Fuel Processing Technology 206 (2020) 106455

Contents lists available at ScienceDirect

Fuel Processing Technology

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

Research article

Liquid oils produced from pyrolysis of plastic wastes with heat carrier in T
rotary kiln
⁎ ⁎
Yutao Zhang, Guozhao Ji , Chuanshuai Chen, Yinxiang Wang, Weijian Wang, Aimin Li
Key Laboratory of Industrial Ecology and Environmental Engineering, School of Environmental Science and Technology, Dalian University of Technology, 2 Linggong Road,
Dalian 116024, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: The conversion of plastic waste to energy product is a promising solution to both energy shortage and en-
Pyrolysis with heat carrier vironment pollution. In this study, plastic wastes were pyrolyzed in a rotary kiln to recover liquid oils that could
Rotary kiln be used as the source of valuable chemicals or fuels. The effects of filling ratio of heat carriers, and plastic wastes
Dynamic models types on the product spectrum were investigated. The dynamic models of heat carrier in pyrolysis of plastic
Plastic wastes
wastes showed that the suitable filling ratio of heat carrier for oil production is 15%. The liquid oils generated
Liquid oils
from a simulated mixture of plastic wastes pyrolysis had the most gasoline range hydrocarbons and reached to
89.1%. The simulated distillation of liquid oils showed that the gasoline fraction was between 49% and 84.5%.
The NMR analysis of liquid oils obtained from polyethylene and a simulated mixture of plastic wastes pyrolysis
showed that loading more heat carrier in the rotary kiln was favorable to produce olefins and paraffin. The NMR
analysis and the heat carrier models revealed that the greater heat transfer enhanced the H+ transfer in radical
reactions.

1. Introduction
The wide application and massive demands of plastic in day-to-day
life leads to the rapid generation of plastic wastes over the world [1,2].
It was reported that the percentage of plastic wastes in municipal solid
wastes (MSW) had been increased from < 1% in 1960s to > 10% in
recent years [3,4]. Although some plastic wastes are landfilled or di-
rectly incinerated in power plants. Unfortunately, there is still a con-
siderable amount of plastic waste discarded, hence causing deteriora-
tion of the ecosystem. On the other hand, the incineration produces
emissions of toxic substances, such as dioxins, acidic gases, and furans
into the atmosphere, causing threat toward human health [5]. Conse-
quently, the end-of-life management of plastic wastes becomes a public
concern. The use of waste for energy production via pyrolysis, which
converts low-grade and non-biodegradable plastic wastes into liquid
oils, syngas and char, would be an alternative valorization route [6,7].
This strategy alleviates the global energy crisis and reduces the waste
impact on the environment [8,9], and has drawn increasing attention in
research.
There have been many reactor configurations to conduct pyrolysis
for wastes. The difference in heating method resulted from the reactor
configuration plays an important role in the distribution of pyrolysis
products. Common heating methods mainly include reactor wall
heating, gas or solid heat carrier heating, and the combination of above-
mentioned techniques [10]. Fluidized bed with bed material heating is
a popular reactor type to pyrolyze wastes. For example, Jung and co-
workers [11] pyrolyzed polyethylene and polypropylene in a fluidized
bed reactor at 650–750 °C with different kinds of fluidized medium to
recover benzene, toluene, and xylene. It was reported in this study that
the product gas reused as the fluidizing medium is favorable for oil
production. This study observed defluidization due to the agglomerates
formed by the molten plastic on the fluidizing sands [12,13]. Thus the
reaction temperature of fluidized bed reactor has to be elevated higher
than that of other types of reactor [13]. Olazar et al. [14] carried out
fast pyrolysis of plastic wastes in a conical spouted bed. They reported
that the heat transfer rate is higher than that in a fluidized bed. The
short residence time of the volatiles and the high velocities of gas and
solid led to the high yield of wax products [15,16]. Although pyrolysis
of plastic wastes has been investigated extensively in many types of
reactors, such as fluidized bed [11], conical spouted bed [17], moving
bed [18], and drop-tube reactor [19]. There is still some technical
barriers between the lab-scale research and the industrial application.
These technical problems include low treatment capacity, high energy
consumption, and high capital cost. Therefore, it is necessary to develop
an adequate treatment method to pyrolysis plastic wastes.
As is known, the rotary kilns were successfully applied in pyrolysis

⁎
Corresponding authors.
E-mail addresses: guozhao.ji@uqconnect.edu.au (G. Ji), leeam@dlut.edu.cn (A. Li).

https://doi.org/10.1016/j.fuproc.2020.106455
Received 20 January 2020; Received in revised form 31 March 2020; Accepted 18 April 2020
0378-3820/ © 2020 Elsevier B.V. All rights reserved.
Y. Zhang, et al.
process, and exhibited several advantages including simple construc-
tion, easy operational control, and high flexibility of feedstock types
and sizes. Besides, rotary kiln process is an attractive option due to its
lower capital cost [20,21]. Godinho et al. [22] conducted pyrolysis of
elephant grass in a rotary kiln at the reaction temperature between 500
and 650 °C with the rotation speeds range from 2 to 4 rpm. They re-
ported that increasing the rotation speed significantly enhanced the bio-
oil yield. Ma et al. [23] carried out pyrolysis of oilfield sludge in a
rotary kiln with and without heat carrier, and the maximum gas and oil
recovery is 87.9% at 550 °C with heat carrier. Yazdani et al. [24]
pyrolyzed waste tire in a rotary kiln at the rotation speed of 1 rpm,
nitrogen flow rate 70 ml/min, and temperature between 400 and
1050 °C. They reported that the maximum liquid recovery was about
44 wt% at 550 °C. To the best of our knowledge, there have not been
many works which investigated pyrolysis of plastic wastes in the rotary
kiln. Especially, the influence of heat carriers on the pyrolysis process
has not been reported in open literatures. In this work, a rotary kiln
based on heat carrier heating has been used in pyrolysis of plastic
wastes, and the effect of heat carrier loading on the product distribution
was investigated by both experimental measurement and EDEM simu-
lation. Direct heat transfer between heat carrier and feedstock facil-
itates the heat supply for waste pyrolysis and promotes treatment ef-
ficiency of waste. Furthermore, the efficient heat transfer led to high
heating rate of plastic wastes, which could overcome the low thermal
conductivity and sticky nature of plastic wastes [25]. Meanwhile, the
rolling of heat carrier in the rotary kiln improves the mixing of parti-
cles, uniforms temperature distribution, and prevents agglomeration.
Thus, this work is to study the pyrolysis of several types of plastic
wastes, including polyethylene (PE), polypropylene (PP), polystyrene
(PS), and a simulated mixture of plastic wastes (SMP), in the rotary kiln
with heat carriers. Since the filling ratio of heat carrier in the rotary kiln
has an impact on the mixing and consequent heat transfer, the effect of
the filling ratio of the heat carrier on the process was explored in de-
tailed, and mechanistic explanation on the process was provided.
2. Materials and methods
2.1. Materials
The plastic wastes were collected from municipal solid waste station
in Dalian, China, and consisted of shampoo bottles, plastic basin, bev-
erage bottles and lunch-boxes that were made of high-density poly-
ethylene (HDPE), polypropylene (PP), polyethylene terephthalate
(PET), and polystyrene (PS) plastic types, respectively. The collected
plastic wastes were washed by deionized water and dried in the oven at
60 °C for 12 h. After that, they were cut and flaked into the size ranging
from 2 to 3 mm. The low-density polyethylene (LDPE), which was
mainly used to produce film or grocery bag, was obtained from
PetroChina Daqing Petrochemical Company in the form of pellets with
a diameter range of 3–4 mm. The quartz sand used as a heat carrier in
all experiments was supplied by SIGMA-Aldrich Co, and the size of the
sands was in the range of 0.9–2.0 mm. The quartz sands were washed
and calcined in a muffle furnace at 500 °C for 1 h before each experi-
mental run.
The proximate analysis of the plastic wastes was determined by the
automatic proximate analyzer (SDTGA5000, Sundy, China). The ulti-
mate analysis was performed using a CHNS analyzer (VarioEL III,
Germany). The lower heating value (LHV) of raw materials was mea-
sured by an automatic oxygen bomb calorimeter (ZDHW-6, Hongtai,
China). The sources and physicochemical characteristics of the plastic
wastes were presented in Table 1.
2.2. Rotary kiln pyrolysis reactor and experimental conditions
The pyrolysis experiments were carried out in a semi-batch rotary
kiln reactor that consists of an inert gas supplying unit, a rotary kiln
2
Fuel Processing Technology 206 (2020) 106455
pyrolyzer, a gas-liquid separation apparatus, and a gas product col-
lector. The schematic diagram of the rotary kiln pyrolysis system was
presented in Fig. 1. The rotary kiln pyrolyzer made of 316 stainless steel
has an inner diameter and a length of 300 mm and 65 mm, respectively.
The heat carrier was heated by the electric plate heater during the
experiment. The temperature profile in the heat carrier was monitored
by two K-type thermocouples that were placed in the center and bottom
of the reactor chamber, and the PID unit was used to control the re-
action temperature. The rotation speed of the rotary kiln reactor con-
trolled by a transducer can be adjusted from 0 to 20 rpm. The gas-liquid
separation apparatus, which was cooled to −15 °C by coolant circu-
lating pump (DLSB-5/25), consisted of four glass condensers to collect
the liquid oil/wax. The uncondensed gas passed through a gas drier and
was collected in a Teflon gasbag.
In this work, the filling ratio of rotary kiln is defined as the ratio of
the solid bed volume to the total volume of a rotary kiln reactor [26],
which was calculated by Eq. (1).
Vheat carrier bed
F= × 100%
Vrotary kiln (1)
where F is the filling ratio of heat carrier in the rotary kiln, Vheat carrier
bed is the volume of the heat carrier bed, and Vrotary kiln is the total
volume of the rotary kiln reactor. Various filling ratios were tested,
including 0%, 5%, 10%, 15%, and 20%. Meanwhile, the masses of heat
carriers are shown in Table S4 which were also the same as the con-
ditions simulated in EDEM® software for the dynamic models of various
filling ratios. Four different types of plastic wastes, polyethylene,
polypropylene, polystyrene, and a simulated mixture of plastic wastes,
were prepared. Polyethylene was prepared by mixing 50 wt% high-
density polyethylene with 50 wt% low-density polyethylene. Besides,
the simulated mixture of plastics consisted of a 50 wt% polyethylene,
25 wt% polypropylene, 15 wt% polyethylene terephthalate, and 10 wt
% polystyrene. The proportions were determined according to a short
review and presented in Table S1, which represents the main polymer
contents in municipal plastic wastes [27–33].
The axial distance of the rotary kiln was only 65 mm which is sig-
nificantly shorter than traditional rotary kiln for pyrolysis. The rotation
speed of the rotary kiln was 6 rpm. Meanwhile, nitrogen was introduced
to the reactor center at a flow rate of 350 ± 10 ml/min to keep the
inert atmosphere. The quartz sand was heated from room temperature
to 500 °C with a rotating speed of 6 rpm. Then 15 g of the sample was
fed to the reactor through the feeder. During the initial stage of the
pyrolysis process, the temperature of the plastic sample and heat carrier
dropped from 500 °C to about 490 °C within seconds. The temperature
variation implied that the plastic sample was immediately mixed with
the heat carrier and heated at an extremely high heating rate [18,23].
After the experiments, the liquid oils were weighed and stored in a
freezer before analysis, and the gas was analyzed by off-line micro-gas
chromatography (Agilent Micro-GC490, USA). Table S2 showed the
method of Micro-GC, and the quantitative analysis of gas content was
determined by means of a standard external method [34,35].
The “yellow” soft wax produced from polyethylene pyrolysis was
identified by the following procedures. Firstly, the liquid oils produced
from the pyrolysis of polyethylene were removed from the flask by
pouring, but there was still a small amount of liquid remaining in the
flask with wax. Then this small amount of pyrolysis oil was extracted
from wax by dichloromethane solvent. The wax products were collected
by extraction with n-octane at 120 °C at which wax could be dissolved.
After cooling down to room temperature, the wax and n-octane could be
separated as solid phase and liquid phase. Finally, the wax was ex-
tracted by filtration and centrifugation [36,37]. The final yields of li-
quid oil, wax, and gas were calculated using the following equation:
Xi
Yi = × 100%
X0 (2)
where Yi is the liquid oil, wax or gas yield, Xi is the mass of liquid oil,
Y. Zhang, et al. Fuel Processing Technology 206 (2020) 106455

Table 1
Origin and physicochemical characteristics of plastic wastes.
Plastic Source Application Proximate analysis (wt% dry basis) Elemental analysis (wt% dry basis) LHV (MJ/kg)

c
Volatile matter Ash C H N S O

a
HDPE Garbage station Household 98.2 1.8 84.5 13.8 0.1 0.1 1.5 43.0
LDPE CNPCb General 99.8 0.0 86.8 12.9 0.1 – 0.2 43.6
PP Garbage stationa Basin 99.6 0.4 85.0 13.9 0.1 0.0 1.0 43.6
PS Garbage stationa General 99.8 0.1 90.5 7.9 0.4 0.2 1.0 38.8
PET Garbage stationa Bottles 92.9 6.9 62.5 4.0 0.1 0.0 33.5 21.1

a
Municipal solid wastes (MSW) transfer stations in Dalian, PR China.
b
PetroChina Daqing Petro-chemical Company.
c
By difference.

Fig. 1. Schematic diagram of the semi-batch rotary kiln reactor system.

wax or gas, and X0 is the initial mass of the plastic waste sample. The
char yield was determined by Eq. (3), Mheat carrier (before) is the initial
mass of heat carrier, and Mheat carrier (after) is the final mass of heat
carrier.
Mheat carrier (after) − Mheat carrier (before)
Char yield = × 100%
X0
Each experiment was repeated three times to ensure the reliability
of the results and the average values were reported in this study [3].
2.3. Analytical techniques of the liquid oil products
2.3.1. GC–MS analysis
An Agilent 7890A GC analyzed the chemical composition of liquid
oil with a 30 m × 0.25 μm DB-5 capillary column coupled with a mass
spectrometry detector (Agilent 5975C, USA). Helium (99.99% pure)
was used as carrier gas at a flow rate of 1.0 ml/min. The initial tem-
perature of the oven was set to 40 °C and held for 5 min, and then the
oven was heated to 300 °C at 5 °C/min with an isothermal holding for
10 min. The injection volume was 1.5 μl at 300 °C. The ion source
temperature was 230 °C, and the mass spectrometry detector at the
condition of full-scan mode ranged from m/z 33 to 533. The chroma-
tographic peaks were identified by NIST library of mass spectral data
based on their retention times using standard compounds, and the
match quality of the identification results was not lower than 85%.
Besides, the percentages of compounds were determined based on the
total ion chromatogram (TIC) peak area.
2.3.2. FTIR and simulated distillation analysis
The chemical structure and functional groups of liquid oil were
obtained by the FTIR spectrometer (ThermoFisher 6700, USA). The li-
quid oils were scanned in the wavenumber range from 400 to
4000 cm−1 with a resolution of 4 cm−1. The boiling point distribution
of liquid oil was performed by simulated distillation gas chromato-
graphy (Scion 456-GC, USA) installed with CP-SimDist column
(10 m × 0.53 mm × 2.65 μm) based on the ASTM D2887 method
[38,39].
(3)
2.3.3. 1H NMR spectroscopy analysis
1
H NMR spectra of liquid oil were obtained with Bruker Avance II
500 (Germany) spectrometer at 500 MHz. Liquid oils were dissolved in
deuterated chloroform (CDCl3) at an operating temperature of 25 °C.
Chemical shifts were recorded by ppm with tetramethylsilane (TMS) as
the internal standard. In this study, the 1H NMR spectra were employed
to detect the information of hydrocarbon types, which helped to esti-
mate the quality of liquid oils [40].
3. Results and discussion
3.1. Dynamic models
In this study, the rheological behavior of the heat carriers in the
rotary kiln is an essential factor that affects the heat transfer between
plastic wastes and heat carriers. In view of this, the dynamic simulation
of the heat carriers was modeled by the discrete element method
(DEM), and the simulated dynamic process was used to evaluate the
motion of sand particles in the rotary kiln. The discrete element method
(DEM) is a reliable and efficient approach for modeling a granular
system, due to the benefits of no oversimplifying assumptions [41,42].
The analysis and simulation of heat carrier at different filling ratios
(5%, 10%, 15%, and 20%) in the rotary kiln reactor by using EDEM®
software were presented in Fig. 2. Generally, the bed materials in the
rotary kiln can be divided into two regions, the thick “passive” region
near the rotary kiln wall and a relatively thin “active” region in the

3
Y. Zhang, et al.
Fig. 2. The heat carrier velocity distribution in the rotary kiln under the different filling ratio.
upper part of the bed. As elucidated in Fig. 2, when the filling ratio of
the heat carrier was 5%, the particles in the active zone was relatively
stable compared to other cases. There was only some slight slippage at
the bottom of the bed. The sand bed behaved like a whole cake slipping
at the kiln wall. This was because the 5% filling rate was too light to
provide sufficient friction on the bottom wall. In view of the easiness of
slippage, most particle movement occurred at the bottom rather than at
the upper part of the bed.
It is well known that the physical mixing and heat transfer efficiency
in the rotary kiln depends on the velocity of particles and momentum
exchange in the active layer [43]. With the increase of filling ratio of
heat carrier, the friction between bed and kiln also increased. There-
fore, the particles along the wall could be rotated up higher, and sub-
sequently, rolling back down along the upper part of the bed. When the
particle rolling was vigorous, the particle exchange in the interface of
active-passive zone was enhanced as well. Besides, the particles could
be rotated higher in the case of higher filling ratios, thus more grav-
itational potential energy was converted to kinetic energy when they
were rolling down. Based on the results, loading more heat carriers in
the rotary kiln, such as the 15% or 20% filling ratio, could produce the
drastic mixing and achieve high heat transfer efficiency in the rotary
kiln.
3.2. Pyrolysis products distribution
The effect of the filling ratio of heat carrier on the pyrolysis products
at 500 °C was shown in Fig. 3. The pyrolysis of PS plastic produced a
maximum liquid yield of 91.8 ± 1.6 wt% when the filling ratio of the
heat carrier increased to 20%. In comparison to PE and PP plastics,
pyrolysis of PS showed higher conversion into liquid oil. This result can
be attributed to the structure of PS plastic that contains lots of phenyl
group [44]. In the process of PS pyrolysis, the high stability of benzylic
radical (reactive intermediate) favored unzip reaction [45], and limited
the further cracking which produces lighter hydrocarbons. Therefore,
the main product from pyrolysis of PS was styrene (a liquid phase). Kim
4
Fuel Processing Technology 206 (2020) 106455
et al. [45] also reported similar results that liquid oil was the dominant
products obtained from pyrolysis of PS plastic in the fluidized bed. The
liquid oils from PE pyrolysis increased from 35.7 ± 1.5 wt% to
43.9 ± 1.0 wt% when the filling ratio of heat carrier increased from
0% to 15%. However, the liquid oil yield dropped slightly to
39.5 ± 1.1 wt% at the filling ratio of 20%. The similar results were
also found for the pyrolysis of PP and SMP. Several reasons contribute
to the above phenomena: (i) Pyrolysis reactions mainly occurred in an
active layer of heat carrier bed, and with increased filling ratio of heat
carrier, the thickness of the active layer expanded. This process en-
hanced the heat and mass transfer efficiency to plastic wastes from heat
carriers. (ii) Loading more heat carrier can reduce the free space of the
rotary kiln reactor as shown in Fig. 2, which decreases the vapor re-
sidence time. Thus, pyrolysis of plastic wastes with a certain amount of
heat carrier in the rotary kiln led to more oil production. (iii) Mean-
while, with 20% filling ratio of heat carrier, the thick active layer
caused vigorous heat and mass transfer, which also led to the further
cracking of reactive intermediate (alkane or alkene radicals) to decrease
the production of liquid oil [23]. It was noteworthy that the wax yield
decreased from 13.0 ± 1.5 wt% to 1.0 ± 0.6 wt% when the filling
ratio increased from 0% to 20%. Besides, no “yellow” soft wax was
obtained from pyrolysis of PP compared to that of PE. This suggested
that the difference in feedstock molecular structure had an effect on the
pyrolysis product. The chain of PP has more methyl group substituent
on alternate carbon atoms [46]. Consequently the dominant products
obtained from PP pyrolysis are branched hydrocarbons with the char-
acteristic of low melting point. Meanwhile, PE pyrolysis produced a
relatively higher gas yield in comparison to the pyrolysis of other types
of plastic wastes in the rotary kiln. Similar results were also reported by
Pinto and Costa et al. [47] who attributed higher gas yield to the
thermal degradation of the straight long chain of PE polymer. In the
cracking process of PE molecular chain, the main random-chain scission
is homolytic rupture of covalent CeC bonds instead of CeH bonds. In
this case, the products produced from pyrolysis of PE are dominated by
linear hydrocarbons, which could undergo excessive cracking reaction.
Y. Zhang, et al. Fuel Processing Technology 206 (2020) 106455

70 PE liquid oil 80 PP Liquid oil

Wax Gas
Gas 70 Char
60
Char
60
Yield/wt.% 50

Yield/wt.%
50
40
40
30
30
20
20
10 10

0 0
500-0% 500-5% 500-10% 500-15% 500-20% 500-0% 500-5% 500-10% 500-15% 500-20%

Liquid oil PS Liquid oil

70 SMP
Gas Gas
100
Char Char
60

80
50
Yield/wt.%

Yield/wt.%
40 60

30
40
20
20
10

0 0
500-0% 500-5% 500-10% 500-15% 500-20% 500-0% 500-5% 500-10% 500-15% 500-20%

Fig. 3. Product distribution for pyrolysis of plastic wastes under various filling ratio of heat carrier at 500 °C (PE: polyethylene; PP: polypropylene; PS: polystyrene;
SMP: simulated mixture of plastic wastes).

These processes facilitated the production of lighter intermediate hydrogen transfer, isomerization, and termination by recombination or
[46,47]. This can also explain that the wax yield decreased during the cyclization, aromatization or poly-condensation [48,49]. On the other
pyrolysis of PE due to the further cracking of wax/aliphatic chains to hand, the reactor types and the operating parameters played an im-
produce gas and liquid oil. portant role on the distribution of products. The high velocity of heat
In summary, the yield of liquid oil from pyrolysis of plastic wastes carriers in the active layer led to the greater heat transfer among heat
followed the order of PS > PP > SMP > PE. Besides, the conversion carrier and volatile matters, which enhanced the interaction of radicals,
ratio to liquid oil increased when the filling ratio of heat carriers in- thus producing more aromatic compounds in the liquid oils.
creased to some extent, and the suitable filling ratio for oil production is The liquid oils generated from the polyolefin pyrolysis contained
15%. more complex chemical compounds compared with liquid oils derived
from PS or a SMP. This is because in SMP pyrolysis, alkene or alkane
radicals from polyolefin cracking would be connected to benzylic ring
3.3. Pyrolysis products from various plastic wastes
as substituent group to form aromatic products such as styrene and
toluene. Therefore, aliphatic product in SMP pyrolysis might not be as
3.3.1. Liquid oil
rich as in polyolefin pyrolysis, thus reducing the variety of SMP pro-
The liquid oils produced from pyrolysis of PE, PP, PS, and SMP at
ducts. In the liquid oils from PE, the content of aromatic and aliphatic
the filling ratio of 15% has been evaluated by GC–MS, and a summary
compounds was 55.5% and 43.1%, respectively. Similarly, in the liquid
of the total aromatics, major aromatic compounds, aliphatic and ga-
oils from PP, the aromatic and aliphatic compounds accounted for
soline range hydrocarbons (based on the number of carbons, C5–C12)
52.9% and 44.7%, respectively. This circumstance is attributed to the
are presented in Fig. 4. Liquid oils obtained by the pyrolysis of PS only
similar chemical bonds in the polyethylene and polypropylene mole-
contained aromatics, mainly including mono-aromatics (79.5%) and di-
cular structure. As shown in Fig. 4, toluene and p-xylene is the most
aromatics (11.5%). Furthermore, the styrene in liquid oil was as high as
abundant component in the aromatic compounds of liquid oils from
53.5% compared to other aromatic compounds. The high stability of
pyrolysis of polyolefins. From the GC–MS spectrum of liquid oil in
aromatic compounds inhibited their further cracking or hydrogenation
Fig. 5, the aliphatic compounds with cyclic-structures were formed in
into paraffin and olefins. This result was evidenced by Miandad et al. as
the pyrolysis of PP more readily compared to PE. It was found that
well [44]. They found styrene (48.3%), ethylbenzene (21.2%), and
cyclohexene, 3,5-dimethyl- (1.54%), cyclohexane, 1,3,5-trimethyl-
toluene (25.6%) in pyrolysis-oil produced from the pyrolysis of PS.
(1.38%), 1.4-cyclohexadiene, 1-methyl- (1.57%), cyclohexane, 1,1′-
For the pyrolysis of SMP, although the polyolefins accounted for
hexylidenebis- (0.81%), dodecane, 1-cyclopentyl-4-(3-cyclopentyl-
75 wt% in the raw materials, the content of aromatic compounds in the
propyl)- (1.30%), and cyclohexane, 1,3,5-trimethyl-2-octadecyl-
liquid oils was surprisingly high (95.5%), and the mono-aromatic
(0.34%) were the main cyclic-structure compounds in liquid oils ob-
compounds accounted for 76.1%. Miandad et al. observed the similar
tained from PP. Cit el al. also reported that pyrolysis of PP produced
results that the dominant products were styrene and styrene oligomers
cyclic-structures aliphatic in pyrolysis oil, while no cyclic structures
when PS was pyrolyzed with other types of plastic [44]. The presence of
were formed in PE pyrolysis [50]. As shown in this work, the linear
anomalous weak links in the polymer causes instability of the macro-
olefins were the main aliphatic component in liquid oils from the pyr-
molecules in the pyrolysis process. Therefore, large amounts of free
olysis of polyethylene, such as 1-octene (1.22%), 1-nonene (3.92%), 1-
radicals were produced after the cracking process, followed by the

5
Y. Zhang, et al.
Fig. 4. The main chemical compounds of liquid oil from plastic wastes pyrolysis under the filling ratio of heat carrier of 15%.
decene (2.94%), 1-undecene (2.72%), 1-tridecene (2.12%), 1-tetra-
decene (2.05%) and the others olefins (> C15, about 15.9%). In the
pyrolysis of plastic wastes, random chain scission generated primary
radicals rapidly. The primary radicals were unstable and need to be
stabilized. They can be stabilized by release H+ to form aromatics or
highly unsaturated hydrocarbon, capture a H+ to form olefins or par-
affin, or combine with other radicals to produced cyclic structure
[48,51]. Hence, the radicals derived from polypropylene pyrolysis were
more favorable to react with each other to generate cyclic structure
hydrocarbons in the liquid oils.
To evaluate the chemical structure in the liquid oils, the functional
groups of liquid oils were detected in FTIR. As shown in Fig. S1, the
absorption peak in the spectra around 3063 cm−1 corresponded to
–CeH stretching vibrations from unsaturated carbon in the aromatic
compounds. Peaks around 1606 cm−1 and 1448 cm−1 were the –C]C–
stretching of aromatic ring skeleton. Moreover, the absorption peaks in
the range of 700–920 cm−1 and 1080–1200 cm−1 were corresponding
to the –CeH vibrations of out-of-plane bending in the aromatic com-
pounds and 960–1022 cm−1 were assigned to the –CeH vibration of in-
plane bending in the aromatic compounds. The absorption peak from
850 cm−1 to 1000 cm−1 was related to the ]CeH stretching vibrations
in the alkenes. The relative intensities of these peaks of liquid oils from
different types of plastic wastes had remarkable differences, which was
attributed to the presence of large amounts of aromatic functional
groups in the liquid oils from PS or SMP. The presence of –CeH stretch
of –CH2 or –CH3 in the liquid oils corresponded to the absorbance peak
in the range of 3000–2755 cm−1 and the absorption intensity was the
greatest in the liquid oil derived from PE, followed PP. This result to-
gether with the GC–MS results indicated that large amounts of aliphatic
compounds in the liquid oil were derived from polyolefin. In addition,
the intensity of absorption in the range from 850 cm−1 to 1000 cm−1
related to the unsaturated hydrocarbons of alkenes in the liquid oil from
polyolefin was also evident. Besides, the intensity of absorption peak
around 1383 cm−1 assigned to the substituent group of –CH3 in the
6
Fuel Processing Technology 206 (2020) 106455
liquid oil obtained from PP was higher than that from PE, which in-
dicated that the radicals underwent a substitution reaction, or inter-
molecular hydrogen transfer to form a stable structure.
Boiling range distribution of liquid oils derived from plastic wastes
was presented in Fig. 6. The four fractions including motor gasoline
(MG, < 190 °C), diesel #1 (D1, 180–300 °C), diesel #2 (D2,
290–360 °C) and vacuum gas oil (VGO, > 350 °C) based on the corre-
sponding boiling point ranges were present in Table 2. Meanwhile,
commercial transport fuels, such as gasoline (GB 17930-2016) and
diesel (GB 19147-2016), were used as a standard to compare with the
liquid oils. MG and D1 fraction are the two major compositions of liquid
oils obtained from the pyrolysis of plastic wastes. In particular, the li-
quid oil derived from the pyrolysis of PS has 84.5 wt% MG fraction,
which is higher than MG fraction of the liquid oils derived from other
types of plastic wastes. This result was consistent to the chemical
compositions of liquid oils determined by GC–MS, which only con-
tained aromatic compounds such as styrene, toluene, and ethylbenzene,
as major contributors to MG fraction due to the low boiling point
(approximately at 145 °C). According to the GC–MS results in Fig. 4, the
gasoline hydrocarbons (C5–C12) was in the range of 71.8–89.1% in the
liquid oils derived from plastic wastes. It was interesting that the
highest gasoline hydrocarbons (C5–C12) content was observed in the
pyrolysis oil from SMP. According to the GC–MS results, the gasoline
hydrocarbons (C5–C12) were dominated by aromatic compounds. In the
case of SMP pyrolysis, there were richer benzylic radicals and they
could form substituted benzene with the alkene and alkane radicals.
However, in single plastic pyrolysis environment, these alkene and al-
kane radicals would eventually contribute to aliphatic compounds.
Further compared with standard gasoline, the liquid oils derived from
SMP or PS was close to commercial gasoline due to the richness of
gasoline hydrocarbons (C5–C12) and high MG fraction. The boiling
ranges of liquid oils produced from pyrolysis of polyolefins were much
wider than that of commercial gasoline and diesel. This revealed that
the liquid oils produced from polyolefins contained relatively low
Y. Zhang, et al. Fuel Processing Technology 206 (2020) 106455

Fig. 5. GC–MS spectrogram of liquid oils generated from the pyrolysis of plastic wastes.

gasoline fraction. Table 3 summarized the main pyrolysis results re-
ported in the literatures and compared them with this study. The results
obtained from fluidized bed reactor showed that the gas yield was in
the range of 54.4–65.9 wt% for PP and 36.6–59.3 wt% for PE, which
was higher than that of the current work [11]. In addition, the aromatic
compounds in the liquid oil produced from PP pyrolysis reached
90.2 wt%. This was because fluidized bed reactor needs relatively
higher temperature to avoid the defluidization of sands in the pyrolysis
process. Table 3 also showed that pyrolysis of polyolefins in the conical
spouted bed reactor favored light hydrocarbon production [17]. In view

7
Y. Zhang, et al. Fuel Processing Technology 206 (2020) 106455

100 3.4. NMR analysis of liquid oils at various filling ratios

The chemical environment information of hydrogens in the liquid

Cumulative yield / wt.%

80
60 350 °C
40
290 °C
20
190 °C
0 Diesel
50 100 150 200 250 300 350 400
Temperature / °C
Fig. 6. Boiling range distributions of liquid oils derived from different types of
plastic wastes, diesel and gasoline.
of the difference in feedstock and reactor type, direct comparison of
those results may lead to inaccurate conclusions. The processes at micro
and macro scale in different types of reactor are different, such as the
residence time which affects the secondary reactions of the products
[21]. However, it is also noteworthy that the secondary reaction is not a
negative effect. The light fractions could be converted into more stable
light aromatics [21]. The liquid oil produced from plastic wastes pyr-
olysis in current work presented relatively high gasoline range hydro-
carbons (71.8–89.1%), and the MG fraction also ranged from 49.0 wt%
to 84.5 wt%. The comparison suggested that pyrolysis with heat carrier
in rotary kiln is also an alternative method to recovery energy products
from plastic wastes. Moreover, the liquid oils contained the significant
quantity of commercial gasoline, diesel fraction, and light hydro-
carbons, which exhibited the potential to be used as transport fuels or
chemical feedstock in the fine chemical industry.
3.3.2. Gas analysis
The properties of gases produced from pyrolysis of PE, PP, PS, and
SMP at the filling ratio of 15% is presented in Table 4. Methane and
ethene were the most abundant hydrocarbon gases produced from
pyrolysis of plastic wastes, and largely determined the high heating
value (HHV) of gases [52]. For instance, the methane content in the
gases produced from pyrolysis of PE is the highest, and the HHV of PE-
derived gas was 50.3 ± 0.8 MJ/kg. Secondly, the HHVs of the gases
from PP and PS were 48.5 ± 0.9 MJ/kg and 41.5 ± 0.6 MJ/kg, re-
spectively, which is in accordance with the trends of methane content
in the gases. This indicated that the pyrolysis gases could be recycled as
the heating source for waste pyrolysis process.
oils produced under the various filling ratio of heat carrier was eval-
uated by 1H NMR analysis [53,54]. Fig. 7 shows the 1H NMR spectra of
liquid oils derived from pyrolysis of PE and SMP. The region of the
spectra protons between 6.3 and 8.3 ppm clearly indicated that the
presence of aromatic hydrogens in the liquid oils. The aliphatic hy-
drogens in the liquid oils in the form of –CH3, –CH2, and –CH functional
groups appeared in the regions between 0.5 and 2.1 ppm of the spectra
PE-15%
protons [55]. Meanwhile, the proton distributions of different liquid
PP-15%
oils are listed in Table 5. Liquid oils generated from SMP had more
SMP-15%
aromatic hydrogens compared with that from PE. This result was also in
PS-15%
accordance with the GC–MS results of liquid oils. Besides, an interesting
Gasoline
phenomenon was that the content of aromatic and olefin hydrogens in
liquid oils obtained from PE and SMP presented similar trends. The
450 500 aromatic hydrogen content decreased and olefins and paraffin hy-
drogen content increased with the filling ratio of heat carrier. As pre-
viously mentioned in Section 3.1, the massive amounts of heat carriers
promoted the heat transfer efficiency of plastic wastes through direct
heat transfer. The radicals generated from polymers were more readily
to capture H+, which led to the formation of paraffin or olefins.
3.5. Mechanism of pyrolysis with heat carriers in rotary kiln
The mechanism of pyrolysis of plastic wastes with heat carriers in
the rotary kiln was provided in Fig. 8. According to previous research
[25,56], the pyrolysis of plastic wastes with heat carriers in the rotary
kiln can be considered as a series of physical processes followed by
chemical processes. Firstly, the plastic wastes immediately contacted
the heat carrier in the active layer. The vigorous heat transfer in the
active layer melted the plastic wastes that were subsequently coated
around the heat carrier. Afterwards, cracking of chemical bonds took
place immediately. The chemical process occurred by random scission
of weaker bonds (SP3 bonds) to create free radicals. It was observed that
the initial breakage of the CeC chain of polyolefins generated large
amounts of radicals and molecules. Then the secondary radicals were
mainly produced from the β-scission of radicals, including end-chain
scission reaction and mid-chain random scission reactions. Therefore,
the long-chain radicals in the volatile phase can be further cracked into
low weight molecular products. Intermolecular and intra-molecular
transfer reactions happened for the hydrogen chain. The intra-mole-
cular transfer reactions moved the hydrogen proton from the end to the
middle of the radicals, which increased the isomer production and
olefin content. The intermolecular transfer reactions were performed by
the radicals and other components, which favored paraffin production.
As depicted in Fig. 8, the termination reactions occurred by dis-
proportionation of the radical or reactions of two radicals. This in-
cluded recombination, cyclization, and aromatization, which formed
the aromatic or cyclic compounds.
Based on the results from 1H NMR analysis and heat carrier motion
model, when the filling ratio of heat carriers increased, the contact

Table 2
Distillation properties and fractional yield of liquid oils using simulated-distillation.
PE-15% PP-15% SMP-15% PS-15% Diesel Gasoline

MG (< 190 °C, wt%) 49.0 59.5 67.5 84.5 – –

D1 (180–300 °C, wt%) 31.5 19.0 21.0 6.0 – –
D2 (290–360 °C, wt%) 8.5 5.0 5.5 6.0 – –
VGO (> 350 °C, wt%) 11.0 16.5 6.0 3.5 – –
IBP (°C) 52.0 52.0 53.5 83.5 – –
10% (°C) 105.0 103.5 104.5 107.5 – 70
50% (°C) 191.5 160.0 137.0 138.5 300 120
90% (°C) 358.0 447.0 302.5 288.5 355 190
FBP (°C) 502.0 522.0 485.0 435.5 365 205

8
Y. Zhang, et al. Fuel Processing Technology 206 (2020) 106455

Table 4

Current study
Reference The composition (vol%) and HHV (MJ/kg) of gas produced from pyrolysis of
plastic waste under the filling ratio of 15%.
[48]

[11]

[17]
Experiment PE-15% PP-15% PS-15% SMP-15%

H2 6.0 ± 0.3 9.4 ± 0.1 7.7 ± 0.6 4.7 ± 0.8

PP fraction (43.1–29.6 wt% pyrolysis oil); PE fraction (38.2–61 wt%); the concentration of

Methane 27.3 ± 0.9 24.4 ± 1.1 8.5 ± 0.7 25.1 ± 1.4

Liquid yield: 72.0–42.9 wt%; 71.7–99.3% aromatic (68–70.8% mono-aromatic); C5–C9

Liquid oils yield increased by filling ratio of heat carrier, C5-C12:71.8–89.1%; gasoline
Ethane 11.0 ± 1.0 12.3 ± 1.0 4.0 ± 0.9 7.4 ± 0.6
Ethene 27.7 ± 0.9 43.9 ± 0.9 3.07 ± 0.8 17.6 ± 0.2
Gasoline fraction (C5–C10) 69 wt% (non-aromatic 44.55 wt%; aromatic 24.1 wt%)

C3 28.2 ± 1.1 5.1 ± 1.0 17.7 ± 1.3 19.8 ± 0.7

C4 3.6 ± 0.8 1.0 ± 0.5 41.6 ± 1.0 7.4 ± 0.8
CO2 1.5 ± 0.6 3.8 ± 0.2 13.6 ± 0.5 4.5 ± 0.5
CO 0.0 ± 0.4 0.1 ± 0.1 3.9 ± 0.8 13.5 ± 1.0
HHV 50.3 ± 0.8 48.5 ± 0.9 41.5 ± 0.6 42.7 ± 0.8

between plastic and sand enhanced the heat transfer efficiency, which
facilitated hydrogen transfer to stabilize the radicals from β-scission,
thus leading to more paraffin and olefins. However, the fast heat
transfer along with limited residence time in the rotary kiln opposed
BTX aromatics increased by the temperature

aromatization reactions and decreased the production of aromatic

compounds.

4. Conclusions
Pyrolysis-oil yield/quality

The plastic wastes, including polyethylene, polypropylene, poly-

fraction: 49.0–84.5%

styrene, and a simulated mixture of plastic wastes, were pyrolyzed in

this study with various filling ratios of heat carriers (0%, 5%, 10%,
15%, 20%) in the rotary kiln reactor at 500 °C. The suitable filling ratio
70.6–79.6%

of heat carrier is 15%, which could achieve vigorous mixing and high
heat transfer efficiency, hence producing the most liquid oil (up to
90%). The aromatics in the liquid oils from simulated mixture of plastic
waste were as high as 96%. The gasoline range hydrocarbons (C5–C12)
T = 500 °C; 100 g HY zeolite catalyst; 3 g HDPE;
T = 668, 703, 727, 746 °C; T = 660, 680, 704,

in the liquid oils accounted for 71–89%. The liquid oils from pyrolysis
of simulated mixture of plastic waste showed the most similar dis-
T = 500 °C; F = 0, 5, 10, 15, and 20%

tillation characteristics to commercial gasoline. Moreover, the liquid

T = 460, 500, 600 °C; t = 30 min

oils contained significant amount of commercial gasoline, diesel frac-

tion, and light hydrocarbons. The chemical composition of liquid oil
suggested that fast pyrolysis of plastic wastes with heat carrier de-
Comparison of liquid oils yield and quality from pyrolysis plastic wastes in various literatures.

monstrated great potential to produce transport fuel and chemicals.

This study found that the loading of heat carrier had a significant effect
Process condition

on the particle movement behavior, the contact with feedstock, the heat
N2 29.3 l/min

transfer efficiency and the consequent pyrolysis products. The EDEM

simulation of the rotary kiln supported direct visualization of heat
728 °C

carrier and facilitated the analysis of its effects. Loading more heat
carrier in the rotary kiln, which facilitated heat transfer, and enhanced
the H+ transfer in the reaction of radicals, produced more olefins and
paraffins in the liquid oils. The current work paves a new pathway to
Pyrolysis reactor type

Fluidized bed reactor

T: temperature; t: residence time; F: filling ratio of heat carriers.

conical spouted bed

Rotary kiln reactor

control the pyrolysis product by adjusting the mass and heat transfer
Semi-bath reactor

behavior. It also provided a guideline for the optimization of heat and

mass transfer for industrial scale pyrolysis.
The following are the supplementary data related to this article.
reactor

CRediT authorship contribution statement

PE; PP; PS; simulated plastic wastes (PE, PP, PS,
Simulated plastic wastes (PE, PP, PS, PET, and

Yutao Zhang: Conceptualization, Methodology, Investigation,

Writing - original draft, Software. Guozhao Ji: Conceptualization,
Software, Visualization, Resources, Writing - review & editing.
Chuanshuai Chen: Investigation. Yinxiang Wang: Investigation.
Weijian Wang: Investigation. Aimin Li: Supervision.

Acknowledgements
and PET)

The study was supported by Open Foundation of Key Laboratory of

PVC)
Material

Industrial Ecology and Environmental Engineering, MOE (KLIEEE-19-

Table 3

PP; PE

HDPE

01) and the Fundamental Research Funds for the Central Universities
[grant number: DUT18RC(3)036].

9
Y. Zhang, et al. Fuel Processing Technology 206 (2020) 106455

×108
a 4

Relative intensity
2

0
PE-5%

PE-10%

PE-15%

PE-20%

10 8 6 4 2 0
Chemical shift (ppm)

×108
b 4

Relative intensity
2

0
SMP-5%

SMP-10%

SMP-15%

SMP-20%

10 8 6 4 2 0
Chemical shift (ppm)

Fig. 7. 1H NMR spectra of liquid oils from plastic wastes pyrolysis at various filling ratios of heat carrier (a, polyethylene; b, simulated mixture of plastic wastes).

Table 5
Proton distribution of liquid oils from polyethylene and simulated mixture of plastic wastes pyrolysis under various filling ratios.
Proton (ppm) Assignments Content (%)

PE5 PE10 PE15 PE20 SMP5 SMP10 SMP15 SMP20

Hα (0.5–1.2) Protons of CH3 in alkanes; CH3 of alkyls in the γ position or further of an alkyl chain away from 29.1 31.6 43.6 42.8 4.6 4.6 5.4 12.6
aromatic rings.
Hβ (1.2–2.1) Protons of CH2 or CH in alkanes; CH2 or CH in the β-position or further of away from aromatic 21.8 22.5 26.3 25.9 22.0 21.9 22.4 25.1
rings; CH3 in the β-position to aromatic rings.
Hγ (2.1–4.3) CH, CH2 or CH3 in the α-position to aromatic rings. 20.2 18.6 10.7 10.8 21.0 20.8 20.3 12.9
Ho (4.3–6.3) Protons of alkenyl of aromatic rings; protons in alkenes. 6.8 7.2 7.5 8.1 10.4 10.4 11.3 10.9
Ha (6.3–8.3) Aromatic protons. 22.2 20.1 11.9 12.3 42.1 41.9 40.7 38.6

Declaration of competing interest influence the work reported in this paper.

The authors declare that they have no known competing financial

interests or personal relationships that could have appeared to

10
Y. Zhang, et al.
Fig. 8. The mechanism of plastic wastes pyrolysis with heat carrier in rotary kiln.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.fuproc.2020.106455.
References
[1] B. Kunwar, H.N. Cheng, S.R. Chandrashekaran, B.K. Sharma, Plastics to fuel: a re-
view, Renew. Sust. Energ. Rev. 54 (2016) 421–428.
[2] W.C. Li, H.F. Tse, L. Fok, Plastic waste in the marine environment: a review of
sources, occurrence and effects, Sci. Total Environ. 566–567 (2016) 333–349.
[3] P. Das, P. Tiwari, The effect of slow pyrolysis on the conversion of packaging waste
plastics (PE and PP) into fuel, Waste Manag. 79 (2018) 615–624.
[4] R. Miandad, M.A. Barakat, A.S. Aburiazaiza, M. Rehan, A.S. Nizami, Catalytic
pyrolysis of plastic waste: a review, Process Saf. Environ. Prot. 102 (2016) 822–838.
[5] X. Zhang, H. Lei, G. Yadavalli, L. Zhu, Y. Wei, Y. Liu, Gasoline-range hydrocarbons
produced from microwave-induced pyrolysis of low-density polyethylene over ZSM-
5, Fuel 144 (2015) 33–42.
[6] R. Geyer, J.R. Jambeck, K.L. Law, Production, use, and fate of all plastics ever
made, Sci. Adv. 3 (2017).
[7] M. Syamsiro, H. Saptoadi, M. Kismurtono, Z. Mufrodi, K. Yoshikawa, Utilization of
waste polyethylene pyrolysis oil as partial substitute for diesel fuel in a DI diesel
engine, Int. J. Smart Grid Clean Energy 8 (2019) 38–47.
[8] J. Zeaiter, F. Azizi, M. Lameh, D. Milani, H.Y. Ismail, A. Abbas, Waste tire pyrolysis
using thermal solar energy: an integrated approach, Renew. Energy 123 (2018)
44–51.
[9] Z. Wang, G. Liu, D. Shen, C. Wu, S. Gu, Co-pyrolysis of lignin and polyethylene with
the addition of transition metals - part I: thermal behavior and kinetics analysis, J.
Energy Inst. 93 (2020) 281–291.
[10] P. Fu, X. Bai, W. Yi, Z. Li, Y. Li, Fast pyrolysis of wheat straw in a dual concentric
rotary cylinder reactor with ceramic balls as recirculated heat carrier, Energy
Convers. Manag. 171 (2018) 855–862.
[11] S.-H. Jung, M.-H. Cho, B.-S. Kang, J.-S. Kim, Pyrolysis of a fraction of waste poly-
propylene and polyethylene for the recovery of BTX aromatics using a fluidized bed
reactor, Fuel Process. Technol. 91 (2010) 277–284.
[12] M.L. Mastellone, U. Arena, Fluidized-bed pyrolysis of polyolefins wastes: predictive
defluidization model, AICHE J. 48 (2002) 1439–1447.
[13] Y. Xue, S. Zhou, R.C. Brown, A. Kelkar, X. Bai, Fast pyrolysis of biomass and waste
plastic in a fluidized bed reactor, Fuel 156 (2015) 40–46.
[14] M. Artetxe, G. Lopez, M. Amutio, I. Barbarias, A. Arregi, R. Aguado, J. Bilbao,
M. Olazar, Styrene recovery from polystyrene by flash pyrolysis in a conical spouted
bed reactor, Waste Manag. 45 (2015) 126–133.
[15] M. Arabiourrutia, G. Elordi, G. Lopez, E. Borsella, J. Bilbao, M. Olazar,
Characterization of the waxes obtained by the pyrolysis of polyolefin plastics in a
conical spouted bed reactor, J. Anal. Appl. Pyrolysis 94 (2012) 230–237.
[16] G. Elordi, M. Olazar, G. Lopez, M. Artetxe, J. Bilbao, Product yields and composi-
tions in the continuous pyrolysis of high-density polyethylene in a conical spouted
bed reactor, Ind. Eng. Chem. Res. 50 (2011) 6650–6659.
[17] G. Elordi, M. Olazar, R. Aguado, G. Lopez, M. Arabiourrutia, J. Bilbao, Catalytic
pyrolysis of high density polyethylene in a conical spouted bed reactor, J. Anal.
Appl. Pyrolysis 79 (2007) 450–455.
[18] Y. Kodera, Y. Ishihara, T. Kuroki, Novel process for recycling waste plastics to fuel
11
Fuel Processing Technology 206 (2020) 106455
gas using a moving-bed reactor, Energy Fuel 20 (2006) 155–158.
[19] X. Zheng, Z. Ying, B. Wang, C. Chen, CO2 gasification of municipal solid waste in a
drop-tube reactor: experimental study and thermodynamic analysis of syngas,
Energy Fuel 32 (2018) 5302–5312.
[20] A.M. Li, X.D. Li, S.Q. Li, Y. Ren, N. Shang, Y. Chi, J.H. Yan, K.F. Cen, Experimental
studies on municipal solid waste pyrolysis in a laboratory-scale rotary kiln, Energy
24 (1999) 209–218.
[21] Liquid fuel from plastic wastes using extrusion–rotary kiln reactors, in: Feedstock
Recycling and Pyrolysis of Waste Plastics, pp. 531–548.
[22] D. De Conto, W.P. Silvestre, C. Baldasso, M. Godinho, Performance of rotary kiln
reactor for the elephant grass pyrolysis, Bioresour. Technol. 218 (2016) 153–160.
[23] Z. Ma, N. Gao, L. Xie, A. Li, Study of the fast pyrolysis of oilfield sludge with solid
heat carrier in a rotary kiln for pyrolytic oil production, J. Anal. Appl. Pyrolysis 105
(2014) 183–190.
[24] E. Yazdani, S.H. Hashemabadi, A. Taghizadeh, Study of waste tire pyrolysis in a
rotary kiln reactor in a wide range of pyrolysis temperature, Waste Manag. 85
(2019) 195–201.
[25] M. Artetxe, G. Lopez, M. Amutio, G. Elordi, J. Bilbao, M. Olazar, Light olefins from
HDPE cracking in a two-step thermal and catalytic process, Chem. Eng. J. 207
(2012) 27–34.
[26] F. Herz, I. Mitov, E. Specht, R. Stanev, Influence of operational parameters and
material properties on the contact heat transfer in rotary kilns, Int. J. Heat Mass
Transf. 55 (2012) 7941–7948.
[27] K. Li, J. Lei, G. Yuan, P. Weerachanchai, J.-Y. Wang, J. Zhao, Y. Yang, Fe-, Ti-, Zr-
and Al-pillared clays for efficient catalytic pyrolysis of mixed plastics, Chem. Eng. J.
317 (2017) 800–809.
[28] J.M. Saad, P.T. Williams, Manipulating the H2/CO ratio from dry reforming of si-
mulated mixed waste plastics by the addition of steam, Fuel Process. Technol. 156
(2017) 331–338.
[29] Y. Aryan, P. Yadav, S.R. Samadder, Life cycle assessment of the existing and pro-
posed plastic waste management options in India: a case study, J. Clean. Prod. 211
(2019) 1268–1283.
[30] G. Bajad, R.P. Vijayakumar, P. Rakhunde, A. Hete, M. Bhade, Processing of mixed-
plastic waste to fuel oil, carbon nanotubes and hydrogen using multi-core reactor,
Chem. Eng. Process. Process Intensif. 121 (2017) 205–214.
[31] G.-H. Zhang, J.-F. Zhu, A. Okuwaki, Prospect and current status of recycling waste
plastics and technology for converting them into oil in China, Resour. Conserv.
Recycl. 50 (2007) 231–239.
[32] S. Honus, S. Kumagai, G. Fedorko, V. Molnár, T. Yoshioka, Pyrolysis gases produced
from individual and mixed PE, PP, PS, PVC, and PET—part I: production and
physical properties, Fuel 221 (2018) 346–360.
[33] P. Das, P. Tiwari, Valorization of packaging plastic waste by slow pyrolysis, Resour.
Conserv. Recycl. 128 (2018) 69–77.
[34] Y. Chen, L. Zhang, Y. Zhang, A. Li, Pressurized pyrolysis of sewage sludge: Process
performance and products characterization, J. Anal. Appl. Pyrolysis 139 (2019)
205–212.
[35] J. Wei, Q. Guo, L. Ding, Y. Gong, J. Yu, G. Yu, Understanding the effect of different
biomass ash additions on pyrolysis product distribution, char physicochemical
characteristics, and char gasification reactivity of bituminous coal, Energy Fuel 33
(2019) 3068–3076.
[36] X. Jia, C. Qin, T. Friedberger, Z. Guan, Z. Huang, Efficient and selective degradation
of polyethylenes into liquid fuels and waxes under mild conditions, Sci. Adv. 2
(2016) e1501591.
[37] A. Chaala, H. Darmstadt, C. Roy, Vacuum pyrolysis of electric cable wastes, J. Anal.
Y. Zhang, et al.
Appl. Pyrolysis 39 (1997) 79–96.
[38] C. Muhammad, J.A. Onwudili, P.T. Williams, Thermal degradation of real-world
waste plastics and simulated mixed plastics in a two-stage pyrolysis-catalysis re-
actor for fuel production, Energy Fuel 29 (2015) 2601–2609.
[39] E.D. Christensen, G.M. Chupka, J. Luecke, T. Smurthwaite, T.L. Alleman, K. Iisa,
J.A. Franz, D.C. Elliott, R.L. McCormick, Analysis of oxygenated compounds in
hydrotreated biomass fast pyrolysis oil distillate fractions, Energy Fuel 25 (2011)
5462–5471.
[40] R. Meusinger, Gasoline analysis by 1H nuclear magnetic resonance spectroscopy,
Fuel 75 (1996) 1235–1243.
[41] B. Liu, Y. Li, Simulation of effect of internals on particulate mixing and heat transfer
in downer reactor using discrete element method, Powder Technol. 297 (2016)
89–105.
[42] R. Kačianauskas, A. Maknickas, A. Kačeniauskas, D. Markauskas, R. Balevičius,
Parallel discrete element simulation of poly-dispersed granular material, Adv. Eng.
Softw. 41 (2010) 52–63.
[43] H. Yin, M. Zhang, H. Liu, Numerical simulation of three-dimensional unsteady
granular flows in rotary kiln, Powder Technol. 253 (2014) 138–145.
[44] R. Miandad, M.A. Barakat, A.S. Aburiazaiza, M. Rehan, I.M.I. Ismail, A.S. Nizami,
Effect of plastic waste types on pyrolysis liquid oil, Int. Biodeterior. Biodegradation
119 (2017) 239–252.
[45] K.-B. Park, Y.-S. Jeong, B. Guzelciftci, J.-S. Kim, Two-stage pyrolysis of polystyrene:
pyrolysis oil as a source of fuels or benzene, toluene, ethylbenzene, and xylenes,
Appl. Energy 259 (2020) 114240.
[46] C. Kassargy, S. Awad, G. Burnens, K. Kahine, M. Tazerout, Experimental study of
catalytic pyrolysis of polyethylene and polypropylene over USY zeolite and se-
paration to gasoline and diesel-like fuels, J. Anal. Appl. Pyrolysis 127 (2017) 31–37.
[47] F. Pinto, P. Costa, I. Gulyurtlu, I. Cabrita, Pyrolysis of plastic wastes. 1. Effect of
12
Fuel Processing Technology 206 (2020) 106455
plastic waste composition on product yield, J. Anal. Appl. Pyrolysis 51 (1999)
39–55.
[48] A. López, I. de Marco, B.M. Caballero, M.F. Laresgoiti, A. Adrados, Influence of time
and temperature on pyrolysis of plastic wastes in a semi-batch reactor, Chem. Eng.
J. 173 (2011) 62–71.
[49] A. Adrados, I. de Marco, B.M. Caballero, A. López, M.F. Laresgoiti, A. Torres,
Pyrolysis of plastic packaging waste: a comparison of plastic residuals from material
recovery facilities with simulated plastic waste, Waste Manag. 32 (2012) 826–832.
[50] İ. Çit, A. Sınağ, T. Yumak, S. Uçar, Z. Mısırlıoğlu, M. Canel, Comparative pyrolysis
of polyolefins (PP and LDPE) and PET, Polym. Bull. 64 (2010) 817–834.
[51] N. Miskolczi, F. Ateş, Thermo-catalytic co-pyrolysis of recovered heavy oil and
municipal plastic wastes, J. Anal. Appl. Pyrolysis 117 (2016) 273–281.
[52] S.D. Anuar Sharuddin, F. Abnisa, W.M.A. Wan Daud, M.K. Aroua, Energy recovery
from pyrolysis of plastic waste: study on non-recycled plastics (NRP) data as the real
measure of plastic waste, Energy Convers. Manag. 148 (2017) 925–934.
[53] M. Bartoli, L. Rosi, A. Giovannelli, P. Frediani, M. Passaponti, M. Frediani,
Microwave assisted pyrolysis of crop residues from Vitis vinifera, J. Anal. Appl.
Pyrolysis 130 (2018) 305–313.
[54] L. Jin, H. Zhao, M. Wang, B. Wei, H. Hu, Effect of temperature and simulated coal
gas composition on tar production during pyrolysis of a subbituminous coal, Fuel
241 (2019) 1129–1137.
[55] L. Dai, Y. Wang, Y. Liu, R. Ruan, Z. Yu, L. Jiang, Comparative study on char-
acteristics of the bio-oil from microwave-assisted pyrolysis of lignocellulose and
triacylglycerol, Sci. Total Environ. 659 (2019) 95–100.
[56] R.K. Singh, B. Ruj, A.K. Sadhukhan, P. Gupta, Thermal degradation of waste plastics
under non-sweeping atmosphere: part 1: effect of temperature, product optimiza-
tion, and degradation mechanism, J. Environ. Manag. 239 (2019) 395–406.