Journal of Analytical and Applied Pyrolysis 142 (2019) 104668

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Journal of Analytical and Applied Pyrolysis

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Assessing the potential of the recycled plastic slow pyrolysis for the T
production of streams attractive for refineries
Roberto Palosa, Alazne Gutiérreza, , Francisco J. Velaa, Jon A. Mañaa, Idoia Hitaa, Asier Asuetab,
⁎

Sixto Arnaizb, José M. Arandesa, Javier Bilbaoa

a
Department of Chemical Engineering, University of the Basque Country UPV/EHU, PO Box 644, 48080, Bilbao, Spain
b
Gaiker Technological Center, Parque Tecnológico, Edificio 202, 48170, Zamudio, Spain

ARTICLE INFO ABSTRACT

Keywords: The slow pyrolysis of recycled high-density polyethylene (HDPE) has been investigated in a batch autoclave
Plastic waste reactor at 430–490 °C and reaction times of 15–60 min, with the aim of obtaining the maximum yield of plastic
Recycled HDPE oil (PO) with an adequate composition for its subsequent valorization in refinery. Specifically, PO yields up to
Slow pyrolysis 85–90 wt% have been achieved operating at 430 °C and 15–37.5 min, noting that the obtained yields strongly
Liquid oil
depend on temperature and, to a lesser extent, on reaction time. Simulated distillation and gas chromatography
Waste-refinery
analyses of PO have shown its potential for its valorization in a waste refinery scheme targeting the production of
Fuel
alternative fuels. Thus, the PO obtained at 430 °C and 15 min is suitable to be cofed to the fluidized catalytic
cracking (FCC) unit since it has a simulated distillation curve similar to that of vacuum gasoil (VGO). On the
other hand, the PO obtained at 430 °C at the longest reaction time and those obtained at 460 °C are suitable to be
fed together with light cycle oil (LCO) into a hydroprocessing unit. The composition of naphtha and middle
distillates of PO reveals that these fractions are appropriate for their blending with commercial diesel and ga-
soline pools after a mild hydrotreating to reduce their olefin content.

1. Introduction composition of the oil to be used as a fuel. Furthermore, Fivga and

Dimitrou [11] have proven that pyrolysis is economically viable at a
The global production of plastics has been steadily increasing, up to large scale. Even though gasification has also acquired a remarkable
348 Mt in 2017, with an annual growth of ca. 1.5% [1]. After reaching technological development [12], the reaction technologies for the
its end of life, a great fraction of these plastics ends up in municipal production of fuels and commodities from syngas require of important
solid waste (MSW), where they constitute around 7 wt%, causing ser- capital investments. Amongst the different pyrolysis alternatives, fast
ious environmental hurdles due to their low biodegradability and the pyrolysis (at low temperatures with high heating rates and short re-
lack of large-scale recycling solutions [2]. Nonetheless, there is a sidence time of the volatiles) can be performed in continuous regime
worldwide pressing need for plastic recycling in order to avoid their with different types of reactors, e.g. fluidized bed, spouted bed, ablative
uncontrolled landfilling, where plastics are degraded forming micro- [7,10,13]. The use of an in-situ located catalyst is a promising option to
plastics (particle size < 5 mm), which have an upsetting ecological control the composition of gaseous and liquid products [14–17].
impact on the soil [3] and on marine [4] and freshwater ecosystems [5]. Moreover, the catalyst can be located exsitu to intensify the recovery of
Primary and secondary (mechanical) recycling routes offer good monomers and adjust the composition of the liquid product [18,19].
perspectives for their implementation at small and medium scale [6]. On the basis of the socio-economic factors that determine the in-
However, the large amount of formed waste plastics formed advices for stallation of waste plastics recycling units, a strong tendency is to as-
ternary recycling routes for the large-scale production of fuels and sociate the recycling of plastics, which are obtained from crude oil
chemicals, as well as the recovery of the monomers [7,8]. Among the processing derivates, with the petrochemical industry. For this purpose,
thermochemical processes for plastic valorization, pyrolysis attracts already depreciated refinery units would be used (waste refinery), i.e.,
great attention [9,10], since it allows for obtaining high oil yields from fluidized catalytic cracking (FCC) and hydroprocessing units, because of
addition polymers, such as polyolefins, and for tailoring the their high capacity and versatility. Thereby, waste plastics could be

⁎
Corresponding author.
E-mail address: [email protected] (A. Gutiérrez).

https://doi.org/10.1016/j.jaap.2019.104668
Received 8 May 2019; Received in revised form 23 July 2019; Accepted 24 July 2019
Available online 25 July 2019
0165-2370/ © 2019 Published by Elsevier B.V.
R. Palos, et al. Journal of Analytical and Applied Pyrolysis 142 (2019) 104668

integrated into different stages of the manufacturing chain of fuels and general trend, all the physicochemical properties interesting for pyr-
commodities, which could be marketed together with those derived olysis are within the ranges commonly established in literature for
from the usual oil streams with their composition fitted to legal re- HDPE wastes [8,9].
quirements. The integration of the valorization of plastics into refinery Density has been calculated according to the ASTM D1895B
streams has been addressed in the literature with different strategies. Standard, whereas glass transition temperature and melting point have
Among them, one can find the co-cracking of plastics and different been determined by differential scanning calorimetry (DSC) in a Mettler
refinery streams, such as light cycle oil (LCO), a highly aromatic stream Toledo DSC 822e apparatus according to the ASTM D3418 Standard.
from FCC units, and vacuum gasoil (VGO), the current feedstock to FCC From the DSC analysis results, fusion enthalpy (ΔHf) and latent heat of
unit which comes from the vacuum distillation unit [20–24], and the crystallization (ΔHc) have been determined by integrating the area
hydroprocessing of plastics blended with LCO [25] or vacuum residue under each characteristic peak. The higher heating value (HHV) has
(VR) [26,27]. The main physicochemical properties of standard VGO been calculated using a Parr 369 M 1356 Isoperibol Bomb calorimeter
and LCO are collected in Table S1. and the content of inorganic ash has been determined by calcination at
For the integration of pyrolysis with other refinery processes, the 1000 °C in a Nabertherm LT 5/12 muffle furnace. The concentration of
slow pyrolysis (long isothermal holding time) of plastics could be per- halogens (Cl, Br, P) has been determined by means of High Performance
formed at small and moderate scale, in delocalized units, obtaining a Liquid Chromatography/Ion Chromatography in a Dionex DX-100 ion
high yield of plastic oil (PO) [28–30]. The pyrolysis unit, of simple chromatograph.
design, would be installed at the MSW plastic collection and segrega- The compositional analysis of the HDPE pellets has been done by
tion point and the PO obtained would be afterwards transported to a means of Fourier Transform Infrared Spectroscopy (FTIR) in a
refinery for its large-scale processing. In addition, with the valorization Shimadzu IRTracer-100 spectrometer equipped with MIRacle 10 ATR
of the PO, the refinery would fulfill the social function of plastics re- sampling technique. Spectra have been collected in the 600-4000 cm−1
cycling. It should also be taken into account that, given the high ca- wave number range. The ATR-FTIR spectra of HDPE, both recycled and
pacity of the FCC and hydroprocessing units, the co-feeding of PO in a pure, are shown in Fig. 1, in which the identified absorbance bands all
small ratio together with the current feedstock would be enough for the correspond to CeH bond vibrations. Considering all the previous, it can
complete recovery of the plastics collected in a wide geographic en- be seen that both pure and recycled HDPE have three main vibration
vironment. bands (highlighted in grey in Fig. 1) showing the purity of the recycled
This work mainly focuses on the interest of the PO from HDPE HDPE. The vibration band located at ca. 500 cm−1 is assigned to
pyrolysis as a potential feedstock for refineries and so, its valorization rocking vibrations of methylene groups (−CH2–), that is, asymmetric
in a refinery unit (FCC or hydroprocessing units) where, depending on flexion vibrations caused by rotations within the plane, whereas at
its composition, it would be co-fed with Vacuum Gas Oil (VGO) or Light 1600–1480 cm−1 there is a CeH bending band of CH2 groups, meaning
Cycle Oil (LCO). Based on all the premises, this work delves into the symmetric flexion vibrations in the plane [31]. Finally, the vibrational
effect of temperature and reaction time on the quality and composition bands located at 2875–2770 and 3000–2875 cm−1 are attributed to
of the PO obtained from the slow pyrolysis of HDPE. The runs have CH2 symmetric and asymmetric stresscompression vibrations, respec-
been performed in a batch reactor pursuing the production of a high- tively [32]. Additionally, an absorption band with weak intensity at
quality liquid product suitable to be considered as a source of fuels and/ 1025 cm−1 is observed in both samples, connected to the wagging de-
or commodities. Insight into product composition and quality has been formation of the CH3 groups [33]. The absence of vibrational bands
gathered by means of simulated distillation and gas chromatography above 3000 cm−1 and in the 1700–1470 cm−1 range suggests that the
analyses for evaluating the properties and composition of the PO to sample presents a lineal and saturated nature.
assess its interest to be co-fed to a refinery unit, as well as the interest of It should be pointed out that four additional absorbance bands
its naphtha and middle distillates fractions as components of the com- (highlighted in yellow in Fig. 1) with weak intensity have been detected
mercial gasoline and diesel pools, respectively. in the recycled pellets (at 2570, 1275, 960 and 625 cm−1), which do
not correspond neither with the composition of the HDPE nor with the
bonds found in the pure sample. Thus, the presence of a possible pol-
2. Experimental
luting agent in the recycled HDPE pellets must be considered, possibly
some kind of silicone trapped during mechanical recycling.
2.1. Characterization of the plastic feed
Thermal degradation analysis (results shown in Section 3.1) has
been performed to determine the temperature range at which plastic
The plastic feed consists on recycled HDPE pellets (obtained after
degradation occurs and estimate its composition. The study has been
sorting, washing and shredding of HDPE waste) supplied by GAIKER
carried out using a Mettler Toledo TGA2 Stare System thermobalance in
Technology Centre (Zamudio, Spain). The main physicochemical
properties of the recycled HDPE pellets are summarized in Table 1. As a

Table 1
Main physical properties of HDPE pellets.
Property Value

−3
Density (kg m ) 957
HHV (MJ kg−1) 46.1
Inorganic ash (wt%) 0.99
DSC analysis
Glass transition (°C) 118.5
Melting point (°C) 134.0
ΔHf (kJ kg−1) −204.8
ΔHc (kJ kg−1) 206.3
Concentration of halogens (ppm)
Chlorine < 500*
Bromine < 25*
Phosphorus 14.2

* below detection limit of the equipment. Fig. 1. ATR-FTIR spectra of pure HDPE and recycled HDPE pellets.

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R. Palos, et al. Journal of Analytical and Applied Pyrolysis 142 (2019) 104668

an inert N2 atmosphere increasing temperature up to 600 °C at a 5 °C

min−1 rate.

2.2. Reaction equipment and protocol

Slow thermal pyrolysis runs have been carried out in an AISI 316
stainless steel, high-pressure 1800 mL Parr batch autoclave (4570
Series) reactor, equipped with a heated oven, a thermocouple inside the
vessel and a cooling coil, with maximum pressure and temperature
capacities of 345 bar and 500 °C, respectively. Tested operating condi-
tions have been: temperature, 430, 460 and 490 °C; and reaction time,
15–37.5–60 min. A typical experiment protocol is the following: the
reactor is loaded with ca. 50 g of HDPE pellets and subsequently flushed
with nitrogen to (i) expel air from the reactor ensuring the inertness of
the reaction environment and (ii) perform a leak test (pressurizing up to
25 bar at room temperature and then returning to atmospheric pres-
sure). Once absence of leaks is checked, at atmospheric pressure and
with all the valves closed (discontinuous pyrolysis) the reactor is heated Fig. 2. Non-isothermal TGA analysis of recycled HDPE pellets.
with an incremental rate of 15 °C min−1 until the reaction temperature
is reached and at this point zero time is established. The pressure of the (length, 5 m; internal diameter, 0.25 mm; thickness, 0.15 μm) capillary
reactor is continuously monitored. Once the reaction time has ended, a columns connected by means of a valvebased flow modulator. The
cooling coil located inside the reactor, which allows the circulation of equipment has been previously described in detail elsewhere [34].
water, cools down the reactor. After the run, gas products are collected The density of PO has been measured according to the ASTM D6822
in a gas-sampling bulb for their analysis by GC. The liquid PO product is Standard, while dynamic viscosity tests have been carried out in a
separated from the remaining solids by vacuum filtration and dried Brookfield DV-III ULTRA rheometer by using a thermal bath to main-
until constant weight was attained at room temperature. Finally, PO is tain the temperature of the sample at 40.6 °C during the analysis.
collected and stored on a refrigerated chamber to ensure its stability.
For each reaction run, the yields of oil and solids have been de-
3. Results
termined by weighing, whereas the gas production has been determined
by mass difference of the starting weight of the charged reactor and the
3.1. HDPE thermal degradation
final weight of the depressurized reactor as follows:

Yield of PO (wt%) =
mass of PO
·100 As depicted in Fig. 2, the degradation of the HDPE occurs over three
mass of HDPE (1) different stages [35]. The first one takes place from 100 °C to ca. 420 °C
mass of dried solids with a weight loss of 3 wt%, corresponding to the volatilization of low-
Yield of solids (wt%) = ·100
(2) molecular weight species located in the smaller lateral chains that have
mass of HDPE
suffered a scission via secondary radicals. The second stage, which
Yield of gas (wt%) = 100 Yield of PO Yield of solids (3) starts at 420 °C and ends at 500 °C, is associated with cracking reactions
of the main hydrocarbon chains via primary radicals. Based on the
derivative curve of the weight loss, it can be seen that the maximum
2.3. Product identification and analysis
weight loss rate is achieved at 479 °C. The last stage takes place above
500 °C as a consequence of the decomposition of the carbonaceous re-
Gas products are analysed through gas chromatography in an
sidue [36]. The obtained results are comparable to those reported in
Agilent Technologies 6890 GC System equipped with: (i) a FID detector;
literature for virgin HDPE, proving the purity of the recycled HDPE
(ii) a HP-PONA capillary column (length, 50 m; internal diameter,
pellets employed for the study [37,38].
0.20 mm; thickness, 0.50 μm); and, (iii) a CO2 gas cylinder to reach
cryogenic temperatures (−30 °C).
POs have been extensively analysed in order to determine their si- 3.2. Product distribution in the slow pyrolysis of HDPE
mulated distillation curve, composition of the naphtha and middle
distillate fractions, and also their density and dynamic viscosity. The product yields obtained from the pyrolysis tests, namely gas, PO
Simulated distillation analyses have been carried out according to the and solids, as well as the maximum pressures of each reaction run, are
ASTM D2887 Standard using an Agilent Technologies 6890 GC System, summarized in Table 2. Additionally, PO has been analyzed by means of
equipped with: (i) a FID detector; and (ii) a DB2887 semi capillary simulated distillation analysis and classified into three different frac-
column (length, 10 m; internal diameter, 0.53 mm; thickness, 3 μm). tions based on a boiling point temperature (TB) criteria: naphtha
The composition of the naphtha fraction has been determined using the (TB < 216 °C), middle distillates (MD) (216 °C < TB < 343 °C) and
same GC setup as the one previously described for gas product analysis heavy cycle oil (HCO) (TB > 343 °C). From the obtained results
but without requiring cryogenic temperatures. Additionally, the com- (Table 2), we observed that both temperature and reaction time have a
pounds of the naphtha fraction have been identified according to the strong influence on product distribution. This way, upon increasing
NIST 147 database by means of gas chromatography/mass spectro- temperature and residence time the total pressure also increases, ob-
metry (GC–MS) analysis performed in a Shimadzu GC–MS QP2010S taining the highest gas product yield at the harshest operating condi-
mass spectrometer coupled in line with a Shimadzu GC-2010 GC tions of 490 °C and 60 min, as a result of the enhancement of thermal
system. The composition of the middle distillates has been determined cracking. Regarding their composition (Table S2), the main products on
by means of comprehensive bidimensional gas chromatography the gas phase are propane and propylene followed by ethane and
(GC × GC) in an Agilent 7890 A chromatograph coupled to a mass ethylene, in agreement with literature [28,29]. The composition of the
spectrometer (MS) Agilent 5975C series GC/MSD provided with: (i) FID gases makes them suitable for energy recovery in order to obtain the
and MSD detectors; and (ii) a DB 5MS J&W 122–5532 (length, 30 m; energy required for pyrolysis. Besides, it is observed that reaction
internal diameter, 0.25 mm; thickness, 0.25 μm) and an HP-INNOWAX temperature has a relevant effect on the composition of the gases. Thus,

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R. Palos, et al. Journal of Analytical and Applied Pyrolysis 142 (2019) 104668

Table 2
Product distribution and PO fractions at different operating conditions.
Temperature (°C) Time (min) Max. observed pressure (bar) Product distribution (wt%) PO fractions (wt%)

Gas PO Solid Naphtha MD HCO

15 1 8.7 90.3 1.0 4.1 25.4 70.5

430 37.5 5.50 14.2 84.8 1.0 34.4 34.9 30.7
60 5.86 18.9 80.1 1.0 39.6 32.5 27.9
15 9.50 19.1 79.9 1.0 44.8 32.3 22.9
460 37.5 15.75 38.8 59.5 1.7 64.6 26.6 8.8
60 15.96 46.4 50.7 2.9 69.4 23.4 7.2
15 20.90 59.3 37.4 3.3 72.2 20.6 7.2
490 37.5 18.93 60.6 34.5 4.9 75.2 18.1 6.7
60 17.78 66.9 26.6 6.5 78.2 17.1 4.7

increasing the temperature increases the concentration of paraffins and VGO and LCO (two conventional refinery streams) supplied by Petronor
decreases that of olefins. Refinery (Muskiz, Spain), have been included in the results shown in
On the other hand, at higher temperatures and reaction times, a Fig. 3 (VGO in Fig. 3a and LCO in Fig. 3c). It can be seen that all the POs
decrease in the PO yield is observed, with a parallel increase in the are lighter than VGO. Just the PO obtained at 430 °C for a reaction time
yields of gases and solids. This result is due to extent of propagation of of 15 min (Fig. 3a) has a similar distillation curve to that of the VGO,
homolytic cleavage process of simple CeC σ-type bonds and of the but more heterogeneous. On the other hand, the POs obtained at 430
propagation of subsequent radical chain reactions, which lead to the and 460 °C (Fig. 3b) show a distillation curve similar to that of the LCO
formation of products with a lower molecular weight and hence in- with a lower initial boiling point and a higher final boiling point,
creased tendency to vaporize [39]. However, at the same time, rates of having therefore a wider distribution of products. The POs obtained at
secondary undesired reactions are also boosted leading to the formation 490 °C (Fig. 3c) have distillation curves clearly lighter than that of the
of higher amounts of solid products [10]. Then, considering the ob- LCO, proving that thermal cracking reactions are highly boosted at this
tained yields (Table 2), the optimal conditions should be those that temperature.
maximize the production of PO. This way, operating at a temperature of Based on the aforementioned results, as the POs show a final boiling
430 °C, PO yields of 90.3–80.1 wt% are obtained at all the investigated point lower than 500 °C, they can be considered as valuable feedstock
reaction time range. Additionally, working at 460 °C an interesting PO for catalytic cracking or hydrocracking units combined with their cur-
yield of 79.9 wt% has been attained in a 15 min reaction. rent feedstock, i.e., VGO or LCO, respectively [41]. Indeed, this strategy
Focusing on the PO fractions (Table 2) and from the SD curves de- has sound industrial prospects with a view to meeting the requirements
picted in Fig. 3, it can be seen that the pyrolysis temperature has a for alternative feedstock in refineries. Therefore, as PO should be sub-
leading effect on the PO fraction distribution, while reaction time is jected to a subsequent upgrading stage in a refinery unit, an ideal PO
secondary. This way, an increase in temperature from 430 to 490 °C should not be excessively light in order to minimize the gas production
implied a rise of the PO naphtha fraction at 15 min from 4.1 to 72.2 wt in the following stage. Hence, a PO with a moderate fraction of naphtha
%. On the other hand, for a temperature of 460 °C, an increase of the and high concentration of middle distillates would have the optimal
reaction time from 15 to 60 min caused an increase of the naphtha composition. On the basis of the results in Table 2 and Fig. 3 and
fraction from 44.8 to 69.4 wt%, indicating that increasing the residence considering the similarity of the distillation curves, the PO obtained at
time enhances thermal cracking [29]. A similar tendency was observed 430 °C and 15 min, with a content of naphtha, middle distillates and
by Das and Tiwari [40] studying the light (C6–C11) and middle HCO of 4.1, 25.4 and 70.5 wt%, respectively, is appropriate for being
(C12–C20) fractions of the PO obtained through low-temperature co-fed together with VGO to the FCC unit. On the other hand, the POs
(300–400 °C) slow pyrolysis of virgin HDPE. obtained at 430 °C for reaction times of 37.5 and 60 min and at 460 °C
In order to obtain a proper idea of the suitability of the produced for a reaction time of 15 min, with contents of naphtha, middle dis-
POs as a potential refinery stream, the simulated distillation curves of tillates and HCO of 34.4–44.8, 32.3–34.9 and 22.9–30.7 wt%,

Fig. 3. Simulated distillation curves for the different POs obtained at 430 °C (a), 460 °C (b) and 490 °C (c) at different reaction times.

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R. Palos, et al. Journal of Analytical and Applied Pyrolysis 142 (2019) 104668

respectively, are suitable for being blended with LCO and fed to a hy- Fig. 4. The hydrocarbon composition is strongly temperature-depen-
droprocessing unit. dent as at 430 °C (Fig. 4a) is mainly dominated by paraffins and olefins
Faussone [42] has assessed an industrial pyrolysis plant located in (44.0–73.7 and 22.3–43.1 wt%, respectively) with minor amounts of
South East Asia that synthesizes transportation fuel from waste feed- aromatics (3.9–17.1 wt%). However, at 490 °C (Fig. 4c) the naphtha
stock. In the pyrolysis stage, they obtain a liquid yield of ca. 65 wt% fraction of the PO is predominantly aromatic (51.6–72.2 wt%) with a
with a distribution of 40 wt% of naphtha, 45 wt% of LCO and the re- lesser content of paraffins (9.6–16.2 wt%).
maining 15 wt% of HCO. These results are in concordance with those Paraffins are obtained through a free-radical transfer reaction in
previously designated in this section as the optimal ones, i.e., the liquid which an H atom bonded to a C atom of a neighbor macromolecule of
products obtained at 430 °C for reactions of 37.5 and 60 min and the the polymer chain is extracted, leading to the formation of a terminal
liquid product obtained at 460 °C for a reaction time of 15 min methyl group (CH3–R) and, consequently, propagating its radical
(Table 2). Indeed, in our work, higher PO yields have been obtained character [43]. This way, the reduction of the concentration of paraffins
(79.9–84.8 wt%) under the same conditions, rendering the possible in the naphtha fraction of the PO when both temperature and reaction
step-up in scale and size encouraging. time are increased is consequence of the propagation of β-scission re-
actions, which lead to the formation of olefins and diolefins as obtained
3.3. Composition of the PO fractions molecules have at least one terminal vinyl group (CH2=CH–R) [22]. It
should be specified that n-paraffins and iso-paraffins have been grouped
Due to the high content of naphtha and middle distillates of the POs, together for analysis of the data in Fig. 4, given that the concentration
an analysis of each fraction of the POs obtained at the different oper- of iso-paraffins is negligible. This phenomenon occurs as the formation
ating conditions has been performed by gas chromatography. The main of iso-paraffins is stereochemically and thermodynamically not favored
aim of these analyses is to determine the concentration of the different due to the transpositions of the methyl groups (CH3–) [44].
hydrocarbon groups and assess the interest of each of these fractions A maximum olefin concentration is attained at the intermediate
(naphtha, middle distillates …), which can be easily separated by dis- temperature of 460 °C (Fig. 4b) due to the increase of the β-scission type
tillation, for their integration into the gasoline and diesel refinery pools. reactions. These reactions are thermodynamically favored at higher
temperatures as they require high amounts of energy to break the ad-
jacent CeC bond leading to the formation of smaller and thermo-
3.3.1. Naphtha dynamically more unstable reaction intermediates [45]. A similar trend
The compounds of the naphtha fraction of the PO have been is observed at longer reaction times; rather, the concentration of olefins
grouped according to their chemical nature in: n-paraffins and iso- goes through a maximum at 460 °C.
paraffins (P + iP), olefins (O) and aromatics (A) as it can be seen in

Fig. 4. Composition of the naphtha fraction of the POs obtained at 430 °C (a), 460 °C (b) and 490 °C (c) at different reaction times.

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R. Palos, et al. Journal of Analytical and Applied Pyrolysis 142 (2019) 104668

Furthermore, aromatics are obtained from the thermal cracking of polymerization and aromatization reactions, to form more stable, larger
long lineal polymeric chains involving different reaction mechanisms: molecules, e.g. aromatic compounds [48].
cyclization of olefins, condensation of olefins and cyclization of n-par-
affins. Through these reaction mechanisms a molecule of naphthene is 3.4. Comparison of the PO fractions with commercial fuels
obtained, which is subsequently easily dehydrogenated into an aro-
matic molecule due to the stability of the aromatic ring. Among the The physicochemical properties of the POs obtained at the optimal
different aforementioned reaction mechanisms, the most thermo- conditions (430 °C and 37.5 min; 430 °C and 60 min; and, 460 °C and
dynamically favored are cyclization and condensation of olefins, being 15 min) have been measured and compared with those of commercial
successive reactions to the β-scission that forms the olefins from the gasoline and diesel (Table 3). The obtained POs show an initial boiling
polymer chains [46]. Therefore, this explains why aromatics increased point (IBP) of ca. 40 °C and a final boiling point (FBP) of ca. 510 °C.
both with the reaction time and temperature in Fig. 4, decreasing the Regulations and specifications of automotive fuels set the boiling range
olefin content. for gasoline in 50–210 °C and for diesel in 172–350 °C according to
The naphtha fraction has also been characterized on a carbon Directive 98/70/EC of the European Parliament. Therefore, and in
number basis and according to the chemical structure of its components order for the boiling points of the naphtha and middle distillates frac-
as shown in Figures S1-S3 in the Supplementary Material, in which the tions to fit in the ranges of gasoline and diesel, a reduction of the
evolution of the distribution of each group with the reaction tempera- average molecular weight of the PO is required in order to comply with
ture and time is depicted. In the case of paraffins (Figure S1), at higher current legislation. For this purpose, POs must be subjected to an up-
temperatures cracking reactions are boosted leading to the formation of grading stage, e.g. catalytic cracking or hydrotreating, as it has been
a higher amount of lower molecular weight paraffins. Olefins (Figure previously laid out in Section 3.3, in order to reduce the amount of
S2) follow a similar trend than that of the paraffins. When temperature heavy molecules and increase the percentage of shorter chains C5-C12
is increased, olefins of lower molecular weight (C5–C8) are produced and/or C12-C20, which correspond to gasoline and diesel fuels, respec-
because of the stabilization of β-scission reactions leading to a reduc- tively.
tion in the amount of long chain olefins (C10 and C11-12). Finally, with With regard to the restrictions in the chemical nature of commercial
regard to aromatics (Figure S3), an increase in the reaction time and fuels, diesel has no specifications, whereas in the gasoline the content of
temperature favors the production of alkyl-substituted aromatics. While olefins, aromatics and benzene is restricted. Thus, as naphtha fractions
the concentration of aromatics increases, dealkylation reactions become of the produced POs are mainly constituted of n-paraffins and olefins
more relevant leading to the formation of BTX fraction (benzene, to- (31–44 and 39–44 wt%, respectively), their composition does not
luene, xylenes), which corresponds to C6–C8 molecules, respectively, comply with the limits, as the concentration of olefins must be below
and the reduction of long chain alkyl aromatics (C10 and C11-12). 18 wt%. However, the concentration of aromatics (17–29 wt%) is lower
However, this latter reduction is not so evident at 490 °C (Figure S3c), than that established by the legislation. Consequently, the goal of re-
when condensation reactions are also boosted producing naphthalene- ducing the content of olefins can be reached by means of a mild hy-
type molecules, known to be coke precursors for their higher C/H ratio. drotreatment stage in refinery, i.e., moderate pressure and temperature,
of the raw PO or of the PO naphtha fraction previously separated by
3.3.2. Middle distillates distillation. On the other hand, sulfur restrictions are avoided for POs,
The compositional analysis of the middle distillates fraction of the as no sulfur has been detected in them. Therefore, after the mild hy-
produced POs has been carried out in an analogue way to the naphtha drotreating stage, the PO or the naphtha of PO would have an appro-
fraction in the previous section. As depicted in Fig. 5, a highly complex priate composition to be blended with refinery streams with higher
composition has been observed for middle distillates in contrast to the aromatic content, which is a really interesting strategy for the valor-
naphtha fraction (Fig. 4) and, hence, a more detailed compound clas- ization of secondary refinery streams, such as LCO.
sification has been established, as follows: n-paraffins (nP), iso-paraffins The average high heating value (HHV) for the POs has been higher
(iP), olefins (O), naphthenes (N), 1-ring aromatics (A1), 2-ring aro- than 45 MJ kg−1, which can be assumed as suitable to be used as a
matics (A2) and 3+-ring aromatics (A3+). source of energy being contained within the range of commercial ga-
The strong impact of reaction temperature is again highlighted in soline (42–46 MJ kg−1) and close to that of commercial diesel
the composition of the MD fraction. This way, at 430 °C (Fig. 5a) n- (42–45 MJ kg−1). The density of the POs (798 kg m-3), is located be-
paraffins and olefins are the main chemical groups with concentrations tween the values established for gasoline and diesel. This indicates that
of 35.4–39.2 and 47.9–32.3 wt%, respectively, for the different reaction after a proper distillation and separation of the fractions, their density
times. It should be mentioned that the formation of 2-ring aromatics is would be the required one.
boosted at the highest reaction time as they increase from 3.5 to 5.6 to
16.1 wt%. Typically, in pyrolysis the H/C atomic ratio decreases with 4. Conclusions
temperature and reaction time, which is consistent with the reported
increasing aromaticity. Hence, the highest reaction time (60 min) pro- The slow pyrolysis of recycled HDPE has proven to be a promising
duces a decline in the H/C ratio favoring the aromatization processes management technique in order to obtain a high yield of liquid product
and the formation of small aromatic clusters that can be found both in (PO) whose composition and properties are adequate to be integrated
liquid and solid products [47]. Focusing on the results obtained at into conventional refinery streams, such as VGO or LCO. Afterwards, in
460 °C (Fig. 5b), n-paraffins and olefins are still the main compounds, the refinery, by means of cracking or hydrocracking, the composition of
32.3–17.8 and 43.3–23.1 wt%, respectively, although the concentration the PO will be tuned to comply with the requirements established for
of 2-ring aromatics starts to increase, particularly at reaction times automotive fuels.
higher than 15 min. This way, at 460 °C condensation and aromatiza- An increase in either the pyrolysis temperature and/or reaction time
tion reactions become relevant in the reaction medium. On the other promotes the formation of gaseous products (C1–C5), producing gas
hand, at 490 °C (Fig. 5c) middle distillates show a significant aromatic yields up to 70 wt% operating at 490 °C. Consequently, pyrolysis should
nature, as these compounds account up to 95.7 wt% for the longest be carried at 430 °C and short reaction times (15 min) in order to
reaction time (60 min), with an important contribution of 3+-ring maximize the production of PO (90.3 wt%). The simulated distillation
aromatics (23.6 wt%). This aromatic formation occurs in pyrolysis curve of this PO is similar to that of the vacuum gasoil (VGO), rendering
processes at high temperature because of the breakage of polymer it suitable to be co-fed with VGO to the fluidized catalytic cracking
macromolecules into smaller fragments in the form of unstable mole- (FCC) unit.
cules. Afterwards, these fragments recombine via pyrosynthesis, i.e., The PO obtained at 430 °C at longer reaction times and 460 °C, is

6
R. Palos, et al. Journal of Analytical and Applied Pyrolysis 142 (2019) 104668

Fig. 5. Composition of the MD fraction of PO obtained at 430 °C (a), 460 °C (b) and 490 °C (c) at different reaction times.

Table 3 HDPE plastic together with a subsequent catalytic cracking or hydro-

Comparison of the physical properties of the PO with those of the commercial processing stage for the final production of fuels in refinery (waste re-
gasoline and diesel and of the composition of the naphtha fraction with the finery) offers promising results in an economically viable manner for
specifications of the commercial fuels. the large-scale chemical recycling of plastic. The employment of al-
Property PO Gasoline Diesel ready depreciated refinery units for the PO tuning reactions (hydro-
treatment or cracking) and subsequent conditioning of the products as
Physical properties fuels is key for the economic viability of the initiative. In addition,
Density (kg m−3)a 789 720–778 957
HHV (MJ kg−1)b 45.4 42–46 42–45
through this strategy, the industrial implementation of the pyrolysis
IBP-FBP (°C)c 40–510 50–210 172–350 units would be facilitated, with the consequent thrust to the develop-
Chemical properties ment of pyrolysis technologies and the recycling industry.
Sulfur content (ppm) – < 10 < 10
Olefins (wt%) 39–44* < 18 –
Aromatics (wt%) 17–29* < 35 –
Declaration of Competing Interest
Benzene (wt%) – < 1 –

Determined according to: a ASTM D6822 Standard; b

ASTM D3523 Standard; c The authors declare that they have no known competing financial
ASTM D2887 Standard. interests or personal relationships that could have appeared to influ-
* on the naphtha fraction. ence the work reported in this paper.

appropriate to be co-fed together with light cycle oil (LCO) to a hy-

droprocessing unit. This PO has high contents of naphtha and middle Acknowledgements
distillates, in the ranges of 34.4–69.4 and 23.4–34.9 wt% (depending on
the reaction time), respectively. Thereby, the high content of olefins of This work has been carried out with financial support of the
the naphtha fraction, which can easily be separated by distillation, will Ministry of Science, Innovation and Universities (MICINN) of the
require a mild hydrotreatment before its blending into the gasoline Spanish Government (grant RTI2018-096981-B-I00), the Basque
pool. Furthermore, the negligible content of sulfur and the low content Government (grant IT2018-19), the European Union’s ERDF funds and
of aromatics boost the interest of this PO for its valorization together the European Commission (HORIZON H2020-MSCA RISE-2018.
with aromatic refinery streams, e.g. LCO. Contract No. 823745).
Consequently, a combined strategy of slow pyrolysis of recycled The authors also acknowledge Petronor Refinery for providing the
LCO and VGO used in this work.

7
R. Palos, et al. Journal of Analytical and Applied Pyrolysis 142 (2019) 104668

Appendix A. Supplementary data [24] S. Biswas, S. Majhi, P. Mohanty, K.K. Pant, D.K. Sharma, Effect of different catalyst
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