Fuel 305 (2021) 121440

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Drop-in fuel production with plastic waste pyrolysis oil over

catalytic separation
Shuang Wang a, Hana Kim a, Doyeon Lee b, Yu-Ri Lee a, Yooseob Won a, Byung Wook Hwang a,
Hyungseok Nam a, *, Ho-Jung Ryu a, Kyong-Hwan Lee a
a
Climate Change Division, Korea Institute of Energy Research, Daejeon 34129, Republic of Korea
b
Department of Civil and Environmental Engineering, Hanbat National University, Daejeon 34158, Republic of Korea

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

Keywords: The catalytic upgrading of plastic pyrolysis oil was conducted in a 2-kg-scale pyrolysis oil separation system with
Plastic waste or without zeolite 4A, Cu-based (MDC-7) and Ni-based catalysts to produce light (F1), middle (F2) and heavy
Pyrolysis oil (F3) oil fractions. From the preliminary separation tests without a catalyst, the separation vapor temperature for
Catalytic reaction
diesel-like middle fraction (C11 - C22) was determined to be in the range of 107–305 ◦ C. After the pyrolysis oil
Separation
separation with catalysts, the heavy carbon range (>C23) sharply decreased from 22.1 wt% in the crude plastic
pyrolysis oil to 0.1–1.6 wt% and 7.3–8.4 wt% in the F1 and F2, respectively. Among three catalysts, Ni-based
catalyst exhibited the highest deoxygenation capacity (1.23% O in F1 and 0.3% O in F2) owing to its strong
acid sites concentration (1.115 mmol/g). Accordingly, the order of the deoxygenation capacity was Ni-based >
MDC-7 > zeolite 4A > no catalyst. Moreover, the catalytic reactions (deoxygenation) and coke formation mainly
occurred on the strong acid sites. MDC-7 catalyst contributed to more production of C6–C10 range (15.8 %) with
aromatic and naphthenic compounds. In contrast, the major catalytic mechanisms of Ni-based catalyst were
dehydration, decarboxylation and decarbonylation reactions. In addition, the physical properties of catalytically
upgraded pyrolysis oil were close to those of the petroleum-based fuels. Finally, the current study suggested that
Ni-based catalyst was a suitable catalyst for the production of diesel-like fraction (C11-C12) with the lowest
contents of oxygen from the plastic pyrolysis oil.

waste (such as burying, discarding and incineration), due to its nature of

1. Introduction
Plastic plays a vital role in improving the human living standard for
more than half of century since its birth, due to its unique advantages
including lightweight, convenient, low cost and durability. Several
representative plastics such as polyethylene (PE), polyethylene tere­
phthalate (PET), polystyrene (PS), polypropylene (PP) and polyvinyl
chloride (PVC) have been widely used in various fields such as pack­
aging, building and construction, light-weight vehicles, electronics,
medical and health, and energy [1,2]. In 2017, 348 million metric tons
of plastic were produced globally and this demand is expected to
quadruple by 2050 [1]. After the large-scale production of plastics in the
1950s, the global plastic waste was estimated to be as high as 6.3 billion
metric tons, of which about 79% was accumulated in landfills or dis­
carded into the environment [3].A series of environmental problems,
including water pollution, air pollution and the destruction of terrestrial
habitats, have been being caused by an improper disposal of plastic
non-biodegradability and possible toxicity [4,5]. Furthermore, it is re­
ported that microplastics may easily enter the food chain through the
ingestion of fish or marine organisms, which even directly remain in tap
water and ordinary salt that undoubtedly poses a serious threat to
human life [6]. Additionally, the vast application of plastic products has
also accelerated the depletion of fossil fuels since the plastics are made
of the petroleum-based materials. Therefore, it is a good strategy to
convert plastic waste into fuel through pyrolysis [2,7] because it not
only solves the problem of plastic waste disposal, but also realizes the
resource recycling and energy recovery [8,9].
Plastic pyrolysis oil mainly contains many alkanes, alkenes and ar­
omatic compounds, which are close to petroleum-based fuels because
plastic waste is primarily composed of carbon and hydrogen elements
[10,11]. Tulashie et al. [12] performed the pyrolysis of the mixture of
different plastic wastes for developing an efficient conversion method
for heterogeneous plastic waste streams. FTIR analysis showed that
plastic pyrolysis oil was rich in aliphatic and aromatic groups of

* Corresponding author.
E-mail address: namhs219@kier.re.kr (H. Nam).

https://doi.org/10.1016/j.fuel.2021.121440
Received 14 January 2021; Received in revised form 16 June 2021; Accepted 12 July 2021
Available online 5 August 2021
0016-2361/© 2021 Elsevier Ltd. All rights reserved.
S. Wang et al.
Nomenclature
ASTM American Society for Testing and Materials
BET Brunauer Emmet and Teller
F1 Fraction 1, light oil (LO), gasoline-like fraction, carbon
number range of C6-C10
F2 Fraction 2, middle oil (MO), diesel-like fraction, carbon
number range of C11-C22
F3 Fraction 3, heavy oil (HO), wax, carbon number range of ≥
C23
FC Fixed carbon
FTIR Fourier Transform Infrared Spectroscopy
GC–MS Gas chromatography–mass spectrometry
HHV Higher heating value
HDPE High-density polyethylene
compounds. In addition, GC–MS analysis showed that the substances in
the plastic pyrolysis oil were in the range of diesel fuel (C12-C24), which
indicates that the plastic pyrolysis oil had a potential to be an alternative
to diesel. Although there is no strict unified standard for the relationship
between the carbon number range and petroleum fractions so far, the
commonly used standards can be obtained from literatures [13,14]. The
carbon number range for petroleum gas (PG), light oil (LO, close to
gasoline fraction), medium oil (MO, close to diesel fraction) and heavy
oil (HO, close to wax) were defined as C1-C5, C6-C10, C11-C22 and ≥C23,
respectively. However, the major shortcomings including high viscosity,
high TAN value, relatively high oxygenated compounds, thermal insta­
bility and chemical instability limit its wide applications [15].
Many technologies for pyrolysis plastic oil upgrading have been
studied through distillation [16], hydroprocessing [17], catalytic hy­
drogenation [18] and emulsification [19]. Hydroprocessing and cata­
lytic hydrogenation are conducted under certain pressure conditions
and consume a large amount of hydrogen. Emulsification require sol­
vents, which also increases the cost of the process. On the other hand,
catalytic cracking technology has garnered a considerable interest
owing to its low hydrogen consumption and operations under atmo­
spheric conditions. During the catalytic cracking process, the catalyst
plays a key role in improving the properties of pyrolysis oil via various
reactions, including selectivity, catalyzed cyclization and aromatization
reactions, catalyzed recombination and disproportionation reactions,
transfer hydrogenation reactions as well as deoxygenation reactions (e.
g., decarboxylation (removal of oxygen as CO2), decarbonylation
(removal of oxygen in the form of CO), and dehydration (removal of
oxygen over H2O))[20]. Zeolite has already been demonstrated to be an
effective catalyst and has been widely used in the catalytic cracking of
plastic pyrolysis oil due to its high surface area, strong and adjustable
surface acidity, unique pore structures, high adsorption ability and
shape selectivity features [21,22] Rehan et al. [23] performed a catalytic
pyrolysis of polystyrene (PS) plastic waste at 450 ◦ C with zeolite cata­
lyst. The catalytic pyrolysis decreased mass yield of plastic pyrolysis oil
to 52% from 81% of non-catalytic pyrolysis. However, the quality of the
plastic pyrolysis oil was improved due to catalytic properties of zeolites
(high surface area and microporous structure). However, limitations still
exist to be improved for the pyrolysis oil catalytic cracking, such as its
insufficient deoxygenation ability, poor thermal stability, weak activity
and easy coke formation.
To address these limitations, a method has been proposed and suc­
cessfully applied to the catalytic cracking of plastic pyrolysis oil. This
method involves the introduction of a metal or two metals (such as Pb,
Mo, Ga, Co, Ni and Zn) to a zeolite catalyst to prepare mono-metallic/
zeolite or bi-metallic/zeolite catalysts, respectively [24–27]. A review
on the recent progress in the catalytic cracking of pyrolysis oil with
metal/zeolite functional catalysts was conducted by Shi et al. [24]. The
2
Fuel 305 (2021) 121440
MI Initial mass of plastic pyrolysis oil (g)
MP Mass of product of F1, F2, F3, and loss (g)
NH3-TPD Ammonia- temperature programmed desorption
PE Polyethylene
PET Polyethylene terephthalate
PP Polystyrene
PS Polystyrene
PVC Polyvinyl chloride
SEM-EDS Scanning electron microscopy with energy dispersive
spectroscopy
Sim-GC Simulated gas chromatography
TAN Total acid number
TGA Thermogravimetric analysis
VCM Volatile combustible matter
XRF X-ray fluorescence
conclusions showed that deoxygenation and acid-catalyzed reactions
were mainly controlled by the metal active centers and zeolitic acid
sites, respectively. In addition, the properties of zeolites and metals
(such as acidity, porosity, activity, metal centers, selectivity and sta­
bility) and their interaction (synergistic effect) can significantly affect
the overall reaction pathways and selectivity. Akubo et al. [27] carried
out the pyrolysis-catalysis of high-density polyethylene (HDPE) plastic
at 600 ◦ C with metal-impregnated zeolite catalysts. Some transition
metal promoters (including Ni, Fe, Mo, Ga, Ru and Co) were impreg­
nated on Y-zeolite to determine their effect on fuel composition. The
metal-impregnated zeolite catalysts produced higher amount of aro­
matic hydrocarbons (especially single-ring aromatic hydrocarbons) in
plastic pyrolysis oil and increased the hydrogen yield from HDPE. The
single ring aromatic compounds are primarily composed of toluene,
ethylbenzene and xylenes [28], which are very important chemical
substances in the petroleum-based fuels.
Although many efforts have been made in the catalytic cracking of
plastic pyrolysis oil, there are still research areas that deserve further
research and improvement to prevent the air pollutions during the usage
of plastic pyrolysis oil and to reduce the price of oil by improving the oil
quality. To the best of our knowledge, limited studies were conducted on
the design of practical pyrolysis oil catalytic separators for the plastic
pyrolysis oil. During the catalytic separation of plastic pyrolysis oil (2-kg
scale), three catalysts were applied to improve the oil quality, which
made them close to diesel grade fuel properties of HHV, viscosity,
density, H/C and O/C ratios, etc. The specific objectives of this work
were, a) to determine a desired direct condensation vapor temperature
during the separation of plastic pyrolysis oil, b) to have the highest
possible mass yield of diesel-grade pyrolysis oil (C11-C22) with or
without catalysts, and c) to understand the effect of catalysts during the
separation of plastic oil. Overall, the current study is expected to design
a cost-effective separation process for the improvement of plastic py­
rolysis oil quality.
2. Experimental
2.1. Materials and catalysts
The plastic pyrolysis oil was obtained from a pyrolysis company,
located in the Gyong-gi province in Korea. A 10 ton/day plastic kiln
pyrolysis facility was used to produce pyrolysis oil at approximately
450 ◦ C using a mixture of different plastic wastes, collected locally. The
composition information of plastic waste used for the plastic pyrolysis
oil was investigated in our previous study as shown in Table 1 [29]. The
plastic waste was mainly divided into two types of Grade-I and Grade-II.
Grade-I mostly contained vinyl plastic (88.4%) and others (8.7 %) while
Grade-II primarily consisted of dirty vinyl plastic (washed:38.7% and
S. Wang et al. Fuel 305 (2021) 121440

Table 1
Composition information of plastic waste for 10 ton/day kiln pyrolysis plant [29].
wt.% Vinyl Thermos-Plastic Thermoset-Plastic Wood Metal Others

washed debris

Grade-I 88.4 1.9 0.0 0.9 0.1 8.7

Grade-II 38.7 11.4 26.6 20.6 0.4 0.3 2.0

debris: 11.4%), thermoplastic (26.6%), thermoset plastic (20.6%), wood

(0.4%), metal (0.3%) and others (2.0%). The washed vinyl-based plastic,
wood and others were mainly responsible for the presence of oxygen in
the plastic pyrolysis oil after pyrolysis. The averaged proximate analysis
results showed that the plastic waste consisted of volatile combustible
matter (VCM: 78–96%), fixed carbon (FC: 0.3–7.8%) and ash (2–11%)
whereas the averaged elemental analysis results were as follows: carbon:
55–73%, hydrogen: 7–11%, nitrogen: 1.5% and oxygen: 11–25% in
accordance to our previous study [29]. Three types of catalyst were
selected as zeolite 4A from Oriental Chemical Industries (OCI) co., Ltd.,
(Korea), commercial catalyst MDC-7 (ShiftMax 210, Cu-based catalyst)
from Clariant co., Ltd, (Korea), and Ni-based catalyst, produced from
Institute for Advanced Engineering (IAE) (Korea), as shown in Fig. 1.

2.2. Experimental setup and procedures

A 2-kg-scale pyrolysis oil separator was designed to ascertain the

feasibility of direct condensation of pyrolysis oil at a specific vapor
temperature during the plastic pyrolysis, as shown in Fig. 2. F1 (fraction
1) is light oil (gasoline-like fraction) and its carbon number range is C6-
C10, while F2 (fraction 2) is middle oil (diesel-like fraction) and its
carbon number range is C11-C22. F3 (fraction 3) is heavy oil (wax) with Fig. 2. Schematic diagram of 2-kg-scale pyrolysis oil separation setup.
carbon number range of ≥ C23. To determine the optimal separation
vapor temperature for more diesel-like F2 (C11–C22 range), several
N2 atmosphere to completely remove the possible moisture and ashes. In
thermal cracking experiments were conducted. The heating mantle
order to determine the appropriate pyrolysis oil feed/catalyst ratio, we
temperature for the oil bath was set at 430 ◦ C, corresponded to those of
referred some similar literatures [30–32], showing the effect of WHSV
the furnace and heating jacket were set at 320 ~ 380 ◦ C and 280 ~
(weight hour space velocity) on the catalytic distillation (separation) of
320 ◦ C, respectively. Three selected temperature conditions for different
pyrolysis oil. Based on these references, the appropriate WHSV for
cases are introduced in S.Table 1. Simulated GC was used to find the
obtaining products with better properties and relatively high yield was
desired separating temperature for the plastic pyrolysis oil. Once the
found to be in the range of 1.5 ~ 4 h− 1. Therefore, the middle value of
temperature was determined, the same temperature conditions were
WHSV (3.5 h− 1) was used in our study. In addition, considering the
applied during the catalytic separation experiments. For the separation
amount of plastic pyrolysis oil used each time (about 800 g) and
experiment without a catalyst, approximately 800 g of pyrolysis plastic
experimental time (around 4 h), the mass of catalyst was calculated to be
oil was initially loaded in a bottom flask (F3). N2 was provided at a rate
about 40 g (the pyrolysis oil feed/catalyst ratio = 20:1). The 40 g
of 1.0 L/min for the first 20 min to remove the air inside the system
calcined catalyst was placed in the catalyst reactor (diameter: 50 mm
before each experiment. Heating mantle then increased from 25 ◦ C to
and height: 100 mm as shown in Fig. 2) for the catalytic separation
200 ◦ C at a rate of 5 ◦ C/min, then hold for 20 min, and finally increase to
experiment. During the experiment, all relevant temperature data were
the target temperature at a rate of 2 ◦ C/min and hold for approximately
recorded using a data logger (midi LOGGER GL840, Graphtec Corpo­
50 min.
ration co., Ltd, Japan). After the separation experiment, the products
For the catalytic separation experiment, the three catalysts (zeolite
were obtained as fraction 1 (F1, gasoline-like fraction), fraction 2 (F2,
4A, MDC-7 and Ni-based catalysts) were calcined at 400 ◦ C for 2 h in a

Zeolite 4A MDC-7 Ni-based

Fig. 1. The pictures of three catalysts of zeolite 4A, MDC-7 (Cu-based), and Ni-based catalysts.

3
S. Wang et al. Fuel 305 (2021) 121440

diesel-like fraction) and fraction 3 (F3, residual oil or wax), as shown in treatment at 130 ◦ C and 60 ~ 70 × 10–3 torr for 4 h. Acidic properties of
Fig. 2. Furthermore, several crucial temperatures for pyrolysis oil fresh and spent catalysts were determined using NH3-TPD (ammonia-
condensation were monitored (marked as yellow box in Fig. 2), temperature programmed desorption) method (Belcat-II (Microtrat
including T1 (pyrolysis oil temperature) of 25 ~ 410 ◦ C, T3 (pyrolysis oil BET)) in the temperature range of 150 ~ 800 ◦ C. Thermogravimetric
vapor temperature) of 280 ~ 305 ◦ C and T7 (top of F2 pipe) of 107 ~ analysis (TGA) of fresh and spent catalysts was performed using a TA
126 ◦ C. These vapor temperatures of T3 and T7 can directly affect the instrument SDT Q600 to understand the thermo stability properties of
yields and the properties of fractions (F1 was controlled by T7 whereas fresh and spent catalyst and determine the coke content in the spent
F3 was by T3). The detail conditions are introduced in S.Table 1. All catalysts.
experiments and analysis were conducted at least twice.
3. Results and discussion
2.3. Analysis of plastic pyrolysis oil and separated fractions
3.1. Determination of separation temperature
The plastic pyrolysis oil and separates were comprehensively
Fig. 3 shows the mass yield of each fraction over three different vapor
analyzed using the following analytic methods. The higher heating value
temperature conditions in accordance with Eq. (1). The highest yield of
(HHV) of the liquid fuels were measured with a PARR 6400 calorimeter
F1 was obtained with case 3 due to the highest vapor temperature at T7
in accordance with ASTM D 711. The ultimate analysis for C, H, N and S
(126 ◦ C) whereas the highest yield of F3 was from case 1 due to its
was carried out using a Thermo Scientific FLASH 2000 series elemental
lowest vapor temperature at T3 (280 ◦ C). As one of aims for the current
analyzer (ASTM D5373). The cloud and pour points of the liquid fuels
study is to have the large quantity of diesel-like F2 (C12 – C22), the
were measured based on ASTM D2500 and ASTM D97 standards. The
condition for case 2 was selected for the subsequent catalytic separation
kinematic viscosity of liquid oils was measured with a DAIHAN Scien­
experiment. The colors of the three fractions were transparent light
tific digital constant temperature viscosity bath (ASTM D445). The TAN
yellow for F1 (similar to gasoline), translucent brown liquid for F2 and
(total acid number) of liquid oils was detected using a Solge DIGI Test kit
black wax for F3, as shown in S.Fig. 1.
(ASTM D974) to understand the acid content of the liquid oils. The
Fig. 4 shows the simulated GC results of petroleum fuels and frac­
chlorine content of each oil sample was quantitatively detected by using
tions from three cases. The boiling point (b.p.) ranges of gasoline,
a combustion ion chromatography method with an AQF-2100H model
kerosene and diesel, obtained from a local gas station, were approxi­
(CIC Mitsubishi). Simulated GC analysis for each oil was performed
mately < 169 ◦ C, 138–278 ◦ C and 138–399 ◦ C, respectively. The boiling
using a simulated GC (Agilent, 6890 N) to determine the product mass at
point range of F1 was slightly higher than that of gasoline whereas F2
each carbon number directly related to each boiling point (b.p.), ac­
was similar to diesel, which can be also confirmed by the results of
cording to the ASTM D2887 standard. Furthermore, a GC–MS of Shi­
simulated GC analysis, presented in S.Fig. 2. The major carbon number
madzu QP2010Plus, ZB-DHA-PONA with 100 m × 0.25 mm diameter ×
ranges of gasoline, kerosene and diesel were C5-C10, C9-C15 and C9-C26,
0.5 μm thickness was applied to determine the chemical composition of
respectively, which were similar to the previous findings [33]. In
the liquid fuels. Mass yield of each oil sample was calculated with the
addition, each fraction (F1, F2 and F3) was compared in Fig. 4 (b),
following equation (1):
showing that the carbon range was C6-C10 for F1, C9-C22 for F2, and
Massyield(wt.%) =
MP
× 100% (1) greater than C22 for F3. In accordance with the experimental conditions,
MI the largest amount of F2 was obtained with case 2, which is consistent
with the mass yields of three cases as shown in Fig. 3.
where: Viscosity is one of the most important parameters among many
MP : Mass of product of F1, F2, F3 and loss (g) physical properties, not just because of safe pyrolysis operation, but also
MI : Initial mass of plastic pyrolysis oil (g). for oil sale and its use. The high viscosity fuel negatively affects its
fluidity, which can even block the pipe and igniter [34]. Therefore, the
2.4. Characterization of catalysts viscosity of each fraction was thoroughly measured to ascertain the
relationship between the separated fractions at different temperatures as
Zeolite 4A is a pellet shape with a diameter of 1.5 ~ 1.7 mm, a pore indicated in Figure 5. Viscosity of F2 (case 3) was slightly higher than
diameter of 4 Å and a density of greater than 0.68 g/mL. MDC-7 and Ni- other F2 (case 2), indicating that F2 (case 3) contains more heavy
based catalysts are tablet shape with an outside diameter of 3.2 and 4.0 chemicals due to its higher vapor separation temperature (T7 = 126 ◦ C).
mm, a height of 3.2 and 4.0 mm and a density of 1.29 and 1.14 g/mL,
respectively. The chemical compositions of catalysts were determined
by X-ray fluorescence (XRF) using a Primus II (Rigaku) spectrometer.
The results showed that the main chemical components for zeolite 4A
are SiO2 (43.49 wt%), Al2O3 (38.02 wt%) and Na2O (16.94 wt%), that
for MDC-7 are CuO (39.74 wt%), ZnO (39.64 wt%) and Al2O3 (17.22 wt
%). Last, Ni-based catalyst is composed of NiO (77.80 wt%), CaO (7.70
wt%) and Al2O3 (6.10 wt%). Among the three catalysts, the chemical
composition of the Ni-based catalyst obtained from XRF analysis was
significantly different from that (NiO 50 wt% and Al2O3 50 wt%) pro­
vide by Institute of Advanced Engineering (IAE, Korea). In order to
compare the changes of catalyst elements, the used catalysts after cat­
alytic separation experiment were analyzed again by XRF. Scanning
electron microscopy with energy dispersive spectroscopy (SEM-EDS)
(QUANTAX 200, Bruker) was used to observe the surface morphologies,
and determine the change of some key elements in catalysts. Brunauer
Emmet and Teller (BET) nitrogen adsorption analysis was adopted to
measure the specific surface area, pore volume and pore size of the fresh
and spent catalysts using an ASAP 2020 (BET Micromeritics). Before BET Fig. 3. Comparison of mass yields of F1, F2, F3 and loss obtained from case 1,
test, the degassing process of the catalysts was performed by vacuum case 2 and case 3.

4
S. Wang et al. Fuel 305 (2021) 121440

Fig. 4. Simulated GC analysis (a) for the boiling point of petroleum fuels and three separation cases and (b) for the carbon number distribution of each fraction (F1,
F2 and F3).

used for the subsequent catalytic separation of plastic pyrolysis oil.

25

Pyrolysis oil
3.2. Mass yields over catalytic separation

Py WAX Catalytic plastic oil separation experiments were carried out with
20
F1 (Case 2) three catalysts under the same temperature conditions of case 2 as
Kinematic viscosity [cSt]

F2 (Case 2) shown Fig. 6. F2 product mass yields of three catalytic separations

exhibited a lower mass yield (57.5 ~ 66.3 wt%) as compared to the case
15 F1 (Case 3) 2 separation experiment without a catalyst (71.1 wt% for F2). Similar to
F2 (Case 3) other literature [35], a decrease in the yield after the catalytic oil
cracking was due to the loss of the large amount of carbon and hydrogen
in the form of gases (such as CO, CO2, CH4, etc.) via decarboxylation,
10
decarbonylation and dehydration reactions during catalytic cracking

80
5 F1 F2 F3 Loss
70

60
Mass yield (wt.%)

0 50
0 10 20 30 40 50 60 70 80 90
Temperature [ ] 40

30
Fig. 5. Kinematic viscosity of F1 and F2 as compared to pyrolysis oil and wax.
20
Considering the high viscous pyrolysis oil at room temperature
(20–25 ◦ C), the pyrolysis oil should be upgraded for the use in the cold 10
areas. Consequently, the separating temperature conditions for case 2 0
was determined to be the optimal condition based on the highest yields Case 2 Zeolite 4A MDC-7 Ni-based
of F2 (71.09 wt%) and its lower kinematic viscosity. Thus, the vapor
temperature condition for case 2 (T3 = 305.1 ◦ C and T7 = 107.6 ◦ C) was Fig. 6. Mass yield of F1, F2 and F3 obtained from thermal cracking and three
catalytic cracking methods.

5
S. Wang et al. Fuel 305 (2021) 121440

process. MDC-7 produced the largest mass yield of F1 (15.8 wt%) and viscosity range (2.40 ~ 2.87 cSt @40 ◦ C) were obtained with F2 as
whereas Ni-based catalyst helped generating the highest yield of F2 compared to F1, indicating more heavy molecular chemicals existed in
(66.3 wt%). According to the Kim et al.[36], the catalytic pyrolysis can F2. This was fully verified by the content of heavy oil fractions (>C23) in
significantly reduce the activation energy (from approximately 300 KJ/ plastic pyrolysis oil as shown in S.Fig. 3. After pyrolysis oil separation
mol to about 200 KJ/mol) due to the presence of catalyst, thereby with or without catalysts, the heavy carbon range (>C23) abruptly
lowering the decomposition temperature. In addition, heavy aliphatic decreased from 22.1 wt% in plastic pyrolysis oil to 0.1 ~ 1.6 wt% in F1s
hydrocarbons, the main product of non-catalytic pyrolysis, were further and 7.3 ~ 8.4 wt% in F2s. In addition, TAN of F2 (12.2 ~ 22.2 mgKOH/
catalytically cracked into small hydrocarbons and form aromatic hy­ goil) was higher than that of F1 (4.4 ~ 7.8 mgKOH/goil), showing that
drocarbons through a series of catalytic reactions. there are more acidic substances included in F2. Furthermore, fractions
(F1, and F2) from catalytic separation methods had lower TAN values
3.3. Physical and chemical properties than that with case 2, indicating a stronger deoxygenation reaction
occurred in the presence of catalysts [24].
Table 2 summarized the physical and chemical properties of the From Table 2, similar ranges were found in some elements such as
samples. The plastic pyrolysis oil (82% C and 13% H) and its wax (84% C carbon (82%-86%), hydrogen (13.0%-13.8%) and nitrogen (0.1%-1.4%)
and 13.6% H) show a similar carbon and hydrogen contents as compared for all fractions before and after upgrading. These element ranges were
to the pyrolysis oil from plastic waste (87% C and 11% H) [37], higher found to be similar to that of petroleum crude oil (C: 83–87%, H:
than that of the pyrolysis oil from algae (72% C and 10% H) [38]. 10–14% and N: 0.1–2%) [33]. However, a significant change in oxygen
Accordingly, HHV of plastic pyrolysis oil (42–45 MJ/kg) was higher content was detected before and after cracking, especially for catalytic
than that of the pyrolysis oils from algae (38.6 MJ/kg). In addition, the cracking with three catalysts, as shown in Fig. 7. The order of the
relatively low concentrations of nitrogen (1.37%), sulfur (0.03%) and deoxygenation capacity: Ni-based > MDC-7 > zeolite 4A > thermal
oxygen (3.63%) in the plastic fuels can result in the stability of fuel for cracking (case 2). The oxygen content of F1 (4.8 wt%) and F2 (1.8 wt%)
longer storage and the low concentration of contaminant gas from fuel
combustion. However, some physical properties of pyrolysis oil
including viscosity and pour point (7.1 cSt @ 40 ◦ C and 35 ◦ C) were
higher than those of petroleum fuels, which is owing to the presence of a
large amount of paraffin wax in pyrolysis oil [33]. Furthermore, TAN
(total acid number) value of pyrolysis oil was 18 mgKOH/goil, much
higher than that of kerosene and diesel (<0.1 mgKOH/goil). The high
value of TAN can lead to the corrosion of pipes, storage containers and
reactors [34].
Over the pyrolysis oil separation, HHVs of F1 from 43.4 to 43.8 MJ/
kg were the lowest values among the separates, which can be explained
by the presence of relatively high oxygen contents based on Boie’s
Euquation (HHV, kJ/kg = 35,160xC + 116,225xH – 11,090xO +
6,280xN + 10,465xS). The cloud and pour points of F1 dropped dras­
tically to that of kerosene and diesel (<− 30 ◦ C) whereas their viscosity
Fig. 7. Comparison of oxygen content in plastic pyrolysis oil and its wax, F1s
(F1: 0.63 ~ 0.75 cSt @40 ◦ C) also decreased to that of petroleum fuels
and F2s obtained from different cracking methods.
(<0.5 cSt @40 ◦ C). However, higher cloud and pour points (-12 ~ 26 ◦ C)

Table 2
Properties of plastic pyrolysis oil and its wax, petroleum fuels, and upgraded fractions.
HHV Viscosity (cSt) Cloud point Pour point TAN (mgKOH/ Density (Kg/m3) C H N S O* O/C H/C
(MJ/kg) @40 ◦ C (oC) (oC) goil) @20℃

Plastic 43.0 7.1 N/A 35 17.8 796 82.0 13.0 1.37 – 3.63 0.03 1.90
pyrolysis oil
a b
Plastic 44.8 N/A 75 N/A 84.0 13.6 0.28 – 2.16 0.02 1.94
pyrolysis wax
Plastic Py-oil 42.3 N/A N/A N/A N/A 860 86.7 10.6 0.21 0.03 2.3 0.02 1.47
[37]
Algae Py-oil 38.6 3.54 N/A 14 12.2 N/A 72.2 9.7 6.0 0.22 11.9 0.12 1.61
[38]
Kerosene 46.4 <0.5 <− 30 <− 30 <0.1 729 85.8 14.2 – – 0.0 0.0 1.98
Diesel 45.7 <0.5 <− 30 <− 30 <0.1 754 86.0 14.0 – – 0.0 0.0 1.95
Case 2 F1 43.7 0.63 <− 30 <− 30 7.78 694 81.9 13.0 0.25 – 4.80 0.04 1.91
F2 44.5 2.66 17 4 22.22 734 84.4 13.6 0.26 – 1.79 0.02 1.93
a b
F3 45.5 N/A 75? N/A 86.0 13.8 0.14 – 0.05 0.00 1.93
Zeolite F1 43.4 0.67 <− 30 <− 30 4.44 688 84.0 13.5 0.32 – 2.25 0.02 1.92
4A F2 44.8 2.76 19 4 16.67 752 85.1 13.7 0.26 – 1.03 0.01 1.93
a b
F3 45.6 N/A 75? N/A 86.1 13.7 0.14 – 0.09 0.00 1.91
MDC-7 F1 43.8 0.72 <− 30 <− 30 5.55 710 84.9 13.4 0.36 – 1.31 0.01 1.90
F2 44.2 2.87 26 − 12 12.2 734 85.2 13.6 0.26 – 0.94 0.01 1.92
a b
F3 45.3 N/A 75? N/A 86.1 13.7 0.14 – 0.05 0.00 1.91
Ni-based F1 43.6 0.68 <− 30 − 30 5.56 710 84.8 13.7 0.26 – 1.23 0.01 1.94
F2 45.0 2.40 16 − 9 20.0 726 85.6 13.8 0.26 – 0.30 0.00 1.94
F3 45.6 N/A N/A N/A N/A N/A 86.0 13.7 0.16 – 0.17 0.00 1.92

N/A: not available.

a
unmeasurable at 40 ◦ C.
b
unmeasurable at 20 ◦ C.
*
By difference.

6
S. Wang et al.
obtained from thermal cracking (case 2) were similar to that of plastic
pyrolysis oil (3.6 wt%) and its wax (2.16 wt%), indicating the less
deoxygenation over that thermal cracking. Moreover, the higher oxygen
content of F1 (4.8 wt%) of case 2 than the raw plastic pyrolysis oil (3.6
wt%) is because of the following reasons: 1) no deoxygenation due to the
absence of catalyst, 2) more oxygen-containing compounds existed in
the F1 after thermal separation, which was supported by GC–MS anal­
ysis (such as alcohols and esters), 3) the presence of weak carbon–carbon
double bonds in olefins, they may be oxidized to oxygenated compounds
during the thermal cracking (without catalyst) [39]. On the other hand,
the catalytic separation dramatically decreased the oxygen content (F1
1.2 ~ 2.3 wt% and F2 0.3 ~ 1.0 wt%) [35]. Furthermore, the oxygen
contents of pyrolysis oil with MDC-7 and Ni-based catalysts were lower
than that of zeolite 4A, indicating better deoxygenation of MDC-7 and
Ni-based catalysts due to the presence of metal oxidation (CuO, ZnO and
NiO). The findings were supported by other study [24]. 1) Deoxygen­
ation mechanisms were mainly controlled by different metal active
centers when the acid-catalyzed reactions were primarily governed by
zeolitic acid sites. 2) The properties of zeolites and metals (such as
acidity, porosity, activity, metal centers, selectivity and stability) can
significantly affect the overall reaction pathways during the catalytic
cracking of pyrolysis oil. 3) The interaction (synergistic effect) between
the zeolite acid sites and metal centers always significantly affected on
the selectivity for the production of desired products over deoxygen­
ation and acid-catalyzed reactions. 4) The metal and acid balance were
important to improve the product selectivity and catalytic activity. The
Van Krevelen diagram was used to further understand the elemental
analysis by comparing the ratios of H/C and O/C in fuels as shown in
Fig. 8. After upgrading the plastic pyrolysis oil, F1 and F2 of case 2
showed higher O/C ratio than those of zeolite 4A, MDC-7 and Ni-based
catalysts, indicating that the catalytic separation leads to better deoxy­
genation than the separation without catalyst. Among three catalysts,
Ni-based catalyst triggered the most close elemental properties of
separated fuels as compared to that of petroleum-based fuels, especially
F2 (O/C: 0.00, and H/C: 1.94). Generally, higher fraction of paraffin
groups result in the higher H/C ratio whereas olefin (c.olefin), aromatic,
naphthene and ketone composition decrease the H/C ratio owing to the
presence of carbon–carbon double bonds or cyclic hydrocarbons. In
addition, higher O/C ratio has a negative impact on HHV and TAN
values.
3.4. GC–MS analysis, catalytic mechanism and reaction pathways
GC–MS analysis was conducted to further identify the chemical
Fig. 8. Van Krevelen diagram of plastic pyrolysis oil and separated samples
with and without catalysts.
7
Fuel 305 (2021) 121440
groups in F1 and F2, obtained from different separation methods as
indicated in Fig. 9. The most concentrated chemical group in F1 were
olefins, followed by paraffins, aromatic and naphthenes whereas F2
primarily contains paraffins and olefins, followed by naphthenes, aro­
matic, esters and alcohols groups. It is worth noting that higher aromatic
content and lower olefins content were found in F1 of MDC-7 as
compared to the separation with other catalyst. In addition, MDC-7
showed a relatively higher aromatics and naphthenes within the range
of C11-C22 of F2, which indicates that MDC-7 has strong aromatization,
catalytic cracking, and cyclization effects. Similar findings were also
found in different studies [40,41] who found that Zn/Zeolite catalyst
can remark an increase in the yield of aromatic hydrocarbons by
enhancing the selective aromatization of alkenes. In addition, Singh
et al. [42] also reported that Cu/Zeolite was beneficial to the production
of paraffin (especially isoparaffin) and naphthenes because the in-situ
hydrogen, produced from the water–gas-shift (WGS) reaction with Cu/
Zeolite, can lead to saturate the branched olefin into the paraffin and the
aromatics into naphthenes. In the Ni-based catalyst case, the highest
content of olefins in F1 (total: 54.49%) and F2 (total: 36.16%) were
observed because the Ni-based catalyst shows no strong aromatization
reaction like MDC-7, thereby resulting in a large amount of olefins in F1
and F2. Similar findings were obtained in the research conducted by
Vichapund et al. [43] regarding the effect of various metals (Ni, Co, Mo,
Ga and Pd) over zeolite (HZSM-5) on the deoxygenation and hydrogen
transfer activities of the catalyst. Especially, Ni and Co contributed to the
formation of olefins whereas Mo, Ga and Pd favored the formation of
aromatics through dehydrogenation. The order of deoxygenation re­
ported was Ni > Pd > Co > Mo > Ga. Therefore, Ni metal mainly
enhanced the deoxygenation reactions thereby reducing the production
of aromatics to a certain degree. In addition, a relatively higher ester
content was found in F2 of Ni-based catalyst (total 4.4%), indicating its
relatively stronger esterification than other catalysts. According to Chen
et al. [44], esterification can significantly increase the saturation of the
pyrolysis oil and reduce the corrosiveness, thereby facilitating the sub­
sequent cracking or reforming processes.
To further study how the catalysts affected the chemical composition
of F1 and F2 products, the GC–MS results of the plastic oil and all
separated F1s and F2s were reorganized, as shown in Fig. 10. The effect
of catalysts on F3 (wax, >C23) was not analyzed because it has not
passed through catalysts. The effect of thermal cracking on the chemical
composition of F1 and F2 was compared with oil from case 2. For F1 of
case 2, the contents of olefins, aromatics, naphthenes and ketones
reduced whereas the contents of paraffins, other oxygenates and esters
increased as compared to the raw plastic oil. The opposite trend was
found in F2 of case 2. A significant increase in aromatics was observed in
F1 from 13.0% of case 2 to 18.3% with MDC-7 whereas an obvious
decrease in olefins was obtained in F1 from 53.6% of case 2 to 44.8%,
which indicates that MDC-7 has a strong aromatization effect and can
convert the olefins into aromatics. This is probably due to the moderate
acidity and porous structure of MDC-7 catalyst, which can be helpful for
producing light aromatics from catalytic cracking of plastic oil as similar
results reported previously [21,41]. F1 of Ni-based catalyst shows
chemical compositions similar to the F1 of case 2. The biggest difference
is that the other oxygenates are almost zero in F1 with Ni-based catalyst,
indicating that Ni-based catalyst has strong deoxygenation as Ni-based
catalyst contains more acid sites content (especially strong acid sites
as shown in S.Table 4), which can promote the deoxygenation [24]. Ni-
based catalyst exhibited the highest catalytic activity of deoxygenation
reaction to produce the oxygenates from plastic oil (with 1.23% O in F1
and 0.3% O in F2) owing to its high contents of strong acid sites (1.115
mmol/g) and large surface area (106 m2/g). On ther other hand, F2 with
each MDC-7 and Ni-based catalyst showed a significant reduction in
other oxygenates from 11.0% of case 2 to 6.7% of MDC-7 and to 6.9% of
Ni-based, respectively, indicating strong deoxygenation of decarboxyl­
ation, decarbonylation and dehydration. Furthermore, according to the
previous studies [20,21and24], the dense acidity and porous structure of
S. Wang et al. Fuel 305 (2021) 121440

20 20
Paraffins Case2 Naphthenes Case2

Composition (wt.%)
Zeolite 4A

Composition (wt.%)
Zeolite 4A
15 15
MDC-7 MDC-7
Ni-based Ni-based
10 10

5 5

0 0
C6-C10 C11-C22 >C23 C6-C10 C11-C22 >C23

60 20
Olefins Case2 Aromatics Case2
50

Compositon (wt.%)
Zeolite 4A
Composition (wt.%)

Zeolite 4A 15
40 MDC-7 MDC-7
Ni-based Ni-based
30 10

20
5
10

0 0
C6-C10 C11-C22 >C23 C6-C10 C11-C22 >C23
(a) F1

40 10
Paraffins Naphthenes
Composition (wt.%)

Case2 8
30 Case2
Composition (wt.%)

Zeolite 4A
6 Zeolite 4A
20 MDC-7 MDC-7
Ni-based 4
Ni-based
10
2

0 0
C6-C10 C11-C22 >C23 C6-C10 C11-C22 >C23

40 10
Olefins Aromatics
8
Composition (wt.%)
Composition (wt.%)

30 Case2
Case2
Zeolite 4A
6 Zeolite 4A
20 MDC-7 MDC-7
Ni-based 4 Ni-based

10 2

0 0
C6-C10 C11-C22 >C23 C6-C10 C11-C22 >C23

10 10
Esters Alcohols
8 8
Composition (wt.%)
Composition (wt.%)

Case2 Case2

Zeolite 4A Zeolite 4A
6 6
MDC-7 MDC-7
4 Ni-based
4
Ni-based

2 2

0 0
C6-C10 C11-C22 >C23 C6-C10 C11-C22 >C23
(b) F2

Fig. 9. GC–MS analysis results of distribution of different chemical composition in different carbon number ranges of LO (C6-C10), MO (C11-C22), and HO (≥C23)
via different separation methods, (a) F1, and (b) F2.

8
S. Wang et al.
Fig. 10. Effect of different catalysts on the chemical compositions of F1 and F2.
catalyst were responsible for its better activity for the catalytic cracking
from plastic oil. Zeolite 4A, MDC-7 and Ni-based catalysts have different
acidities and specific surface areas; the order of acid sites content with
surface area was zeolite 4A < MDC-7 < Ni-based catalyst, as shown in S.
Table 4 and 5. In addition, F2 over MDC-7 and Ni-based catalyst
cracking showed higher naphthenes and olefins as compared to that of
case 2, respectively. The previous studies also reported similar findings
that MDC-7 contributes to the production of naphthenes [42] and Ni-
based catalyst favors to form of olefins [43].
Some specific chemical compositions (greater than1.0% in GC–MS)
of F1 and F2 obtained from catalytic separation with three different
catalysts were summarized in S.Table 2. The changes in the content of
these specific chemicals can also reflect the influence of the different
catalysts on the chemical compositions of F1 and F2. A very high content
of 2,4-dimethyl-1-heptene (C9H18, 15.6%) and a relatively high content
of 2-hexene, 4,4,5-trimethyl- (C9H18, 6.9%) are found in the F1 of zeolite
4A. This is consistent with the highest content of olefins (53.4%) in F1
(carbon range: C6 – C10) of zeolite 4A. The two highest components in F2
(carbon range: C11 – C22) of zeolite 4A are nonadecane (C19H40, 11.5%)
and 3-hexadecene, (z)- (C14H28, 7.3%). This follows the order of content
of components in F2 of zeolite 4A, as shown in Fig. 10. In addition, more
aromatics (styrene, benzene, ethyl- and benzene) are found in F1 of
zeolite 4A as compared to F2 of zeolite 4A. This confirms that zeolite 4A
contributes to the formation of aromatics in F1. Similarly, since olefins
and paraffins are the highest components in F1 and F2 of MDC-7,
respectively, F1 of MDC-7 contains more olefin components, such as
2,4-dimethyl-1-heptene (C9H18, 12.3 %) and 2-hexene, 4,4,5-trimethyl-
(C9H18, 7.6%) while F2 of MDC-7 has higher paraffin components, such
as nonadecane (C19H40, 15.4%) and heptadecane (C17H36, 8.6%). In the
case of Ni-based catalyst, olefins account for more than half (54.7%) of
F1 of Ni-based catalyst, resulting in high olefin components such as, 2,4-
dimethyl-1-heptene (C9H18, 14.7%) and 2-hexene, 4,4,5-trimethyl-
(C9H18, 8.3%) in F1 of Ni-based catalyst. Correspondingly, the main
components of F2 of Ni-based catalyst are olefins [3-hexadecene, (z)-
(C16H32, 5.5%) and 3-octadecene, (e)- (C18H36, 4.5%)] and paraffins [
nonadecane (C19H40, 9.0%)].
Based on the above analysis, both MDC-7 and Ni-based catalysts have
more prominent catalytic mechanisms than zeolite 4A. It can be inferred
9
Fuel 305 (2021) 121440
that the catalytic mechanism and reaction pathways [45] of MDC-7 and
Ni-based catalysts can be obtained, as shown in Fig. 11. For MDC-7
catalyst, long-chain olefins, long-chain alcohols and ester, and long-
chain paraffin were converted into short-chain olefins and parafffins
via catalytic cracking, dehydration, decarbonylation, and decarbon­
xylation reactions, then further formed aromatic through aromatization
(main reaction), and naphthenes through cyclization (secondary re­
actions). In case of Ni-based catalyst, a large amount of olefins was
produced by dehydration and catalytic cracking reactions of long-chain
alcohols (main reaction). Benzoic acid and phenol were converted into
aromatic via strong deoxygenation such as dehydration, decarboxyl­
ation and decarbonylation reactions [46]. In addition, some long-chain
paraffins were catalytically cracked into short-chain paraffins (second­
ary reaction). However, according to Seo et al. [47], the chemical
compositions for commercial gasoline are composed of paraffin
73–87%, olefin 3–12%, naphthene 2–6%, and aromatic 8% while
paraffin 30%-40%, olefin 2%-8%, naphthene 18%–23%, and aromatic
35%-39% are for commercial diesel. Therefore, significantly higher
olefins were found in F1 (44–55%) and F2 (32–36%) compared to the
commercial petro-based fuels (2–12%), indicating that further refining
is required to reach the composition standards of petro-based fuels.
Additionally, it is typically known [39] that the large fraction of par­
affins and napthenes decreases the viscosity although the viscosity
showed higher in F2 with lower paraffins and napthens relative fraction
as compared to that in F1. This is because of the presence of the higher
carbon ranged paraffin wax in F2. Hydrogenation-cracking [17] was
demonstrated to be a suitable refining method because it can not only
break the double bonds through hydrotreating, but also further lower
the oxygen content via catalytic cracking and prolong the life of catalyst
by reducing the coke formation. Additional GC–MS comparison chro­
matograms of F1 and F2 over separation with or without different cat­
alysts are shown in S.Fig. 4. The upgraded fractions (F1 and F2) from
zeolite 4A, MDC-7 and Ni-based catalysts showed more overlapped
peaks compared to these from case 2 (separation without catalyst)
because zeolite 4A, MDC-7, and Ni-based catalysts belong to catalytic
cracking.
S. Wang et al. Fuel 305 (2021) 121440

(a) MDC-7 (Cu-based catalyst)

(b) Ni-based catalyst

Fig. 11. Schematic diagram of the catalytic mechanism and reaction pathways of (a) MDC-7 and (b) of Ni-based catalyst.

Table 3
Chemical composition of catalysts before and after experiment.
Zeolite 4A MDC-7 Ni-based

Components (wt.%) Before After Components (wt%) Before After Components (wt.%) Before After

SiO2 43.50 43.50 CuO 39.74 43.15 NiO 77.80 68.44

Al2O3 38.02 36.93 ZnO 39.61 40.57 CaO 7.70 8.65
Na2O 16.94 16.13 Al2O3 17.22 13.12 Al2O3 6.10 4.79
Fe2O3 0.44 0.48 SiO2 3.01 0.64 La2O3 1.86 1.70
SO3 0.30 0.33 MgO 0.14 0.03 SiO2 1.81 1.60
TiO2 0.29 0.30 CaO 0.06 0.04 CeO2 1.41 1.29
K2O 0.19 0.20 SO3 0.05 0.38 MgO 1.34 1.06
MgO 0.09 0.10 P2O5 0.05 0.05 P2O5 1.13 2.30
CaO 0.08 0.11 Fe2O3 0.05 0.04 Fe2O3 0.36 0.42
SnO2 0.06 0.19 Cl 0.04 1.95 ZnO 0.21 8.67
P2O5 0.03 0.03 K2O 0.02 0.01 Cl 0.07 0.37
Cl 0.02 1.57 MnO 0.01 0.01 SO3 0.07 0.16

10
S. Wang et al.
3.5. Analysis of catalysts
The chemical compositions of fresh and spent catalysts were deter­
mined by XRF as presented in Table 3. The main chemical composition
of zeolite 4A showed an insignificant difference before and after
cracking, while MDC-7 and Ni-based catalysts had an obvious difference
in chemical composition such as CuO and NiO. This can be explained by
the fact that zeolite catalyst mainly exhibits a selectivity over its shape
characteristics, whereas metal-based catalyst is primarily responsible for
deoxygenation via chemical reactions [24]. Interestingly, the chlorine
content of three catalysts increased after separation, which implies the
presence of chlorine in the plastic pyrolysis oil. Chlorine, mainly ob­
tained from PVC plastics, is an undesirable element in plastic pyrolysis
oil. In addition to easily corroding steel equipment, storage tanks and
boilers, chlorine also poisons and deactivates the catalysts during py­
rolysis. The chlorine content of the plastic pyrolysis oil, as shown in S.
Table 3, was approximately 6100 mg/kg, which decreased abruptly to
1600 mg/kg in F2 of case 2, and to 1000–1200 mg/kg in F2 of all three
catalyst cases after cracking. However, these values are still significantly
higher than the chlorine content (<1mg/kg) in standard fuel oil ac­
cording to ASTM D4929 [48], therefore further dechlorination is
required. Calcium oxide (CaO) is an effective dechlorination agent,
widely used in various applications. Veksha et al. [49] conducted an
upgrading of non-condensable plastic pyrolysis gas over catalytic
decomposition and dechlorination using an adsorbent (5% NiO loaded
on CaCO3). The results showed that Ca can remove 98.8% of HCl and
decompose 89% of alkynes and 23% of dienes at 700 ◦ C. Coincidentally,
the Ni-based catalyst used in the current work, contained NiO and CaO,
could explain why F2 and spent catalyst contained less chlorine content
compared to other catalysts.
The SEM analysis was shown in S.Fig. 5, a loose rough surface with
white spots was detected on zeolite 4A, a compact and flat surface was
found on MDC-7, and a rough and uneven black surface was observed on
Ni-based catalyst. After catalytic separation, a significant number of floc
particles deposited on the surface of spent zeolite 4A, and the particles
deposited on spent MDC-7 gradually agglomerated and formed clusters.
For the spent Ni-based catalyst, a layer of black substance was deposited
on the surface, the rough and uneven surface became very smooth and
compact. These substances blocked the framework of catalysts and
lowered the activity of catalysts. A similar finding was found in other
research [50], which pointed out these substances deposited on the
spent catalysts were mainly coke precursors. This was verified in EDS
analysis (S.Fig. 6) because the content of “C” was abruptly increased
from 12 to 24 wt% of fresh catalysts to 62–97 wt% of spent catalysts.
Details on the formation of coke is discussed the subsequent TGA
analysis.
The NH3-TPD profiles of fresh and spent catalysts were illustrated in
16000
Zeolite 4A Spent-Zeolite 4A
MDC-7 Spent-MDC-7
14000 Ni-based catalyst Spent-Ni-based catalyst
12000
TCD sign (uV)
10000
8000
6000
4000
2000
0 tential to be an alternative for commercial diesel as the heating value
100 200 300 400 500 600
Temperature ( )
Fig. 12. NH3-TPD profiles for different catalysts before and after experiment.
Fuel 305 (2021) 121440
Fig. 12 and the acidic properties were summarized in S.Table 4. Zeolite
4A mainly contained a large amount of weak acid sites at the peak of
258 ◦ C whereas MDC-7 and Ni-based had more strong acid sites at the
peaks of 670 and 745 ◦ C, respectively. This phenomenon existed owing
to the introduction of metal oxides (such as CuO, ZnO and NiO), which
corresponded to the findings of Singh et al. [42]. According to Che et al.
[51], some important reactions such as deoxygenation reactions mainly
occur on strong acid sites. To further verify this point, the plots of ox­
ygen content in F2 samples against the strong acid sites content of
catalyst was drawn as S.Fig. 7. High correlation coefficient (R2 =
0.9966) indicated that the strong acid sites played a significant role in
catalytic reactions (especially deoxygenation reactions). After catalytic
separation, the strong acid sites content of three spent catalysts
increased significantly compared to that of fresh catalysts, and the de­
gree of increase remained Ni-based > MDC-7 > zeolite 4A. This can be
explained by the fact that catalytic reactions and coke formation pri­
marily occurred in strong acid sites [51], and also because the oligomers
required for coke formation may contained acid sites [26]. This was
verified by the coke contents of the spent catalysts, as shown in S.
Table 5. In other words, the higher the strong-acid site content, the
higher the coke content.
The textural properties of fresh and spent catalysts were summarized
in S.Table 5. Ni-based catalyst showed the highest textural properties
(SBET = 106.31 m2/g and Vpore = 0.188 cm3/g), followed by MDC-7
(SBET = 56.86 m2/g and Vpore = 0.170 cm3/g) and zeolite 4A (SBET =
11.97 m2/g and Vpore = 0.044 cm3/g). After catalytic separation, the
surface area and pore volume of the spent catalysts dropped sharply to
SBET = 0.2 ~ 0.5 m2/g and Vpore = 0.001 ~ 0.007 cm3/g, respectively,
which was due to pore blockage by coke deposition. The TGA-DTG
analysis for fresh and spent catalysts was carried out to investigate the
thermal stability propertiesand determine the coke content, and the
results were shown in S.Fig. 8 and S.Table 5. Three fresh catalysts
showed different thermal stability properties in the order of Ni-based
(89.49 wt% at 800 ◦ C) > MDC-7 (84.55 wt% at 800 ◦ C) > zeolite 4A
(84.54 wt% at 800 ◦ C). It should be noted that peak of fresh zeolite 4A at
around 150 ◦ C (S.Fig. 8 b magnification) appeared was due to the loss of
water caused by dehydration. After catalytic separation, the curves of
three spent catalysts basically contained two decreasing stages: the
decomposition of oil adsorbed on the surface of spent catalyst at a
moderate temperature (due to the boiling point range of 130–400 ◦ C for
F2), and the decomposition of coke at a high temperature. The spent Ni-
based catalyst had two obvious peaks at around 210 ◦ C and 500 ◦ C,
which were responsible for decomposition of oil and coke, respectively.
Spent zeolite 4A and MDC-7 had similar peaks at about 260 ◦ C, which
were attributed to the decomposition of oil (as shown in magnification).
A relatively obvious peak for decomposition of coke on spent MDC-7 was
found at about 400 ◦ C, while an insignificant peak for decomposition of
coke on spent zeolite 4A was detected at approximately 550 ◦ C (as
shown in magnification). Similar findings were reported by Wang et al.
[52], in which hydrogenation-cracking was also proposed as an effective
method to ease formation of coke and prolong catalyst lifetime.
4. Conclusion
A 2-kg-scale pyrolysis oil separator was designed for the catalytic
separation of plastic pyrolysis oil to evaluate the feasibility of direct
condensation at a specific vapor temperature during the pyrolysis of
plastic wastes. Each fraction (F1 and F2) obtained from the catalytic
separation using different catalysts was comprehensively analyzed. The
optimum separation vapor temperature for diesel-like middle fraction
(C11 - C22) production was determined to be in the range of 107–305 ◦ C.
Among the all fractions, the F2 of Ni-based catalyst showed a high po­
700 800
was 45.0 MJ/kg with the H/C ratio of 1.94 and O/C ratio of 0.00. Metal-
loading can produce more strong acid sties on the surface of catalyst, and
the catalytic reactions and the coke formation mainly occurred on the
11
S. Wang et al.
strong acid sites. Nickel-based catalysts contributed to the production of
MO containing more olefins, while MDC-7 catalysts favored the pro­
duction of LO containing more aromatic and naphthenic compounds,
due to their different catalytic mechanisms. Overall, the F2 can be
substitute the petroleum liquid fuels over further deoxygenation and
hydrotreatment to reduce the total acid content and olefin content.
CRediT authorship contribution statement
Shuang Wang: Investigation, Formal analysis, Writing – original
draft, Writing - review & editing. Hana Kim: Formal analysis, Investi­
gation, Validation. Doyeon Lee: Methodology, Supervision. Yu-Ri Lee:
Writing - review & editing. Yooseob Won: Resources, Methodology.
Byung Wook Hwang: Formal analysis, Methodology. Hyungseok
Nam: Methodology, Writing - review & editing, Supervision, Project
administration, Funding acquisition. Ho-Jung Ryu: Resources, Funding
acquisition. Kyong-Hwan Lee: Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
This work was conducted under framework of the research and
development program of the Korea Institute of Energy Research (C1-
2429-02), Republic of Korea (South Korea).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.fuel.2021.121440.
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