Journal of the Energy Institute 102 (2022) 384–394

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Journal of the Energy Institute

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Insight into synergistic effect of co-pyrolysis of low-rank coal and waste

polyethylene with or without additives using rapid infrared heating
Yunfei Wu, Guijin Wang, Jialong Zhu, Yiming Wang, He Yang, Lijun Jin, Haoquan Hu *
State Key Laboratory of Fine Chemistry, Institute of Coal Chemical Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024, China

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

Keywords: A newly infrared-heated reactor with a high heating rate (20 ◦ C/s) was applied to explore the co-pyrolysis in­
Low-rank coal teractions between low-rank coal and waste polyethylene (PE), and further observe the effect of organic plastic
Waste polyethylene additives (OPAs) in PE on co-pyrolysis interactions. PEs pyrolysis results revealed that white PE hose without
Co-pyrolysis
additives (WPE) and black PE threading pipe with additives (BPE) exhibit significantly different product dis­
Infrared heating
Synergistic effects
tribution. Co-pyrolysis results indicated that the addition of WPE in coal is conducive to forming tar, with a
maximum tar yield increment of 6.23 wt% observed at coal/WPE (7:3). However, adding BPE in coal has a slight
impact on the tar yield but significantly enhances the light fractions in tar, with a maximum light tar content
increment of 6.00% at coal/BPE (9:1), revealing the interactions between OPAs volatiles and coal volatiles. The
volatile-volatile interactions promote the cracking of waste PE to form short-chain aliphatic hydrocarbons and
inhibit coal pyrolysis to generate aromatics and phenols. Furthermore, the chars from co-pyrolysis have a lower
H/C ratio and higher C-centered radical concentration than coal char, further demonstrating that hydrogen has
been transferred to the liquid products, which can provide an effective complement for understanding the co-
pyrolysis interactions.

1. Introduction
Coal, as a vital part of the global energy structure, is an essential fuel
to boost the rapid development of power, chemical, and steel industries.
However, immoderate exploitation and utilization of coal have an
enormous impact on the ecological environment [1,2]. Hence, exploring
further clean and efficient conversion pathways of coal is valuable for
environmental protection. Coal pyrolysis, as a promising pathway, can
convert coal into high value-added chemicals, H-rich gases, and char
under mild conditions [3–5]. In general, coal pyrolysis has a low tar
yield and poor quality due to the low H/C ratio [6,7], and hydro­
pyrolysis of coal was considered to be a vital technique to obtain
high-yield and high-quality liquid products [8,9].
Currently, as a practical and effective upgrading technique, the co-
pyrolysis of low-rank coal with H-rich materials has been received
widespread attention [4,6,10]. Waste plastics, as a non-degradable
polymer, have greatly challenged the environmental pressure [11–14].
However, it can be considered as a good hydrogen source, especially for
polyolefins such as polyethylene (PE) and polypropylene (PP), which
have a high H/C ratio up to about 2.0 [15,16]. As a practical solution,
co-pyrolysis of coal and waste plastics can not only make full use of
H-rich components from plastics for obtaining the high value-added
fuels and chemicals but also relieve the energy and environmental
pressures. Zhou et al. [17] revealed the emergence of synergistic effects
between coal and plastics during the co-pyrolysis process. Meanwhile,
Qian et al. [4] found that the yields of tar and gas were promoted during
the co-pyrolysis of lignite and plastic. Nevertheless, various coal and
plastics are generally involved in varied pyrolysis temperature ranges
[6,18,19]. When the two materials selected have a large pyrolysis
temperature difference, the co-pyrolysis interaction will be greatly
restricted. Especially at lower heating rates (i.e., slow pyrolysis), there is
a high requirement for the suitability of coal and plastics pyrolysis
temperatures [20,21]. In comparison, high heat transfer rates, namely
fast pyrolysis, are essential to avoid the discrepancy of materials py­
rolysis temperatures in the co-pyrolysis process. Many studies have
verified that fast pyrolysis can accelerate the escape of primary volatiles,
which is helpful to avoid the secondary cracking of gaseous tar, thereby
promoting the yield of tar instead of gas and char [22–24]. Recently,
several researchers have investigated the co-pyrolysis interaction be­
tween varied materials with a higher heating rate. Among them, Yang

* Corresponding author.
E-mail address: hhu@dlut.edu.cn (H. Hu).

https://doi.org/10.1016/j.joei.2022.05.005
Received 27 February 2022; Received in revised form 29 April 2022; Accepted 4 May 2022
Available online 8 May 2022
1743-9671/© 2022 Energy Institute. Published by Elsevier Ltd. All rights reserved.
Y. Wu et al.
et al. [22] reported co-pyrolysis of low-density polyethylene (LDPE)
with varied biomass in a drop tube reactor and found that the oil yield of
LDPE/biomass (1:1) co-pyrolysis is higher than that of individual py­
rolysis at 600 ◦ C. While Zhu et al. [25] revealed the emergence of
interaction between low-rank coal and cedar at a high heating rate
(1200 ◦ C/min), and the tar yield (20.27 wt%) is 1.54 times higher than
that of Gray-King assay. But up until now, few studies have closely
focused on the co-pyrolysis interaction between low-rank coal and waste
plastics at high heating rates. Hence, it is necessary to comprehensively
investigate the synergistic effects and interaction mechanism of fast
co-pyrolysis.
Additionally, owing to society’s strong demand for plastic safety and
practicability, various organic plastic additives (OPAs) were introduced
to polymers during the manufacturing process to modify and improve
their properties, so that the produced plastics have antioxidant, flame-
retardant, antiultraviolet, heat-resisting, and antistatic, which leads to
the diversification of plastic materials and species [3,26]. For most
OPAs, such as flame retardants, antioxidants, and light stabilizers
contain certain volatile compounds. Yanagisawa et al. [27] observed
that OPAs were decomposed weakly at a low pyrolysis temperature
(<300 ◦ C), while they can be pyrolyzed along with polymer matrix at
higher temperature. This result elucidated that the pyrolysis product
composition of polymer with additives will be more complicated than
that of polymer without additives. Furthermore, the proportion of OPAs
within the polymers is also very disparate, varying from 0.005% to 70%
[28]. This also further results in a difference in the synergistic effect
from co-pyrolysis with coal, which affects the products distribution, tar
compositions, and char characteristics. Herein, it is essential to explore
and compare the synergistic effect of co-pyrolysis between coal and
varied waste plastics (with and without OPAs).
This paper purposes to systematically explore volatile-volatile in­
teractions from low-rank coal and waste PE based on high heating rates
(20 ◦ C/s). Herein, the infrared heating technique was applied to provide
a heat source for a fixed-bed reactor due to the features of high heating
rates, reliable temperature control, and well-distributed heating [24,
25]. The effect of pyrolysis temperature and mixing ratio on the prod­
ucts distribution, tar fraction and compositions, as well as char char­
acteristics, were investigated in detail. Meanwhile, the differences in the
co-pyrolysis behaviors of low-rank coal blended with two waste PE (with
and without OPAs) were compared. The obtained results will not only
help to gain a deeper understanding of co-pyrolysis synergistic effects of
volatiles from low-rank coal and waste plastics but also reveal OPAs’
effect on the product distribution and tar compositions.
2. Experimental
2.1. Materials
Pingshuo coal, a sub-bituminous coal, was collected from Pingshou
coalfield, Shanxi Province, China. Two different waste PE were used in
this study, including conventional white PE hoses for agricultural irri­
gation (WPE) and black PE threading pipe with antioxidant (BPE),
Fig. 1. Photos of waste PE: (a) WPE and (b) BPE.
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Journal of the Energy Institute 102 (2022) 384–394
which were purchased from Taiwei pipe factory outlet store, as shown in
Fig. 1. Before experiments, coal was crushed and sieved to below 80
mesh (<0.178 mm), while WPE and BPE were cut into 1–3 mm chips,
and then placed in a vacuum oven to dry for 24 h at 65 ◦ C. The results of
proximate and ultimate analyses of coal, WPE, and BPE are listed in
Table 1. As can be seen, coal has a H/C atomic ratio of 0.78, which is
rather lower than 1.96 for WPE and 1.99 for BPE. The WPE used herein
contains 85.58% carbon, 13.98% hydrogen, and 0.44% oxygen, which
are close to the element composition of virgin PE [29], indicating that
WPE has high purity and is hardly exist OPAs. In comparison, BPE has a
relatively low carbon content of 75.58% and an extremely high oxygen
content of 10.36%, which illustrates that phenols antioxidants and ester
plasticizers contained in BPE, but the specific type and content of OPAs
were not available. Meanwhile, the ash composition of BPE was detected
via X-ray fluorescence spectrometer (XRF) and found that it has an
extremely high CaO content of 69.6% (Table S1), which is derived from
inorganic filler additive in BPE. Additionally, the obtained coal was
mechanically premixed with BPE and WPE according to the mass ratios
of 9:1, 7:3 and 1:1, which are marked as coal/WPE (1:0), coal/WPE
(9:1), coal/WPE (7:3), coal/WPE (1:1), coal/WPE (0:1) and coal/BPE
(1:0), coal/BPE (9:1), coal/BPE (7:3), coal/BPE (1:1), coal/BPE (0:1),
respectively.
2.2. Infrared heating pyrolysis process
An infrared-heated device was adopted in this study, which is mainly
composed of gas supply, fixed-bed pyrolysis reactor with built-in quartz
tube (Inner diameter: 16 mm, Length: 60 mm), tar condensation, and
non-condensable gases collection systems, as shown in Fig. S1. For each
experiment, about 2 g sample was loaded into a quartz tube and placed
in the pyrolysis region of the reactor. Then, high-purity N2 (Purity:
>99.999%, Flow-rate: 200 mL/min) was employed to purge the reactor
and as a shielding gas for the entire pyrolysis process. Subsequently, it
was heated to the set pyrolysis temperature (450–650 ◦ C, interval 50 ◦ C)
at 20 ◦ C/s, and held for 20 min. Eventually, the produced tar-water
mixtures were collected in a cold trap (− 25 ◦ C), while the non-
condensable gases were metered via a wet type gas flowmeter and
collected in a gas bag for gas chromatographic analysis.
2.3. Characterizations
Tar compositions were analyzed by using gas chromatography/mass
spectrometry (GC/MS, Agilent 7890A/5975C), and tar fractions were
evaluated by simulated distillation gas chromatograph (SCION 456-GC
with CP-SimDist column) according to the ASTM D2887 method.
Meanwhile, it was classified into three fractions based on the boiling
point, namely, light fraction (<200 ◦ C, gasoline), medium fraction
(200–350 ◦ C, include kerosene, diesel), and heavy fraction (>350 ◦ C,
include vacuum gas oil and vacuum residue). Non-condensable gas
compositions were identified by gas chromatography (GC, 7890 II),
including H2, CO, CO2, CH4, and C2–C3 hydrocarbon gases (C2H4, C2H6,
and C3H8). The morphology of char samples was measured via scanning
Y. Wu et al. Journal of the Energy Institute 102 (2022) 384–394

Table 1
Proximate and ultimate analyses of coal, WPE, and BPE samples.
Sample Proximate analysis (wt%) Ultimate analysis (wt%, daf) H/C
a
Mad Ad Vdaf FCdaf C H N S O

Coal 1.26 23.52 42.65 57.35 78.42 5.08 1.38 0.77 14.35 0.78
WPE – – 99.93 0.07 85.58 13.98 – – 0.44 1.96
BPE – 4.54 98.88 1.12 75.58 12.50 1.47 0.09 10.36 1.98

Mad: moisture content on air-dry basis; Ad: ash content on dry basis; Vdaf: volatile matters content on dry and ash-free basis; FCdaf: fixed carbon content on dry and ash-
free basis.
a
by difference.

electron microscope (FEI Quanta 450, SEM). Additionally, the stable

∑
2
radicals in char were analyzed by electron paramagnetic resonance Wchar − xi W0 Aad,i
(EPR, Bruker EMXnano spectrometer). EPR spectrum was scanned by Ychar (wt.%) = i=1
× 100 (3)
∑ ( )
using Bruker Xenon-nano 1.6 software, and then the “Spinfit” function
2
xi W0 1 − Aad,i − Mad,i
was applied to obtain the g-values, line-shapes, line-widths, and spin i=1

concentrations. The detailed information and operating conditions were

described in our previous study [30,31]. Ygas (wt.%) = 100 − Ytar − Ychar − Ywater (4)
Pyrolysis products were classified as tar, gas, water, and char, and
where W0, Wtar, Wwater, Wchar, and Wgas represents the weight of py­
the yields of pyrolysis products on a dry ash-free basis (Ytar, Ygas, Ywater,
rolysis sample, tar, water, char, and gas, respectively. Aad,i and Mad,i is
and Ychar) were calculated by Eqs. (1)–(4).
ash and moisture content of coal, WPE, or BPE on an air-dried basis,
Wtar respectively. xi is the mass content of coal or PE in the mixture. It is
Ytar (wt.%) = × 100 (1)
∑
2 ( ) noteworthy that the obtained results are the average of at least three
xi W0 1 − Aad,i − Mad,i
i=1 equivalent experiments.
The synergistic effect of co-pyrolysis of coal and waste PE was esti­
∑
2
mated according to the deviation values, which were defined by the
Wwater − xi W0 Mad,i
difference (ΔY) between experimental (Yexp.) and calculated yields
Ywater (wt.%) = i=1
× 100 (2)
∑
2 ( ) (Ycal.), as depicted by Eq. (5). In detail, the Ycal. is the sum of coal and
xi W0 1 − Aad,i − Mad,i
i=1 waste PE individually in proportion to mass, and its formula is shown by
Eq. (6).
ΔY = Yexp. − Ycal. (5)

Fig. 2. Effect of pyrolysis temperature on products distribution (a), gas compositions (b), and content of fractions in tar (c) during coal pyrolysis at 20 ◦ C/s.

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Y. Wu et al.
Ycal. = x1 Y1 + x2 Y2
where x1, x2 are the mass content of coal (or waste PE) in mixture, while
Y1, Y2 are the experimental yields from individual pyrolysis of coal and
waste PE.
3. Results and discussion
3.1. Effect of pyrolysis temperatures on coal pyrolysis
Fig. 2a shows the effect of pyrolysis temperature on the product
distribution of coal pyrolysis at 20 ◦ C/s. As can be seen, the tar yield
increases from 15.37 wt% to 20.46 wt% with the pyrolysis temperature
from 450 ◦ C to 550 ◦ C but slightly decreases at 650 ◦ C. In comparison,
the char yield exhibits an opposite trend, sharply decreasing from 78.22
wt% to 64.37 wt% at below 550 ◦ C. Moreover, the yields of gas and
water gradually increase from 3.07 wt% and 3.34 wt% to 11.09 wt% and
6.87 wt%, respectively, with the increasing temperature. These results
indicate that high temperature is conducive to the secondary cracking of
volatiles to form small molecule gases, and enhances the esterification
and dehydrogenation reactions of phenolic hydroxyl and carboxyl
groups to form H2O [32].
Fig. 2b displays the yields of gas compositions from coal pyrolysis. It
can be observed that the pyrolysis temperature has an obvious effect on
the release of CH4 and H2. When increasing the temperature, the H2
yield slowly increases at below 550 ◦ C and then sharply rises from 20.03
mL/g to 52.42 mL/g at 550–650 ◦ C. Meanwhile, the CH4 yield gradually
increases from 9.95 mL/g to 26.15 mL/g. These results illustrate that
higher temperature is conducive to promoting the secondary reactions
of aromatics and hydrocarbons to form small molecule gases [33,34]. In
comparison, the yields of CO, CO2, and C2–C3 are relatively low and
mildly increase at temperatures of 600 ◦ C and 650 ◦ C. Among them, CO
is mainly generated from the cleavage of ether linkages, carbonyl,
Fig. 3. Products distribution and their synergistic values (ΔY) during co-pyrolysis of coal with WPE or BPE at varied mixing ratios: (a) tar; (b) gas; (c) char; and
(d) water.
Journal of the Energy Institute 102 (2022) 384–394
(6) phenolic, and oxygen heterocycles groups, while CO2 is derived from the
decomposition of aliphatic, aromatic carboxyl, carboxylate groups, and
some carbonate minerals [24,25,35]. For C2–C3 hydrocarbon gases, the
formation mainly comes from the scission of aliphatic hydrocarbons and
alkyl side chains on aromatic rings.
Fig. 2c depicts the distribution of tar fractions from coal pyrolysis at
varied pyrolysis temperatures. As can be seen, the content of light
fraction reaches the maximum value of 11.0% at 600 ◦ C and is low at
650 ◦ C. This indicates that too high pyrolysis temperature is unfavorable
to the generation of light fraction in tar because high temperature
intensified the polycondensation of light volatiles from coal pyrolysis,
resulting in the formation of more heavy components in tar. In addition,
the medium fraction exhibits a mild change with pyrolysis temperature,
and the tar produced from coal pyrolysis at 600 ◦ C contains the highest
medium fraction of 39.5%.
3.2. Products distribution in co-pyrolysis of coal with WPE or BPE
3.2.1. Product yields
In our previous work, it was found that the LDPE pyrolysis has the
highest tar yield and higher tar quality at 550 ◦ C [29], and this tem­
perature also corresponds to that with the highest tar yield during coal
pyrolysis, as shown in Fig. 2a. Consequently, 550 ◦ C was determined as
the temperature for fast co-pyrolysis of coal and waste PE.
Fig. 3 presents the products distribution and their synergistic values
(ΔY) during co-pyrolysis of coal with WPE or BPE at varied mixing ra­
tios. As can be seen, WPE and BPE exhibit different pyrolysis behaviors.
In detail, the WPE pyrolysis produces more liquid tar with a yield of
93.22 wt% (see Fig. 3a), which is consistent with that of virgin LDPE
pyrolysis (93.42 wt%) [29], while the BPE pyrolysis has a low yield of
tar, but high yields of char and water being 6.70 wt% and 1.41 wt%,
respectively (see Fig. 3b and c). Among them, the pyrolysis residue is
mainly derived from inorganic filler in BPE because they have high
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stability, while water formation is attributed to the dehydroxylation of

phenolic antioxidants in BPE. These results indicate that the presence of
additives in PE causes the diversity of PE pyrolysis products. Obviously,
the mixing ratio also has a vital effect on products distribution during
the co-pyrolysis process. As shown in Fig. 3a, co-pyrolysis with a lower
WPE (or BPE) content in mixtures (i.e., coal/PE = 9:1) has a negative
synergetic effect (ΔY < 0) on tar yield, whereas appears the positive
synergetic effect (ΔY > 0) when the WPE (or BPE) content exceeds 30%
(i.e., coal/PE = 7:3, 1:1). These results illustrate that higher content of
WPE (or BPE) in blends is conducive to promoting volatile-volatile in­
teractions during the co-pyrolysis process to form liquid tar. Moreover,
the co-pyrolysis of coal and WPE shows a better promotion effect for tar
than that of coal and BPE, and the best performance corresponding to
the ΔY = 6.23 wt% is observed at the mixing ratio of 7:3 for coal/WPE.
The gas yield (Fig. 3b) is lower than the calculated value (ΔY < 0),
which illustrates that co-pyrolysis inhibits the release of gases. This is
since the molten plastic is easy to coat the surface of coal particles at the
initial stage of co-pyrolysis, thereby suppressing the release of volatiles
from coal pyrolysis [30,36]. However, this negative synergetic effect
gradually decreases with the increase of WPE (or BPE) ratio. It is likely
since a higher PE content can release abundant volatiles, which helps
expand the interstice of the material layer, thus promoting the second­
ary cracking of char. Meanwhile, this is also the main reason for the
negative synergy in char yield, especially for the coal/WPE char, the ΔY
values have an obvious decline from 6.33 wt% to − 4.18 wt% (see
Fig. 3c). As shown in Fig. 3d, the water yield was inhibited with the
addition of WPE into the coal, and the largest negative synergistic effect
(ΔY = − 1.22 wt%) can be observed at coal/WPE ratio of 7:3 but was
promoted with the addition of BPE, which illustrates that the interaction
between volatiles from coal and phenolic antioxidants facilitated
dehydroxylation to form H2O.

3.2.2. Gas compositions

Fig. 4 shows the experimental and calculated gas yields during co-
pyrolysis of coal with WPE or BPE at varied mixing ratios. Obviously,
WPE and BPE exhibit different effects on the escape of gases during the
co-pyrolysis process. As described in Fig. 4a, co-pyrolysis of coal/WPE
has a greater inhibition effect on H2 production than that of coal/BPE,
especially in the mixing ratios of 9:1 and 1:1. Additionally, co-pyrolysis
also inhibits CO production, in which coal/WPE has a more distinct
inhibition than that of coal/BPE (see Fig. 4b). When the mixing ratio
reaches 1:1, the CO yield is the same as that of individual WPE or BPE
pyrolysis, indicating that excessive molten PE covers the surface of coal
particles to inhibit the formation of CO from the cracking of ether bonds,
carbonyl groups, phenols [24,37]. Moreover, BPE pyrolysis alone can
produce 2.66 mL/g CO2 (see Fig. 4c), which is derived from the degra­
dation of OPAs in BPE. This also results in higher CO2 yield from
co-pyrolysis of coal/BPE than that of coal/WPE. As for the CH4 (Fig. 4d),
its yield is higher than the calculated values at a low WPE or BPE mixing
ratio (i.e., coal/WPE = 9:1), when the mixing ratio increases to 7:3 and
1:1, the CH4 yield is lower than the calculated values (ΔY < 0). As for the
C2–C3 hydrocarbon gases, its yield from BPE pyrolysis is 12.99 mL/g,
higher than that from WPE (10.30 mL/g), and far higher than the yield
of 3.46 mL/g from coal pyrolysis. In the co-pyrolysis process, the gen­
eration of C2–C3 exhibits a distinct inhibition effect.
Fig. 4. Gas contents and their calculated values during the co-pyrolysis of coal
with WPE or BPE at varied mixing ratios: (a) H2; (b) CO; (c) CO2; (d) CH4; and
(e) C2–C3.
ratio of WPE. Compared to the light fraction, the medium fraction shows
a higher negative synergetic effect, and the ΔYMedium is from − 12.40%
to − 13.80%. In comparison, the addition of BPE can improve the light
tar fraction (Fig. 5b), and the light tar fraction content is higher than the
calculated value. When the coal/BPE mixing ratio is 9:1, the ΔYLight is
6.00%, but it decreases to 0% with the increasing BPE ratio. For the
medium fraction, its content is lower than the calculated values, and the
ΔYMedium shows a decreasing trend from − 1.05% to − 6.75% with the
increasing BPE ratio, which indicates that the co-pyrolysis of coal/BPE
inhibits the formation of medium fraction. Conversely, the ΔYHeavy for
heavy fraction exhibits an increasing trend from − 4.95% to 6.75%.

3.3. Tar characterization 3.3.2. Tar composition

3.3.1. Tar fractions distribution
Fig. 5 illustrates the tar fractions distribution and synergistic effects
(ΔY) during co-pyrolysis of coal with WPE or BPE at varied mixing ra­
tios. As can be seen from Fig. 5a, the addition of WPE evidently increases
the content of heavy fractions in tar, with a remarkable positive syner­
getic effect of ΔYHeavy from 14.50% to 17.00%. Conversely, the content
of light and medium fractions decreases, and the inhibition effect of light
fraction increases from − 2.10% to − 4.50% with the increasing mixing
The detailed analysis of tar compositions was conducted on GC-MS,
and the compounds in tar were qualified according to the NIST 05 li­
brary and quantified using the area normalization method [38,39], the
results are listed in Table 2. Herein, the main compounds in tar are
divided into alkenes, alkanes, aromatics, and phenols. As can be
observed, most of alkenes are derived from the pyrolysis of WPE (or
BPE), such as 1-decene (WPE: 1.99%, BPE: 2.13%), 1-undecene (1.84%,
1.92%), 1-tetradecene (1.86%, 1.86%), 1-pentadecene (1.98%, 1.89%),

388
Y. Wu et al.
Fig. 5. Tar fraction distribution and their synergistic values (ΔY) during the co-pyrolysis of coal with WPE or BPE at varied mixing ratios: (a) coal/WPE, (b)
coal/BPE.
1,13-tetradecadiene (0.55%, 0.63%), and 1,19-eicosadiene (0.56%,
0.66%), while only a few alkenes are attributed to the coal pyrolysis,
such as 1-nonene (0.49%), 1-dodecene (1.57%), 1-tetradecene (0.61%),
which are mainly derived from the decomposition of aliphatic side
chains in coal [40]. Similarly, the alkanes, formed in pyrolysis of WPE
(or BPE), mainly consist of undecane (1.20%, 0.76%), pentadecane
(1.24%, 0.75%), hexadecane (1.32%, 0.95%), and heptadecane (1.31%,
0.80%). However, the content of alkanes is lower than that of alkenes,
which is mainly that high temperature facilitates the H-transfer in
saturated alkanes to form unsaturated alkenes, thereby increasing the
content of unsaturated alkenes [41]. Compared to aliphatic hydrocar­
bons, aromatics are mainly produced from coal pyrolysis. The aromatic
compounds in coal pyrolysis tar are composed of monocyclic aromatic
hydrocarbons (MAHs) and polycyclic aromatic hydrocarbons (PAHs).
Among them, MAHs mainly include toluene (1.41%), p-xylene (1.69%),
1-ethyl-3-methyl-benzene (0.72%), and 1,2,3-trimethyl-benzene,
(0.87%), while PAHs mainly consist of 2-methyl-indene (1.27%),
1-methyl-naphthalene (1.16%), 2,3-dimethyl-naphthalene (0.86%), 1,
6-dimethyl-naphthalene (1.01%), and 2,3,6-trimethyl-naphthalene
(0.92%). Intriguingly, MAHs are found in BPE pyrolysis tar such as
toluene (0.49%), p-xylene (0.13%), and o-xylene (0.35%) but not
detected in WPE pyrolysis tar, indicating that MAHs are formed ascribes
to the pyrolysis of OPAs in BPE. Phenols, as another major product in
coal pyrolysis, mainly include phenol (5.50%), 2-methyl-phenol
(3.76%), 4-methyl-phenol (6.81%), 2,3-dimethyl-phenol (3.34%),
3-ethyl-5-methyl-phenol (1.20%), 2-methyl-1-naphthalenol (0.77%),
and 4-methyl-1-naphthalenol (0.15%).
The difference from the volatile-volatile interactions between coal
with WPE (or BPE) was further evaluated by comparing the deviation
ΔY between the experimental and calculated values, which represents
the synergetic effect between coal and PE. Fig. 6 gives the synergetic
effects from alkenes, alkanes, aromatics (MAHs and PAHs), and phenols
in tars under varied coal/WPE (or BPE) mixing ratios.
It can be seen that the experimental values of alkenes and alkanes are
generally higher than the calculated values (ΔY > 0) (see Fig. 6a, b, e, f),
suggesting that the co-pyrolysis can promote the cleavage of C–C bond in
PE to form aliphatic hydrocarbons. In the coal/WPE co-pyrolysis, the
mixing ratio of 7:3 shows a stronger positive synergetic effect on alkenes
production than other mixing ratios, such as 1-decene and 1-undecene,
the ΔY is 1.40% and 1.18%, respectively (see Fig. 6a). In comparison,
adding less BPE, namely coal/BPE (9:1), is more favorable to alkenes
production such as 1-octene (0.90%), 1-decene (1.68%), 1-undecene
(1.42%), and 1-pentadecene (1.51%) (see Fig. 6e). However, the ΔY
gradually decreases with the increasing mixing ratio of BPE, indicating
that adding excessive BPE weakens the positive synergetic effect. As for
the alkane products, they are significantly promoted with the addition of
WPE (or BPE), and the C13–C20 hydrocarbons are higher than C7–C12
ones, which indicates that the co-pyrolysis interactions inhibit the
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secondary cracking of C13–C20 long-chain alkanes (see Fig. 6b, f).
Moreover, the co-pyrolysis of coal/BPE exhibits a positive performance
than coal/WPE for alkanes production under a high PE mixing ratio (i.e.,
1:1). Compared with alkene and alkane compounds, aromatics and
phenols show a significantly opposite effect (ΔY < 0), as shown in
Fig. 6c, d, g, h. This result indicates that the long-chain aliphatic hy­
drocarbons from PE pyrolysis adhere to the surface of coal particles,
inhibiting the breaking of chemical bonds such as C–C, C–O in coal to
generate aromatics and phenols [30]. However, the negative synergetic
effects in the formation of aromatic and phenolic compounds such as
toluene, 1-methyl-naphthalene, 1,6-dimethyl-naphthalene (see Fig. 6c,
g), as well as phenol, 4-methyl-phenol (see Fig. 6 d, h) are weakened
with the addition of WPE (or BPE). Generally, it was well accepted that
adding large amounts of PE in blends during the co-pyrolysis process
could suppress the escape of volatiles from coal pyrolysis. However, the
unescaped volatiles can undergo cross-link reactions with alkyl or
alkenyl radicals from PE cracking to form heavy tar or char in coal pores
or surfaces [42,43]. With the escape of large amounts of volatiles from
PE pyrolysis, char pores are enlarged, while the heavy tar attached to the
pore wall escapes and further undergoes secondary reaction with char to
form MAHs or phenols, thereby reducing the negative synergistic effect.
3.4. Char characteristics
3.4.1. Char morphology, proximate and ultimate analyses
As mentioned above, excessive molten PE coats the surface of coal
particles affected the escape of volatiles, and initiating secondary re­
actions on char surfaces. To verify this viewpoint, the characteristics of
pyrolytic chars were investigated. Fig. 7 displays the morphologies of
pyrolysis/co-pyrolysis chars of coal, WPE (or BPE), and their blends at
550 ◦ C. As can be seen, the surface of coal char is relatively slick and has
no obvious potholes (Fig. 7a). However, when the mixing ratio of coal/
WPE is 1:1, visible pores can be observed on the surface of char particles
(Fig. 7d), indicating that the rapid escape of PE volatiles promotes the
expansion of char pores, which can well explain the volatilization and
secondary cracking of heavy tar attached to pores. Meanwhile, the
surface of coal/BPE char particles becomes highly rough (see Fig. 7b–g),
which further explained the above results that the aliphatic radicals
generated from molten PE cracking reacted with volatiles from coal on
the surface of char particles. In addition, it can be observed from Fig. 7h
that the particle size of BPE char is relatively small, and the surface is
smooth and flat, which is mainly the filler in BPE, while WPE char
cannot be observed due to the char yield is almost zero.
Table 3 lists the proximate and ultimate analyses results of char
samples obtained from pyrolysis of coal, WPE (or BPE), and their mix­
tures at 550 ◦ C. Compared with the proximate analysis of coal char,
adding WPE has a slight effect on the ash content in coal/WPE char
(32.21 wt%− 32.84 wt%), whereas the addition of BPE significantly
Y. Wu et al. Journal of the Energy Institute 102 (2022) 384–394

Table 2
Main compounds detected in tars from co-pyrolysis of coal with WPE or BPE at varied mixing ratios.
No. R.T. Compounds coal coal/WPE coal/WPE coal/WPE WPE coal/BPE coal/BPE coal/BPE BPE
(min) (1:0) (9:1) (7:3) (1:1) (0:1) (9:1) (7:3) (1:1) (0:1)

Alkenes
1 5.70 1-Heptene 0.00 0.05 0.15 0.17 0.20 0.15 0.17 0.35 0.29
2 8.27 1-Octene 0.00 0.41 0.71 0.69 0.79 0.97 0.54 0.75 0.69
3 11.62 1-Nonene 0.49 0.73 1.08 1.06 1.09 0.85 0.65 0.85 0.95
4 15.08 1-Decene 0.41 1.49 2.28 2.10 1.99 2.26 1.70 2.09 2.13
5 18.44 1-Undecene 0.45 1.50 2.05 1.83 1.84 2.02 1.64 1.96 1.92
6 22.91 1-Dodecene 1.57 1.49 1.84 1.84 1.64 1.74 1.36 1.62 1.55
7 27.18 1-Tridecene 0.50 1.25 1.59 1.50 1.66 1.47 1.42 1.64 1.57
8 30.65 1-Tetradecene 0.61 1.52 1.91 1.79 1.86 1.65 1.65 1.98 1.86
9 33.59 1-Pentadecene 0.00 1.50 1.87 1.81 1.98 1.70 1.68 2.02 1.89
10 36.20 7-Hexadecene, (Z)- 0.00 1.34 1.67 1.62 1.79 1.43 1.43 1.74 1.59
11 38.58 1-Heptadecene 0.17 1.14 1.50 1.54 1.72 1.38 1.26 1.66 1.58
12 41.31 1-Octadecene 0.00 1.09 1.50 1.58 1.66 1.26 1.39 1.59 1.59
13 44.64 1-Nonadecene 0.00 0.97 1.22 1.49 1.50 1.26 1.23 1.43 1.53
14 47.62 5-Eicosene, (E)- 0.00 0.82 0.98 1.36 1.19 1.08 1.03 1.19 1.41
15 11.31 1,8-Nonadiene 0.00 0.00 0.00 0.15 0.11 0.00 0.08 0.08 0.15
16 14.78 1,9-Decadiene 0.00 0.00 0.32 0.28 0.19 0.22 0.37 0.26 0.28
17 18.11 1,10-Undecadiene 0.00 0.20 0.30 0.50 0.22 0.09 0.47 0.51 0.50
18 22.46 1,11-Dodecadiene 0.29 0.00 0.19 0.29 0.24 0.00 0.23 0.35 0.45
19 26.83 1,12-Tridecadiene 0.00 0.41 0.54 0.62 0.47 0.59 0.48 0.50 0.62
20 33.35 1,13-Tetradecadiene 0.00 0.40 0.53 0.63 0.55 0.53 0.43 0.56 0.63
21 38.38 1,19-Eicosadiene 0.00 0.42 0.48 0.66 0.56 0.58 0.49 0.57 0.66
Alkanes
22 5.87 Heptane 0.00 0.04 0.11 0.11 0.19 0.16 0.11 0.23 0.23
23 8.53 Octane 0.00 0.31 0.50 0.44 0.64 0.35 0.36 0.48 0.44
24 11.91 Nonane 0.26 0.52 0.69 0.62 0.88 0.43 0.47 0.73 0.48
25 15.36 Decane 0.61 0.68 0.86 0.68 0.94 0.61 0.66 0.53 0.61
26 18.75 Undecane 0.39 0.77 1.00 0.81 1.20 0.62 0.73 0.87 0.76
27 23.29 Dodecane 0.76 0.84 0.96 0.80 1.16 0.54 0.75 0.86 0.74
28 27.48 Tridecane 0.00 1.10 1.02 0.80 1.12 0.56 0.88 0.90 0.69
29 30.88 Tetradecane 0.00 0.83 0.92 0.77 1.05 0.66 0.77 0.85 0.62
30 33.79 Pentadecane 0.34 0.83 0.97 0.83 1.24 0.59 0.80 0.94 0.75
31 36.36 Hexadecane 0.00 0.91 1.04 0.92 1.32 0.96 1.05 1.24 0.95
32 38.74 Heptadecane 0.32 0.82 0.99 0.89 1.31 0.65 0.86 0.98 0.80
33 41.51 Octadecane 0.17 0.73 1.24 0.88 1.23 0.68 1.00 1.12 0.75
34 44.85 Nonadecane 0.13 0.75 1.02 0.90 1.29 0.59 0.82 1.13 0.79
35 47.80 Eicosane 0.10 0.82 0.99 0.90 1.21 0.50 0.98 1.14 0.84
Aromatics
36 7.61 Toluene 1.41 0.41 0.35 0.16 – 0.14 0.19 0.17 0.49
37 10.64 Ethylbenzene 0.37 0.11 0.14 0.08 – 0.25 0.08 0.00 –
38 10.93 p-Xylene 1.69 0.46 0.31 0.13 – 0.71 0.20 0.13 0.13
39 11.74 o-Xylene 0.71 0.21 0.13 0.06 – 0.43 0.47 0.42 0.35
40 14.12 Benzene, 1-ethyl-3- 0.72 0.23 0.15 0.00 – 0.19 0.07 0.00 –
methyl-
41 14.35 Benzene, 1,3,5-trimethyl- 0.22 0.09 0.07 0.00 – 0.09 0.04 0.00 –
42 15.24 Benzene, 1,2,3-trimethyl- 0.87 0.28 0.23 0.12 – 0.36 0.20 0.15 –
43 16.19 Benzene, 1,2,4-trimethyl- 0.39 0.20 0.14 0.07 – 0.13 0.09 0.00 –
44 16.93 Benzene, 1-propynyl- 0.60 0.09 0.07 0.06 – 0.21 0.03 0.00 –
45 20.53 Benzene, 1-ethenyl-4- 0.17 0.11 0.09 0.05 – 0.22 0.00 0.00 –
ethyl-
46 21.02 2-Methylindene 1.27 0.33 0.15 0.00 – 0.41 0.15 0.00 –
47 28.09 Naphthalene, 1-methyl- 1.16 0.38 0.17 0.10 – 0.23 0.11 0.00 –
48 31.68 Naphthalene, 2,3- 0.86 0.28 0.17 0.14 – 0.27 0.09 0.07 –
dimethyl-
49 31.79 Naphthalene, 2,6- 0.83 0.32 0.18 0.14 – 0.30 0.09 0.06 –
dimethyl-
50 32.27 Naphthalene, 2,3- 0.44 0.11 0.04 0.08 – 0.19 0.08 0.08 –
dimethyl-
51 32.36 Naphthalene, 1,4- 0.37 0.17 0.07 0.00 – 0.19 0.09 0.08 –
dimethyl-
52 32.72 Naphthalene, 1,6- 1.01 0.23 0.08 0.05 – 0.10 0.00 0.02 –
dimethyl-
53 34.69 Naphthalene, 1,4,6- 0.34 0.18 0.08 0.06 – 0.15 0.07 0.06 –
trimethyl-
54 35.25 Naphthalene, 1,6,7- 0.42 0.13 0.11 0.00 – 0.13 0.03 0.00 –
trimethyl-
55 35.71 Naphthalene, 2,3,6- 0.92 0.14 0.06 0.03 – 0.11 0.03 0.04 –
trimethyl-
Phenols
56 14.76 Phenol 5.50 1.33 0.51 0.18 – 1.01 0.37 0.26 –
57 17.20 Phenol, 2-methyl- 3.76 0.94 0.49 0.09 – 1.19 0.28 0.18 –
58 17.96 Phenol, 4-methyl- 6.81 1.56 0.70 0.16 – 2.02 0.40 0.50 –
59 20.29 Phenol, 2-ethyl- 0.43 0.15 0.10 0.06 – 0.04 0.00 0.00 –
(continued on next page)

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Y. Wu et al. Journal of the Energy Institute 102 (2022) 384–394

Table 2 (continued )
No. R.T. Compounds coal coal/WPE coal/WPE coal/WPE WPE coal/BPE coal/BPE coal/BPE BPE
(min) (1:0) (9:1) (7:3) (1:1) (0:1) (9:1) (7:3) (1:1) (0:1)

60 20.86 Phenol, 2,3-dimethyl- 3.34 0.83 0.34 0.12 – 0.22 0.29 0.21 –
61 21.83 Phenol, 3,5-dimethyl- 2.60 0.70 0.36 0.00 – 0.53 0.13 0.00 –
62 25.03 Phenol, 2-ethyl-4-methyl- 0.65 0.25 0.12 0.05 – 0.17 0.04 0.03 –
63 25.93 Phenol, 3-ethyl-5-methyl- 1.20 0.52 0.17 0.03 – 0.33 0.17 0.07 –
64 36.88 1-Naphthalenol, 2- 0.77 0.21 0.16 0.03 – 0.12 0.06 0.09 –
methyl-
65 37.28 1-Naphthalenol, 4- 0.15 0.29 0.12 0.08 – 0.18 0.04 0.08 –
methyl-

Fig. 6. Synergetic effects from main compounds in tars obtained at varied coal/WPE (or BPE) mixing ratios: (a, e) alkenes; (b, f) alkanes; (c, g) aromatics; (d, h)
phenols. The numbers 1–65 correspond to the compounds in Table 2.

increases ash content in coal/BPE char from 32.50% to 35.52 wt%.
Meanwhile, the mixing of WPE and BPE also increases the volatile
content in coal/WPE and coal/BPE chars from 11.33 wt% and 11.19 wt
% to 12.24 wt% and 15.38 wt%, respectively. This is since the volatiles
from coal pyrolysis were blocked in char pores by molten PE. As pre­
sented in the ultimate analysis, the H/C ratio of coal char is 0.36, but the
H/C ratios of mixture chars decrease with the addition of PE, revealing
that hydrogen is transferred from solid char to liquid products. As for the
oxygen content in the char, the content of coal char is only 4.37 wt%, but
the co-pyrolysis with PE hinders the escape of O-containing compounds,
especially for the oxygen content in coal/BPE chars increase from 6.49
wt% to 7.76 wt%. In addition, the nitrogen and sulfur contents in char
increase, which elucidated that co-pyrolysis also can restrain the escape
of nitrogen and sulfur in coal.
3.4.2. EPR analysis
To further reveal the complicated interaction mechanisms during the
co-pyrolysis process, the evolution of stable radicals in co-pyrolysis
chars was investigated by EPR analysis. Fig. 8 gives the EPR spectrum
and corresponding fitted sub-curves of char samples from coal/WPE (or
BPE) pyrolysis with varied mixing ratios. In comparison, no EPR signal
was detected in BPE residue (see Fig. S2), indicating that no stable
radicals were produced during BPE pyrolysis. While WPE residue could
not be collected for EPR detection because only a small amount of res­
idue (0.80 wt%, see Fig. 3c) was obtained during WPE pyrolysis. Among
them, the EPR spectrum in chars are symmetrical absorption lines
without hyperfine structure, and the multiple sub-curves obtained via
Xenon-nano software can determine the hybrid nature of stable radicals
[31,44]. The detailed fitted parameters including g-value, linewidth,
lineshape, and spin concentration are listed in Table S2. As indicated in
Fig. 8, the fitted sub-curves are attributed to the C-centered with oxygen
radicals (g = 2.00373–2.00382), 1–3 rings π-type quinone radicals or
mono-, di-, tri-methoxybenzene ethers radicals (g = 2.00387–2.00401),
nitroxide radicals (g = 2.00640–2.00776), and peroxide radicals (g =
2.01172–2.01251), respectively [45–47].
The evolution of stable radicals during co-pyrolysis of coal with WPE
or BPE was quantified by spin concentrations (Ng) using the area
normalization method, and the results of different nonmagnetic nucleus-
centered radicals (i.e., C-, O-, N-centered) were depicted in Fig. 9.
Clearly, adding WPE and BPE exhibited a diverse effect on the Ng of C-,

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Y. Wu et al. Journal of the Energy Institute 102 (2022) 384–394

Fig. 7. SEM images of char samples with varied WPE (or BPE) addition: (a) coal char, (b–d) coal/WPE char under varied mixing ratios, (e–g) coal/BPE char under
varied mixing ratios, and (h) BPE char.

Table 3
Proximate and ultimate analyses of char samples from coal and WPE (or BPE) mixtures pyrolysis at 550 ◦ C.
Sample Proximate analysis (wt%) Ultimate analysis (wt%, daf) H/C
a
Ad Vdaf FCdaf C H N S O

Coal char 32.10 11.18 88.82 88.26 2.68 3.89 0.80 4.37 0.36
Coal/WPE char 9:1 32.21 11.33 88.67 87.90 1.98 4.69 0.76 4.67 0.27
7:3 32.84 11.70 88.30 87.85 2.05 5.20 0.87 4.03 0.28
1:1 32.98 12.24 87.76 84.97 2.13 5.30 1.20 6.40 0.30
Coal/BPE char 9:1 32.50 11.19 88.81 86.46 2.00 4.20 0.85 6.49 0.28
7:3 33.74 13.08 86.92 85.23 1.92 4.29 0.86 7.70 0.27
1:1 35.52 15.38 84.62 84.93 1.91 4.47 0.93 7.76 0.27

Ad: ash content on dry basis; Vdaf: volatile matters content on dry and ash-free basis; FCdaf: fixed carbon content on dry and ash-free basis.
a
by difference.

Fig. 8. EPR spectrum and fitted sub-curves of char samples at 550 ◦ C: (a) coal char, (b–d) coal/WPE chars under varied mixing ratios, (e–g) coal/BPE chars under
varied mixing ratios.

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Y. Wu et al.
Fig. 9. Spin concentrations of char samples from co-pyrolysis of coal and WPE
(or BPE) mixtures at 550 ◦ C.
O-, N-centered radicals. In detail, the Ng of C-centered radicals in coal/
WPE chars increased from 5.24 × 1018 spins/g to 7.22 × 1018 spins/g
with the addition of WPE, while the BPE addition has a slight promotion
on the C-centered radicals in coal/BPE chars, its Ng increases from 5.76
× 1018 to 5.99 × 1018 spins/g. This result indicates that the co-pyrolysis
of coal/WPE is more favorable to form C-centered radicals than that of
coal/BPE. As for the O-centered radicals in chars, coal char has a lower
Ng value of 10.37 × 1018 spins/g, while the co-pyrolysis chars from
coal/WPE and coal/BPE increase to 10.93 × 1018–11.81 × 1018 spins/g
and 10.96 × 1018–10.93 × 1018 spins/g with the waste PE addition,
which verifies that co-pyrolysis interaction inhibits the escape of phe­
nols and converted to stable O-centered radicals. Furthermore, with the
addition of WPE and BPE, the Ng of N-centered radicals gradually de­
clines from 4.07 × 1018 spins/g to 2.54 × 1018 and 2.45 × 1018 spins/g,
respectively. It was generally accepted that the H-radicals from PE py­
rolysis can hydrogenate with the N-containing aromatics in coal to form
NH3 during the co-pyrolysis process [48,49], thus resulting in the con­
sumption of N-centered radicals.
4. Conclusion
In this work, a newly infrared-heated fixed-bed reactor was applied
to provide a rapid heating rate to explore the synergistic effects between
volatile-volatile interactions during co-pyrolysis of coal and waste PE
and observe the effect of OPAs in waste PE on co-pyrolysis interactions.
The results show that the optimal temperature of coal pyrolysis at a high
heating rate of 20 ◦ C/s is determined as 550 ◦ C. Under the same con­
ditions, the pyrolysis of two waste PE exhibits significantly different
products distribution, in which WPE has a high tar yield of 93.22 wt%,
while BPE produces more char and water due to the high thermal sta­
bility of inorganic fillers and the dehydroxylation of phenolic antioxi­
dants. During the co-pyrolysis of coal with waste PE, coal/WPE is
conducive to promoting the volatile-volatile interactions to form liquid
tar, the maximum ΔY is 6.23 wt% at mixing ratio 7:3 for coal/WPE. In
comparison, coal/BPE co-pyrolysis has a slight impact on the tar yield
but significantly enhances the light fractions in tar, the maximum
ΔYLight reaches 6.00% at mixing ratio 9:1 for coal/BPE due to the in­
teractions between antioxidant volatiles in BPE and coal volatiles. Tar
compositions analysis revealed volatile-volatile interactions promoted
the cracking of long-chain PE to form short-chain aliphatic hydrocar­
bons, and inhibited the cleavages of C–C and C–O bonds in coal to
generate aromatics and phenols. Moreover, the volatile-volatile
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Journal of the Energy Institute 102 (2022) 384–394
interactions also were affected by the mixing ratio of coal/PE. Adding
excessive PE can weaken the negative synergistic effect of MAHs and
phenols, indicating that the primary volatiles from coal pyrolysis were
hindered cross-linked with alkenyl and alkyl radicals from PE cracking
to produce heavy oil in pores and surface of coal particles, and further
undergoes secondary cracking and escape. Furthermore, co-pyrolysis
chars have a lower H/C ratio and higher C-centered radical concentra­
tions than coal char, further demonstrating that H has been transferred
to the liquid products, which can provide an effective complement for
understanding the co-pyrolysis interactions.
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.
Acknowledgments
The authors are grateful to the financial support from the National
Natural Science Foundation of China (No. 22078053), Innovation Team
Support Program in Key Areas of Dalian Science and Technology Bureau
(2019RT10), the Fundamental Research Funds for the Central Univer­
sities (DUT2021TB03), and Liaoning Revitalization Talent Project
(XLYC1908033).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.joei.2022.05.005.
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