and controller. The reactor is thermally insulated with ceramic wool jacket.
aromatics. A thermocouple in direct contact with the sample was used to monitor
The main disadvantage of using zeolite catalyst is coke formation the actual temperature of the process.
which is due to the deposit of heavy by-products on the catalyst surface. Prior to the experiment, the system was purged for 15 min with
Coke formation occurs during catalytic reactions and causes the gradual nitrogen (N2) at room temperature to ensure an inert atmosphere, and
deactivation of the catalyst which also affects the product distribution then 2 series of experiments were carried out. In the first series, 100 g of
and selectivity [16]. Several authors investigated the deactivation of PP and PE were loaded individually without any catalyst into the re-
zeolites in polymer cracking. actor, while in the second series; 100 g of PP and PE were mixed in-
Marcilla et al. [17] studied the deactivation of HZSM5 and HUSY dividually with 10 g of catalyst and loaded into the reactor. The tem-
zeolites during the catalytic pyrolysis of polyethylene and reported that perature of the reactor was then raised from ambient temperature to
HUSY showed a higher initial relative activity as it presents large pore 450 °C. The pyrolysis products pass through a stainless steel condenser
size but it lead to a fast deactivation, while small pore size in HZSM5 cooled with tap water at 15 °C and then, the condensate is collected in a
prevented coke deposition. container. The uncondensed gases are discharged through an exhaust
Previous studies have compared the thermal and catalytic de- system. The products of degradation were classified into three groups:
gradation of polyethylene and polypropylene, but most of these works liquid products, gaseous products and residues. The liquid fraction was
were performed using catalysts that favored gas production [18] and then characterized in order to be used as an alternative fuel oil. For this
did not focused on the quality of the liquid fraction produced. In the purpose liquid product was fractioned at different temperatures to find
present work, the main objectives were to produce useful fuels from PE the optimal temperature for separating the liquid into gasoline-like and
and PP over USY zeolite which enhance liquid formation and to in- diesel-like oil fractions.
vestigate the quality of the liquid fraction produced. Furthermore, the
influence of USY zeolite on the yield and composition of the derived oils 2.3. Liquid products characterization
from catalytic cracking of PP and PE was studied. Moreover, the se-
paration of the pyrolytic oils of PP and PE into light, gasoline-like and The samples were analyzed to determine the main parameters. The
heavy, diesel-like fractions was studied in order to find a single tem- calorific value of the samples was measured using a Parr 6200 calori-
perature where the boiling range distributions and physical properties meter. The density of the pyrolytic oil was measured at room

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Fig. 1. Schematic diagram of pyrolysis plant.

temperature using pycnometer M50T (700–750 G/L) and a pycnometer Table 2

M50T (750–800 G/L).The viscosity of the oils produced in each ex- Effect of catalyst type on the product yields and reaction time
periment were measured at 40 °C using an AND vibro viscometer, and
Non-catalytic Degradation Catalytic Degradation
the distillation curve of the obtained oil was measured by a NORMALAB
NDI440 automatic distiller. The vapor pressure of the light fraction was Plastic type PE PP PE PP
measured by a vapor pressure analyzer ERAVAP using ASTM D6378 Yield (wt.%)
testing method, while the flash point of the heavy phase was measured Wax 80 – – –
using a PENSKY MARTENS NPM440 device with a precision of 2 °C. Liquid 85.5 71 82
The analyses were realized in three replicates, and error bars were used Solid – – 2.2 1.2
Gas 20 14.5 26.8 16.8
to represent the standard error.
The cetane index (CCI) was calculated using temperature values of Reaction time (min) 120 80 50 45
10%, 50% and 90% of recovered volume (T10, T50 and T90) and of
density at 15 °C (D) in an equation of four variables [20] presented in
mi
Eq. (1). Yield (%) =
m (3)
CCI = 45.2 + 0.0892T10N + (0.131 + 0.901B ) T50N + (0.0523 − 0.420B)T90N
2
Where mi is the weight of products (liquid oil, wax and residue) and m
+ 0.00049(T10N − T290N) + 107 B+ 60B2 (1) is the weight of the initial plastic waste used. The yield of gas was
Where T10N = T10 − 215, T50N = T50 − 260, T90N = T90 − 310 calculated by difference. The reaction time of non-catalytic and cata-
AndB = (e−3.5(D − 0.85) ) − 1 lytic degradation of PE and PP are also presented in Table 2.
The octane number was calculated using a correlation between the As it can be seen, condensable products (Liquid/wax) were by far
research octane number (RON) of unleaded motor gasoline and its 90% the major fraction of products with different feedstock and for both
volume boiling point [21] shown in Eq. (2). processes. Non-catalytic pyrolysis of PE lead to a high yield of wax with
80 wt.% and gas with 20 wt% and a reaction time of 120 min. On the
2
RON = 179.5415 − 0.136428T90% − 1.3072 × 10−3T90% other hand, the degradation of PP gave 85.5 wt.% of liquid and 14.5 wt
3
− 113222.4 × 103T90% (2) % of gas with a reaction time of 80 min and no coke deposits were
observed. No wax was observed in the non-catalytic degradation of PP,
In order to quantify the dominant chemical compounds of the due to the difference in products structure compared to that of PE. The
produced oils, samples were analyzed using a Perkin Elmer CLARUS products obtained from the non-catalytic pyrolysis of PP are branched
600 Mass Spectrometer coupled with a gas chromatograph and a flame hydrocarbons which have lower melting points compared to linear al-
ionization detector (GCMS-FID). An Agilent SLB-5MS column kane. While the products obtained from PE pyrolysis contain large
(30 m × 0.250 mm; 0.25 μm film thickness) was used with a helium proportion of heavy linear hydrocarbons, with a high carbon chain
flow rate of 1 ml/min. The temperature program began with a hold at number which could undergo over cracking reactions [22,23].
70 °C for 1 min followed by an increase at 12 °C/min to 180 °C, then an When USY zeolite was added with the different plastic wastes type,
increase at 7 °C/min to 240 °C and finally an increase at 12 °C/min to catalytic decomposition yielded a light yellow liquid and no wax was
330 °C, which was held for 6.76 min. The temperature of FID detector produced. The catalytic pyrolysis of PE resulted in 71 wt.% of liquid,
was fixed at 275 °C. Injections of 0.5 μl of oil samples were realized 26.79 wt.% of gas and produced a deposit of coke with 2.21 wt.% and
with a split ratio of 10:1. The mass spectrometer was set at an ionizing the reaction lasted 50 min. In the catalytic pyrolysis of PP, the oil yield
voltage of 70 eV and a range of m/z 30–450. Identification of chro- decreased to 82 wt.% with an increase in the gas yield to 16.76 wt.%
matographic peaks was established from MS data. and a production of 1.24 wt.% of coke and a reaction time of 45 min.
The increasing in liquid yield is due to the decomposition of the heavier
3. Results and discussion hydrocarbons into lighter liquid hydrocarbons over USY zeolite cata-
lyst, while the increase in gas production for PP degradation was due to
3.1. Pyrolysis yields (wt%) the fact that the heavier components were converted into gas compo-
nents through secondary cracking reactions. The formation of coke is
The yields of liquid, gaseous and solid products obtained at 450 °C due to several mechanisms like aromatization and dehydrogenation on
from the non-catalytic and catalytic degradation were calculated using the catalyst surface [24].
Eq. (3), and results are presented in Table 2.

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Fig. 2. Carbon number distribution of oil derived

from catalytic and non-catalytic pyrolysis of
Polypropylene (PP).

3.2. Gas chromatography (GC–MS-FID) Fig. 3. As it can be seen, the liquid hydrocarbon products derived from
the non-catalytic pyrolysis were distributed in a wide range carbon
The GC–MS FID analysis of the liquid fuel sample obtained by cat- numbers (C8–C39) with a maximum fraction (C18-C21), while the liquid
alytic and non-catalytic pyrolysis of waste PP and PE was carried out to fraction derived from the catalytic pyrolysis was a mixture of C5-C39
analyze the compounds present in the fuel. Figs. 2 and 3 show the compounds with a maximum fraction (C10-C13). This changing in
difference in the pyrolysis liquids composition derived from non-cata- composition between non-catalytic and catalytic degradation can be
lytic and catalytic pyrolysis of PE and PP respectively, grouped ac- explained by the mechanisms that took place during the process.
cording to their carbon number. As it can be seen in Fig. 2, the liquid Thermal degradation of polyolefins has been reported to take place
obtained from non-catalytic PP pyrolysis contained hydrocarbons ran- through two mechanisms: (1) random scission to yield long-chain hy-
ging from C7-C30 with a maximum peak in C9 fraction. The use of the drocarbons; and (2) chain-end scission of the oligomers to yield low-
catalyst caused a shift of the products into lower molecular weights molecular weight products [25]. Following these two mechanisms, free
with products rich in C5–C11 compounds whose yields were as high as hydrogen radicals are formed from the scission of the polymer chain.
70%. On the other hand, the hydrocarbon composition of liquid oil Thereafter, a molecule with an unsaturated end and the other with a
derived from non −catalytic and catalytic pyrolysis of PE is shown in terminal free radical are formed through β-scission. Then, stabilization

Fig. 3. Carbon number distribution of oil derived

from catalytic and non-catalytic pyrolysis of
Polyethylene (PE).

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Table 3
Characteristics of liquid products obtained from non-catalytic and catalytic pyrolysis of PE and PP compared to the European standards.

Non-Catalytic Degradation Catalytic Degradation EN 590 EN 228

Plastic type PE PP PE PP
Density (kg/m3) – 777 749 754 820–845 720–775
Viscosity (mm2/s) – 0.6 0.7 0.6 2–4.5 –
Lower heating value (LHV)(MJ/kg) – 44.9 45.1 45.8 43.4 44.4

of the free radicals occurs by hydrogen chain transfer reactions in- they represent more than 70% of the recovered oil. Olefins have much
cluding intermolecular transfer reaction and intra-molecular transfer higher reactivity over acidic catalysts than paraffins since they can be
reaction. The radical fragments were transformed into straight chain easily converted to carbocations on zeolite surface.
dienes, alkenes and alkanes. Termination reaction occurs by dis-
proportionation of the free radicals or combining of two free radicals
[26]. The formation of wax through non-catalytic pyrolysis of PE is 3.3. Physical properties of oil sample
related to the fact that PE consists of straight long carbon chains and
thermal degradation occurs by random-chain scission. Hydrocarbons From the Gas chromatograph analysis, there was a significant dif-
are decomposed through the homolytic rupture of covalent CeC bonds, ference among molecular weights of oils obtained by pyrolysis of PE
rather than CeH bonds. In this case, a relatively small proportion of and PP in the presence and absence of catalyst.
branched molecules are detected which accurate a homolytic me- The main properties of the pyrolysis oils obtained from the non-
chanism. catalytic and catalytic pyrolysis of PP and PE at 450 °C are summarized
We can notice that higher volatile compounds were obtained from in Table 3. The non-catalytic pyrolysis of PE gave a wax with a high
PP in contrast to PE, using the same pyrolysis parameters. This can be viscosity, while the non-catalytic pyrolysis of PP gave a less viscous
due to the difference in their structure since PP is a polymer whose liquid. Those properties are directly linked to the composition of those
chains present a greater cross-sectional area than PE, due to the pre- oils. Non-catalytic pyrolysis oil from PE is essentially composed of
sence of the methyl group substituent on alternate carbon atoms of the normal paraffins/olefins with high viscosity while pyrolysis oil from PP
chain. The presence of these methyl groups increase the number of is a mixture of branched paraffins/olefins with low viscosity. In non-
tertiary carbons in the molecule, which have considerably lower re- catalytic conditions, reaction time was too long and consumed a lot of
sistance against degradation and promotes the thermal cleavage of CeC energy, and produced a liquid which could not be recovered into va-
bonds and due to the branched structure, methyl, primary and sec- luable fuel oil. For this reason, the rest of the present study will be
ondary alkyl radicals are formed [27]. In fact, the mechanism of the focused on the catalytic pyrolysis of both PP and PE.
thermal degradation of polypropylene and polyethylene initiates by As it can be seen, liquids obtained by catalytic pyrolysis of waste PP
random chain scission with a formation of secondary and tertiary ra- and PE have LHVs in the range of gasoline and diesel. According to
dicals via rearrangement reactions (backbiting) and propagates through ASTMD 975, there are no limits for density of diesel fuel, but EN 590
the β-scission of the radicals [28]. The difference in the cracking me- specifies a density of 820–845 kg/m3 at 15 °C. Neither the liquid oil
chanism between PP and PE and the formation of secondary and ter- obtained from pyrolysis of PP (754 kg/m3) nor the liquid oil obtained
tiary radicals was explained by the lower degradation reaction time of from pyrolysis of PE (749 kg/m3) provided densities meeting the range
PP compared to that of PE. Transfer reactions play a minor role in specified in EN 590. On the other hand, both liquids densities meet the
polypropylene degradation compared to polyethylene degradation due range of gasoline specified in EN 228.
to the lower alkane concentration [29]. The specific carbon number Viscosities of both pyrolytic oils obtained from pyrolysis of PP
distribution presented in Fig. 2 with maximum at C9, C12, C15, C18 and (0.64 mm2/s) and from pyrolysis of PE (0.72 mm2/s), were out of the
C21 showed preferential cracking position, corresponding to the tertiary EN590 range and are very low compared to conventional diesel fuel
carbons. (2–4.5 mm2/s). This could be explained by the presence of light olefins
To explain the products observed from the catalytic cracking of PE and the presence of high branched isomers due to the carbon-chain
and PP over USY zeolite, two carbocationic mechanisms have been isomerization that takes place in the presence of catalysts [34].
suggested: (1) the classical bimolecular mechanism or β-cracking [30]
and (2) the monomolecular mechanism, through carbonium ions [31].
Table 4
Catalytic cracking of PE initiates with formation of free radicals along
Distillation properties of the produced oils according to EN 228 standard limits estab-
the polymer chains, which results in breakage of CeC bond. Due to lished for gasoline and En 590 standard limits established for diesel.
abstraction of hydride ion from the PE chain by USY, carbenium ion is
formed and undergoes isomerization, β-scission, and hydrogen transfer Distillation Properties Units limits EN228 Feedstock
to form smaller fragments [32]. Catalytic degradation of PP is known to
PE PP
proceed by carbenium ion mechanism [33]. The catalytic degradation
of PP initiates by either the abstraction of hydride ion (by Lewis acid Evaporated @ 70 °C % (V/V) 20–48 10 9
sites) from the oligomer chains, or the attack of one Brønsted acid site Evaporated @ 100 °C % (V/V) 46–71 27 26
to the double bonds of the thermally degraded PP molecules. Fragments Evaporated @ 150 °C % (V/V) 75(min) 49 47
Initial boiling point (IBP) °C – 46.8 47.7
having lower molecular weights were produced in the catalytic de-
Final boiling point (FBP) °C 210 (max) 352 346
gradation of PP compared to that of PE, since the catalyst has a higher
catalytic cycle in order to degrade the PE chain than that of PP, and this
Distillation Properties Units limits EN590 Feedstock
is consistent with the higher degradation reaction time of PE than that
of PP. It is well known that the pyrolysis of PE and PP produce olefins PE PP
and paraffin but the use of USY catalyst modified their composition
while it is difficult to notice a variation in PP pyrolysis product, PE Recovered @ 250 °C % (V/V) 65 (max) 76 77
Recovered @ 350 °C % (V/V) 85 (min) 89 91
pyrolysis product were radically changed. There are no normal paraf- Temp @ 95% V/V rec °C 360 (max) 360 360
fins recovered in catalytic condition while in non catalytic cracking

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3.4. Distillation fraction of pyrolytic oils

Table 4 shows the boiling range distributions of the oil obtained

from the catalytic pyrolysis of PP and PE in the presence of USY zeolite
compared to the two major commercial fuels, gasoline and diesel. It is
observed that the boiling range of the oil is out of the range of gasoline
and diesel because of the presence of a mixture of light and heavy
compounds, which suggests the separation of oils into different frac-
tions as gasoline-like, kerosene-like and diesel-like fuels. According to
EN228 requirements, minimum 20% of the volume should be evapo-
rated at 70 °C, and in order to meet this requirement, the max final
boiling point was 170 °C. The oil obtained from the pyrolysis was after
separated by distillation to two fractions, a heavy phase and a light
phase, at 3 different temperatures (130, 150 and 170 °C). The fuel
properties of the different fractions are presented in Fig. 4.
As it can be seen in Fig. 4 (a), the optimal temperature of separation
is 170 °C where the densities of the light phase from the liquid oil ob-
tained from pyrolysis of PP and the liquid oil obtained from pyrolysis of
PE meet the range of gasoline specified in EN 228. In addition, ac-
cording to the volatility classes, the light phase ranged in classes A & B
has a vapor pressure between 45 and 70 kPa. As shown in Fig. 4 (b), at a
separation temperature of 170 °C, the light phase belongs to classes
A & B.
Fig. 4 (c, d) shows the densities and the flash point of the heavy
phase obtained after distillation of the pyrolytic oils at different tem-
peratures. The densities and flash point obtained at 170 °C are very
close to the range of EN 590.
Tables 5 and 6 show the boiling range distributions of the oil after
separation at 170 °C compared to the two major commercial fuels,

Table 5
Distillation and physical properties of the gasoline-like oil obtained after separation@
170°C according to EN 228 standard limits established for gasoline fuel.

Distillation Properties Units limits EN228 Feedstock

PE PP

IBP °C – 46.8 47.7

Evaporated @ 70 °C % (V/V) 20–48 21 21
Evaporated @ 100 °C % (V/V) 46–71 52 50
Evaporated @ 150 °C % (V/V) 75 90 87
FBP °C 210 (max) 170 170

Physical Properties
RON 95 (min) 97 96
Density @ 15 °C kg/m3 720–775 708 710
Vapour pressure kPa 45–60 (class A) 44.7 45

Table 6
Distillation and physical properties of the diesel-like oil obtained after separation @
170 °C according to EN 590 standard limits established for diesel fuel.

Distillation Properties Units limits EN590 Feedstock

PE PP

IBP °C – 159.5 160.1

Recovered @ 250 °C % (V/V) 65 (max) 61 60
Recovered @ 350 °C % (V/V) 85 (min) 100 100
Temp @ 95% V/V rec °C 360 (max) 350 350

Physical Properties
Calculated cetane number 46 (min) 53 52
Fig. 4. Physical properties of (a,b) light phase and (c,d) heavy phase at different se- Density @ 15 °C kg/m3 820–845 797 800
paration temperatures. Viscosity @ 40 °C mm2/s 2–4.5 1.4 1.5
Flash point °C 55 (min) 54 49

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