Fuel 359 (2024) 130519

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Fuel
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Co-pyrolysis of Hami coal and mixed plastic: An interaction between

primary volatiles study via in-situ Py-TOF-MS
Tingting Zhang a, b, Zongqing Bai a, *, Hongyan Zheng c, Haoyu Dou a, b, Zhenxing Guo a,
Lingxue Kong a, Jin Bai a, Wen Li a
a
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, PR China
b
University of Chinese Academy of Sciences, Beijing 100049, PR China
c
Department of Chemistry and Chemical Engineering, Taiyuan Institute of Technology, Taiyuan 030008, PR China

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

Keywords: Online detection of pyrolysis volatiles is essential for exploring the mechanism of coal and plastics co-pyrolysis.
Low rank coal In-situ pyrolysis time-of-flight mass spectrometry (Py-TOF-MS) equipped with double ionization sources, vacuum
Mixed plastic ultraviolet photoionization (VUVPI) and electron ionization (EI), was used to analyze the release of primary
Co-pyrolysis
volatiles during the pyrolysis and co-pyrolysis of Hami coal (HM) with mixed plastic (PP/LDPE and PP/LDPE/PS,
In-situ Py-TOF-MS
with ratios of 3:2 and 12:8:1, respectively). Meanwhile, the interaction mechanism was discussed at the mo­
lecular level. According to the thermogravimetric (TG) results and the total ion currents (TIC) of primary vol­
atiles with temperature, the inclusion of plastic shortens the overall reaction time. In-situ Py-TOF-MS results
indicate that the volatiles produced from HM pyrolysis at lower temperatures induce the decomposition of PP
and promote further dehydrogenation of long-chain C–C. Besides, the addition of PP visibly facilitates the
transportation of hydrogen, which reacts with phenoxy from HM pyrolysis to produce diphenol. The further
addition of LDPE after PP enhances the inhibitory effect of molten plastic on HM pyrolysis, resulting in a decrease
in the content of diphenol, such as benzenediol (from 1.34% to 0.71%), methyl-benzenediol (from 1.12% to
0.68%) and dimethyl benzenediol/ethyl benzenediol (from 0.68% to 0.50%). The co-pyrolysis of HM with PP/
LDPE/PS generates more aromatic products compared to that of theoretical value, such as styrene (from 0.29% to
3.16%), 1-ethenyl-3-methyl benzene (from 0.07% to 0.31%) and 1-butene-2,4-diphenyl (from 0.19% to 0.65%).
This indicates that co-pyrolysis strengthens the breakage of Car-Cβ bond in the PS backbone. The addition of PS to
the mixture plastic also promotes intramolecular and intermolecular hydrogen transfer in the system. For the
evolution of inorganic gases, the addition of mixed plastics promotes the decomposition of aliphatic and aromatic
carboxylic acids in coal at lower temperatures, resulting in a decrease in CO2.

1. Introduction
The increase in population and continuous improvement in the
standards of people’s living have led to a continuous rise in the energy
demand. Until 2021, coal is still the main source of energy consumption
in China, accounting for 57.7 % of total energy consumption [1].
Therefore, the energy structure dominated by coal will not change in the
short term. Low-rank coal is increasingly valued in the field of coal
utilization due to their large reserves and low mining costs. Pyrolysis is
regarded as a promising method for converting coal into chemicals with
high added-value under mild operating conditions [2,3]. Nevertheless,
the lower H/C of low-rank coal leads to a decrease in the yield and
quality of tar. Extensive research has been devoted to finding suitable
hydrogen-rich resources for co-pyrolysis with low-rank coal [4–7]. As
one of the three major synthetic materials, plastic has widely used in
various aspects of production and life due to its high strength, corrosion
resistance and impact resistance. The widespread use of plastic products
has brought great convenience to people’s lives. At the same time,
“white pollution” has also become one of the urgent environmental
problems to be addressed [8,9]. The effective treatment of waste plastic
and the recycling of resources have attracted widespread attention.
Plastic products are derived from petrochemicals and belong to hy­
drocarbon polymers in terms of their structure. Co-pyrolysis of plastic
and low-rank coal can be used to recover hydrogen resources from

* Corresponding author.
E-mail address: baizq@sxicc.ac.cn (Z. Bai).

https://doi.org/10.1016/j.fuel.2023.130519
Received 19 July 2023; Received in revised form 29 October 2023; Accepted 27 November 2023
Available online 2 December 2023
0016-2361/© 2023 Elsevier Ltd. All rights reserved.
T. Zhang et al.
plastic. On the other hand, it can alleviate the shortage of non-renewable
coal resources. Until now, abundant researches have focused on the co-
pyrolysis interactions between coal and plastic. Zhou et al. [10]
demonstrated the presence of significant synergistic between plastic and
coal in high-temperature region. Qian et al. [11] found that the inter­
action between coal and waste plastic is crucial in enhancing the yield
and quality of tar. Saha et al. [12] co-pyrolyzed coal with various types
of plastic and found that the tar from pyrolysis of coal/low-density
polyethylene (LDPE) or coal/polypropylene (PP) have high calorific
values (almost twice as high as coal tar). However, due to the limitations
of detection methods, many studies have been conducted to analyze the
co-pyrolysis products properties by conventional method, such as using
GC–MS to detect the composition of tar and using GC to analyze the
pyrolysis gas, etc. However, these pyrolysis products inevitably undergo
secondary reactions during their formation and are collected as the final
products after reaching the target temperature and cooling. Most of the
current research still remains at the macro level of analyzing stable
products to our knowledge. Understanding the interaction between low-
rank coal and plastic at the molecular level is crucial for their recycling
and utilization.
In recent years, in-situ Py-TOF-MS has achieved more attention
because of its online capture of primary volatiles and intermediate
radicals during pyrolysis with the high sensitivity. It has been widely
used in the study of the pyrolysis properties of coal, waste plastic and
biomass. Zhou et al. [13] detected the primary products of pyrolysis of
sub-bituminous coal catalyzed by calcium nitrate with the help of Py-
TOF-MS. Zhu et al. [14] performed Py-TOF-MS test to examine the
primary volatiles fraction of dealkylated lignin pyrolysis, and found that
the cleavage of β-O-4 linkages is the main reason for lignin depoly­
merization at 100–300 ◦ C. Yang et al. [15] employed Py-TOF-MS to
capture primary volatiles from PVC pyrolysis, revealing the mechanism
of Cl evolution-induced aromatization and the interactions between
radical intermediates. Wu et al. [16] examined the distribution of pri­
mary volatiles and the evolutionary behavior of the co-pyrolysis of coal
and polystyrene (PS) using the same monitoring tool. Remarkably, most
of the waste plastic comes from municipal waste, which is typically a
mixture of different types of plastic. Separating mixed plastic into in­
dividual types requires complex processes and high-precision separation
equipment, which greatly increases the recycling cost [17]. Moreover,
the mechanism of the pyrolysis reaction of mixed plastic may be differ
due to the interaction between the various components [18]. Hence, it is
essential to investigate the interaction between low-rank coal and mixed
plastic.
PP, PS, PE, polyethylene terephthalate (PET) and polyvinyl chloride
(PVC) are common polymer materials that we encounter in our daily
life, which are major components of waste plastic [19]. Considering the
fact that PE/PP/PS account for 50%-70% of plastic waste, this study
focuses on LDPE, PP and PS. Real-time mass spectra and temperature
evolution curves of primary volatiles were obtained through in-situ Py-
TOF-MS to investigate the co-pyrolysis interactions between low-rank
coal and mixed plastic at the molecular level. Moreover, the in­
teractions were quantitatively analysis through comparing the contents
of major volatiles. The results obtained contribute to a better under­
standing of the complex interactions during low-rank coal and mixed
waste plastics co-pyrolysis.
2. Material and methods
2.1. Material
Hami coal (HM), a low-rank coal from Xinjiang, was used as feed­
stock for pyrolysis experiments along with PP, LDPE and PS purchased
from Macklin Company. Before experiments, HM coal and the three
types of plastic were crushed. The samples with a particle size of less
than 80 mesh were dried in an oven at 105 ◦ C for 24 h to eliminate the
moisture. The ultimate and proximate analyses of the samples are listed
2
Fuel 359 (2024) 130519
in Table 1. First, the mixed plastic with a mass ratio of PP/LDPE (3:2)
and PP/LDPE/PS (12:8:1) were prepared, respectively. The proportion
of each type of plastic in the sample is determined based on the actual
yield (Mass) in China. Then, HM was mixed with PP, PP/LDPE, and PP/
LDPE/PS in a ratio of 3:1 (excessive plastic tends to inhibit the coal
pyrolysis), and named as HP, HPE and HPES, respectively. Subse­
quently, all samples were sealed and stored in containers for later use.
2.2. TG analysis
The pyrolysis behavior of HM, PP, LDPE, PS and their mixtures was
tested by a TG analyzer (Setsys Evolution, SETARAM, France). For each
test, approximately 10 mg of the sample was heated from 25 ◦ C to 900 ◦ C
at the rate of 10 ◦ C/min under argon with a specified flow (100 mL/
min). The theoretical value of weight loss from co-pyrolysis was calcu­
lated according to formula. (1).
wCal = x1 w1 + x2 w2 + x3 w3 (1)
where, x1, x2, and x3 refer to the weight percentage of coal and different
types of plastic pyrolysis in mixture; w1, w2, and w3 are the laboratory
values of individual pyrolysis of samples.
The theoretical peak temperature was obtained based on the deri­
vation of the theoretical weight loss curve.
2.3. Py-TOF-MS analysis
The main primary volatiles produced from the pyrolysis of HM, PP,
LDPE, PS, and their mixtures were analyzed using an in-situ Py-TOF-MS
(QuanTang Science Instruments, China). As depicted in Fig. S1 (sup­
plementary material), the device consists of a vacuum system, a pyrol­
ysis module with programmed temperature rise, an ion source, a mass
analyzer, and an ion detector. Remarkably, the pyrolysis zone is just 2
cm away from the ionization zone, which helps to prevent secondary
reactions between primary volatiles. Additionally, both the pyrolysis
and flight zones are maintained under a high vacuum conditions (≤10− 5
Pa), which helps to retain the original structure and mass information of
the intermediate and primary volatiles [13,15,16]. For each test, about
5 mg of the sample was loaded into a sample tube and heated from 25 ◦ C
to 700 ◦ C with a specified rate of 10 ◦ C/min after the vacuum conditions
required for the experiment were reached. The volatiles generated from
the thermal decomposition of the sample were ionized and then reached
the detector under the action of electric field, where they were finally
captured and recorded. The relative volatiles content was obtained by
semi-quantitative analysis [15,20] according to formula. (2).
Sumi
Y(%) = ∑n × 100% (2)
1 Sumi
where, Y is the relative content for species i, sumi represents the sum of
∑
the intensity of the mass peak for species i, n1 Sumi means the accu­
mulated intensity of total volatiles mass peak in mass spectrometry.
YCal (%) = (x1 Y1 + x2 Y2 + xn Yn ) × 100% (3)
where, Y1, Y2 and Yn are the percentage content of coal and different
types of plastic pyrolysis alone, respectively.
3. Results and discussion
3.1. TG and DTG analyses of samples
The TG and DTG curves of typical plastic (PP, LDPE and PS) and HM
coal pyrolysis alone are shown in Fig. 1(a). As shown in the TG, there is
only one stage for PP, LDPE and PS pyrolysis, with a weight loss of nearly
99 wt%. The peak temperature corresponding to the maximum rate of
weight loss follows the trend: PS < PP < LDPE, which are 412, 451, and
T. Zhang et al. Fuel 359 (2024) 130519

Table 1
The ultimate analysis of samples.
Sample Proximate analysis (wt/%) Ultimate analysis (daf, wt/%) St, ad

Mad Ad Vdaf C H O* N

PP – – 99.55 83.69 14.76 1.44 – <0.01

LDPE – – 99.42 83.09 13.97 – – <0.01
PS 0.16 – 99.64 92.20 7.95 – – <0.01
HM 7.46 9.93 53.01 74.36 5.46 17.58 0.92 1.40

ad, air dried basis; St, ad, total sulfur (air dried basis); *, by difference; -, not detected.

474 ◦ C, respectively. The degradation temperature of PP is lower than

that of LDPE due to the present of branched-chains on the PP polymer
chain [21]. The HM pyrolysis involves a wide temperature range of
232–715 ◦ C, which is related to the rich types of covalent bond in coal. It
can be observed that the weight loss of HM pyrolysis is 46.59 wt%, with
the peak located at 446 ◦ C.
Fig. 1(b) depicts the TG/DTG curves of mixed plastic co-pyrolysis.
The major weight loss temperature of PP/LDPE co-pyrolysis is
255–484 ◦ C, with the maximum weight loss rate at 457 ◦ C. The pyrolysis
process is basically completed after 500 ◦ C, accompanied by a weight
loss of 96.99 wt%. The major temperature for weight loss during PP/
LDPE co-pyrolysis is between that of PP and LDPE pyrolysis alone. PP
has higher degree of branching and methyl as side chain, which are more
easily shed to form CH3 and H radicals during pyrolysis. The tempera­
ture range of PP/LDPE/PS co-pyrolysis is 267–485 ◦ C, with the
maximum weight loss rate at 456 ◦ C. Approximately 94.97 wt% of PP/
LDPE/PS degrades before 500 ◦ C, which is lower than that of PP/LDPE
co-pyrolysis. Part of polycyclic aromatic hydrocarbons (PAHs) is pro­
duced during PS pyrolysis, which reacts with long-chain molecules and
tends to produce residues [22].
The TG/DTG curves of HM and mixed plastic co-pyrolysis are shown
in Fig. 1(c). To illustrate the synergistic effect, four characteristic tem­
peratures including the initial temperature (Ti), peak temperature
(Tmax), and final temperature (Tf), and the maximum weight loss rate are
summarized in Table 2. The weight loss occurs in the range of
209–663 ◦ C for the co-pyrolysis of HP and the weight loss is 59.57 wt%,
which is similar to the theoretical value (59.84 wt%). The maximum
mass loss rate is found at 451 ◦ C. The weight loss of HPE quickly in­
creases in the range of 228–660 ◦ C. The thermal weight loss rate is 59.30
wt% with a theoretical value of 59.84 wt%. The maximum mass loss rate
is found at 455 ◦ C, which exceeds the theoretical value by 6 ◦ C. The
thermal weight loss is 59.79 wt%, and the theoretical value is 59.85 wt
%. The weight loss rate of HPES reaches its maximum at 464 ◦ C, which is
significantly higher than the theoretical value (449 ◦ C). Clearly, the co-
pyrolysis of different plastic blends with HM coal does not have a sig­
nificant effect on weight loss, as the weight loss of these plastics during
pyrolysis is above 99 wt%. However, the temperature for maximum
weight loss rate varies with the composition of the plastic mixture,

Table 2
Characteristic temperature of pyrolysis and co-pyrolysis of HM and typical
plastics.
Sample Pyrolysis range Peak temperatures (◦ C) Weight loss (wt.%)
(◦ C)

Ti Tf Tmax W

HM 232 715 446 46.59

PP 234 469 451 99.60
LDPE 430 486 474 99.62
PS 356 427 412 99.90
PP/LDPE 372 484 457 96.99
Fig. 1. TG/DTG curves of PP, LDPE, PS, HM and their mixture pyrolysis: (a) PP, PP/LDPE/PS 371 485 456 94.97
LDPE, PS, HM, (b) PP/LDPE, PP/LDPE/PS and (c) HP, HPE, HPES. HP 209 663 451 59.57
HPE 228 660 455 59.30
HPES 256 658 464 59.79

Ti: Temperature at 5 wt.% conversion; Tf: Temperature at 95 wt.% conversion.

3
T. Zhang et al. Fuel 359 (2024) 130519

which is associated with the structure of different types of plastic. LDPE
has a single C-long chain structure, while PP and PS both have branched
chains, which are more easily shed during pyrolysis. In addition, the
value of Tf shifts towards a lower temperature with an increase in plastic
type (Table 2). In other words, the inclusion of LDPE and PS shortens the
overall reaction time compared to HP, which illustrates the occurrence
of interaction between HM and mixed plastic during co-pyrolysis.
3.2. Identification of the released primary volatiles during pyrolysis/co-
pyrolysis by Py-PI-TOF-MS
As shown in Fig. 2, in-situ detection of volatiles from the pyrolysis of

Fig. 2. PI-MS spectrum of volatiles from pyrolysis of (a) PP, LDPE, PS and HM (b) PP/LDPE, PP/LDPE/PS and (c) HP, HPE, HPES.

4
T. Zhang et al.
HM, PP, LDPE and PS during pyrolysis or co-pyrolysis were performed
by Py-PI-TOF-MS and identified based on the m/z value and the refer­
ences reported in literatures [16,23,24]. And the detailed assignment of
peaks is presented in Table S1. The major primary volatiles of LDPE can
be summarized into five types: alkenes (m/z: 56, 70, 84, 98), alkadienyls
(m/z: 82, 96, 110, 124), alkyl radicals (m/z: 57,71, 85, 99), alkene
radicals (m/z: 55, 69, 83, 97), and alkadienyl radicals (m/z: 81, 95, 109,
123). The primary volatiles of PP pyrolysis are similar to LDPE. This is
due to the fact that the main structures of both PP and LDPE are
composed of C-long chains. However, compared with LDPE, PP contains
more methyl-branched chains and has lower stability, resulting in a
lower pyrolysis temperature than that of LDPE (Fig. 1(a)). The organic
volatiles from PS pyrolysis can be categorized into four main parts:
alkenyl benzene represented by styrene monomer (m/z: 104), toluene
(m/z: 92), a small amount of alkadienyl benzene (m/z: 130, 220), rad­
icals generated during the pyrolysis process, mainly including alkyl
benzene radicals (m/z: 91, 105, 313) and alkenyl phenyl radicals (m/z:
117, 193, 207).
Fig. 3. TIC curves of volatiles from (a) PP, LDPE, PS, HM and (b) PP/LDPE, PP/LDPE/PS and (c) HP, HPE, HPES pyrolysis.
5
Fuel 359 (2024) 130519
As for the co-pyrolysis of PP/LDPE or PP/LDPE/PS (Fig. 2(b)), the
spectral peaks of the mixed plastic are almost all the characteristic
products of PP, LDPE, and PS pyrolysis. Nevertheless, the relative con­
tent of the volatiles differs significantly from those produced during the
pyrolysis of PP, LDPE and PS, indicating that there are interactions be­
tween plastic mixture during co-pyrolysis. Fig. 3 depicts the temperature
evolution curve of the TIC. The temperature evolution curves for the
pyrolysis of the main volatiles are shown in Figs. S2 and S3. Apparently,
the TIC peak of PP, LDPE and PS is 448, 460 and 403 ◦ C, respectively.
The TIC for PP/LDPE co-pyrolysis exhibits two peaks at 430 ◦ C and
454 ◦ C, which correlate to the pyrolysis of PP and LDPE alone, respec­
tively. Apparently, the temperature of TIC peak of PP/LDPE is appre­
ciably lower than that of PP and LDPE pyrolysis alone. During the co-
pyrolysis of PP and LDPE, CH3 radicals are easily generated due to the
methyl substitution of PP, and these radicals can rapidly activate the
uncracked macromolecular, promoting the degradation of LDPE [25]. In
case of PP/LDPE/PS, the TIC still exhibits 2 peaks at 394 ◦ C and 439 ◦ C,
respectively. However, as shown in Fig. S3, there are three peaks of the
T. Zhang et al. Fuel 359 (2024) 130519

main volatiles (394, 402, and 439 ◦ C), corresponding to the peaks of PS,
PP, and LDPE, respectively. This is attributed to the fact that the peak
temperature of TIC of PS and PP are similar, and the percentage of PS is
only 1/12 that of PP, resulting in only 2 peaks observed on the TIC.
Obviously, the TIC peak temperature of the mixed plastic is considerably
lower than that of plastic pyrolysis alone. This further confirms the ex­
istence of interaction during the co-pyrolysis of mixed plastic, which
promotes the release of volatiles at lower temperatures.
In the case of HM pyrolysis, the volatiles mainly contain alkenes (m/
z: 56, 70, 84, 98); phenols, including monophenols (m/z: 94, 108, 122)
and diphenols (m/z: 110, 124, 138); aromatic hydrocarbons, including
monocyclic aromatic hydrocarbons (m/z: 78, 92, 106), bicyclic aromatic
hydrocarbons (m/z: 142, 156, 170) and anthracene (m/z: 192, 206,
220). Furthermore, some sulfur-containing materials (m/z: 34) are
produced during the process of HM pyrolysis. Fig. 2 (c) displays the PI-
MS spectrum of HP, HPE and HPES case. No new compounds were
observed during the co-pyrolysis of HM and mixed plastic, but the
relative intensity of the primary volatiles was affected. As can be seen
from Fig. 3, the peak temperature of HP, HPE and HPES are 446, 451 and
456 ◦ C, respectively, which are much higher than that of theoretical
values (440, 442 and 441 ◦ C). This reveals that the addition of plastic is
detrimental to the release of volatiles. It results from the interaction
between the volatiles produced during HM pyrolysis and the molten
plastic, which impedes the release of radicals.

3.0 PP Alkenes Alkadienyl

radical radical
2.5 Alkenes Alkadienes Alkyl radical
2.0
1.5
1.0
0.5
0.0
56 70 84 98 112 126 82 96 110 124 57 71 85 99 113 127 69 83 97 111 125 81 95 109 123

3.0 LDPE Alkenes Alkadienyl

Alkenes Alkadienes Alkyl radical radical radical
2.5
2.0
Relative intensity (%)

1.5
1.0
0.5
0.0
56 70 84 98 112 126 82 96 110 124 57 71 85 99 113 127 69 83 91 111 125 81 95 109 123

24.5 PS
Alkyl phenyl radical
24.0 Alkenyl benzene Alkenyl phenyl Alkadienyl
Alkyl benzene
4.0 radical benzene
3.5

1.5
1.0
0.5
0.0
104 118 194 208 312 117 129 193 207 221 91 92 105 131 313 130 220

3.0 HM
Alkyl phenols
Alkenes Alkyl naphthalenes
2.5 Diphenols Alkyl benzenes
Alkyl anthracenes
2.0
1.5
1.0
0.5
0.0
42 56 70 84 94 108 122 136 150 110 124 138 78 92 106 120 134 148 142 156 170 184 192 206 220
m/z
Fig. 4. Relative content of main volatiles from PP, LDPE, PS and HM pyrolysis.

6
T. Zhang et al.
3.3. Quantitative analysis of pyrolysis and co-pyrolysis of coal and
plastics
3.3.1. Quantitative analysis of primary volatiles during the HM, PP, LDPE
and PS pyrolysis alone by Py-PI-TOF-MS
A semi-quantitative approach was used to evaluate the relative
content of primary volatiles during the pyrolysis of HM and typical
plastic, as illustrated in Fig. 4. In order to examine the interaction more
closely, the relative content of primary volatiles and the theoretical
value were also compared.
Based on the data presented in Fig. 4, the alkene products resulting
from the pyrolysis of PP consist mostly of C4-C8 with relative contents of
0.44 %, 0.96 %, 1.32 %, 0.54 % and 1.08 %, respectively. The alkadienyl
products obtained by polymerization of PP pyrolysis intermediates, such
as hexadiene (m/z: 82) and heptadiene (m/z: 96), have relatively high
contents, which are 0.98 % and 0.81 %, respectively. In addition,
numerous reactive radicals, such as alkenyl radicals (m/z: 69, 83) and
alkyl radicals (m/z: 57, 71), are also detected with high content, which
are 3.19 %, 2.90 %, and 2.40 %, 1.57 %, respectively. Also, it can be
found that the content of alkenyl radicals is significantly higher than
that of alkyl radicals. This is because numerous of alkyl radicals are
generated during the thermal decomposition of polyolefins through C–C
bond, and high-carbon alkyl radicals further decompose to produce al­
kenes and small molecular alkyls [23].
The types of alkene products, such as butene (m/z: 56), pentene (m/z:
70), hexene (m/z: 84) and heptane (m/z: 98), formed by pyrolysis of
LDPE are the same as those of PP, but the content of them is significantly
higher than that of PP, with 1.33 %, 2.08 %, 1.60 % and 1.48 %,
respectively. The content of alkadienyl products such as hexadiene (m/z:
82), heptadiene (m/z: 96), octadiene (m/z: 110) and nonadiene (m/z:
124), obtained from the polymerization of alkene intermediates from
LDPE is also clearly higher than that of PP. However, the content of
alkenyl radicals and alkyl radicals from pyrolysis of LDPE is much lower
than that of PP, such as butyl radicals (m/z: 57, 69, 83, 109), which are
1.98 %, 0.45 %, 1.38 %, and 0.49 %, respectively. It’s due to the absence
of branched chains in LDPE and the higher polymerization degree of the
products obtained by cleavage of LDPE than that of PP.
The products from PS pyrolysis are mainly styrene monomers with a
relative content of 24.55 %; the free radicals are mainly divided into
phenyl alkyl radicals (m/z: 91, 105, 313) and phenyl alkenyl radicals
(m/z: 117, 193, 207) with contents of 4.25 % and 6.95 %, respectively.
Compared with PP, the composition of PS pyrolysis products is relatively
simple. This is mainly caused by the introduction of substituents, which
makes the energy distribution of C–C covalent bond is PS polarize to
varying degrees [22]. In contrast, PP has a more even covalent bond
structure, and its bond dissociation is irregular during the pyrolysis
process, resulting in a scattered variety of pyrolysis products. PP, LDPE
and PS all contain long carbon chains connected by C–C single bonds,
but only the structure of the substituents is different. The major products
from PP, LDPE and PS can be summarized into the following categories:
monomers and their homologous series, dimers or polymorphs, alkenyl
derivatives of monomers or polymorphs, and various radicals. Extensive
alkylation radicals are produced by the C–C cleavage at the β-position
during plastic pyrolysis. The combination of radicals produces the cor­
responding volatiles (monomers, dimers and multimers).
More phenolic products are produced during HM pyrolysis, such as
phenol (m/z: 94), methyl-phenol (m/z: 108), and dimethyl-phenol (m/z:
122) with relative contents of 1.71 %, 1.83 %, and 1.30 %, respectively.
Additionally, lots of benzenediol (m/z: 110, 1.53 %), and methyl-
benzenediol (m/z: 124, 1.11 %) are also generated. Moreover, various
aromatic products including toluene (m/z: 92, 0.68 %), ethylbenzene
(m/z: 106, 0.71 %), dimethyl-naphthalene (m/z: 156, 0.46 %) and
methyl-naphthalene (m/z: 192, 0.44 %) are also produced. It can be
observed that the proportion of benzene during HM pyrolysis is signif­
icantly lower compared to other aromatic compounds, at only 0.24 %.
This is consistent with the conclusion reached by Wu [24] et al. Benzene
7
Fuel 359 (2024) 130519
is typically produced through the dissociation of C-Car on phenyl [26], as
well as the cleavage of naphthalene, anthracene, and phenanthrene at
high temperatures.
3.3.2. Quantitative analysis of primary volatiles during the PP/LDPE and
PP/LDPE/PS co-pyrolysis by Py-PI-TOF-MS
Fig. 5 displays the relative content of the major volatiles from mixed
plastic co-pyrolysis. Based on the laboratory values of PP and LDPE
pyrolysis alone, the theoretical values of the content for the main vol­
atiles of PP/LDPE and PP/LDPE/PS co-pyrolysis were calculated.
It can be observed that during the co-pyrolysis of PP and LDPE, the
production of alkene products is lower than the theoretical values, while
the content of alkene radicals and alkadienyl radicals is significantly
higher than the theoretical value. Among them, the content of butene
(m/z: 56) and pentene (m/z: 70) reduces by 0.36 % and 0.40 %,
respectively. In contrast, the pentene radicals (m/z: 69), hexene radicals
(m/z: 83), hexadiene radicals (m/z: 81), heptadiene radicals (m/z: 95),
and octadiene radicals (m/z: 109) increase by 0.78 %, 0.63 %, 0.25 %,
0.40 %, and 0.59 %, respectively. PP contains lots of methyl-branched
chains, which leads to the production of numerous alkene molecules
during the cracking process. Co-pyrolysis of PP and LDPE promotes the
further breakage of alkene molecules and generates more alkene radicals
and alkadienyl radicals.
In the case of PP/LDPE/PS, it can be found that the content of aro­
matic products generated from PS pyrolysis, such as alkenyl-benzene,
alkenyl-benzene radicals and alkylbenzene radicals, is higher than that
of theoretical value. Among them, the content of styrene (m/z: 104), p-
divinylbenzene (m/z: 130) and 2,4-diphenyl-1-butene radicals (m/z:
207) increases by 4.40 %, 0.67 %, and 1.43 %, respectively. Sophonrat
et al. [27] also found the yield of aromatics significantly increases
during the process of PP/PS blends and cellulose co-pyrolysis. Plenty of
radicals containing benzene rings are produces in the initial chain re­
action of PS due to its low initial pyrolysis temperature. The radicals
participate in the initial chain reaction of PP and LDPE, which affects the
intermolecular transfer of hydrogen and the β-cleavage [28].
3.3.3. Quantitative analysis of primary volatiles during the co-pyrolysis of
HM and mixed plastic by Py-PI-TOF-MS
The relative content of the main volatiles of co-pyrolysis of HM with
mixed plastic is shown in Fig. 6.
For the co-pyrolysis of HM with PP (Fig. 6(a)), the relative content of
pentadiene (m/z: 68), hexadiene (m/z: 82), and heptadiene (m/z: 96)
increases from 0.18 % to 0.48 %, 0.25 % to 0.77 % and 0.20 % to 0.91 %,
respectively, compared to the theoretical values. From this point, it can
be seen that co-pyrolysis interaction promotes the cracking of long-chain
C–C of PP, which nicely explain the increase in the yield of alkadienyl.
The content of monophenols decreases to varying degrees compared to
theoretical values. For example, the relative content of phenol and
methyl phenol reduces from 1.28 % to 0.91 % and from 1.37 % to 1.09
%, respectively. This is due to the molten PP coating on the surface of
HM and impedes the HM pyrolysis, resulting in a decrease in phenols’
content [29]. Benzenediol (m/z: 110) and methylphenidate (m/z: 124)
increase from 1.15 % to 1.34 % and from 0.83 % to 1.12 %, respectively.
This is related to the hydrogenation reaction between the phenoxy
groups produced by the pyrolysis of PP and hydrogen radicals (⋅H) [30].
Furthermore, the content of radicals is noticeably higher than the
theoretical value, such as alkyl radicals, alkenyl radicals and dienyl
radicals, indicating that the co-pyrolysis of HM and PP contributes to the
generation of reactive radicals.
Compared with the pyrolysis of HP, the alkene products from the co-
pyrolysis of HPE (Fig. 6(b)) decrease considerably. For example, the
relative content of propylene, butene, pentene, and hexene (m/z: 42, 56,
70, 84) decreases by 0.50 %, 0.34 %, 0.45 %, and 0.56 %. This is related
to the fact that LDPE has no methyl-branched chains and more long-
chains fragments are generated by cleavage. The content of diphenols
produced through pyrolysis of HPE are much lower than the theoretical
T. Zhang et al.
Fig. 5. Relative content of main volatiles during co-pyrolysis of (a) PP/LDPE and (b) PP/LDPE/PS.
values, which is different from the case of HP. Among them, the content
of benzenediol (m/z: 110) and methylphenidate (m/z: 124) decreases
from 1.15 % to 0.71 %, and 0.83 % to 0.68 %, respectively. Compared
with PP, the pyrolysis temperature of LDPE is higher (474 ◦ C). The
weight loss of PP is 90.02 wt%, when the weight loss of LDPE is only
39.71 wt% and its main structure still exists in the molten state.
Therefore, the inhibition effect of molten mixed plastic (PP/LDPE) on
the pyrolysis of HM is enhanced compared to that of HP, resulting in a
decrease in the content of diphenol products. Meanwhile, PAHs, such as
methyl-anthracene (m/z: 192) and tetramethyl-anthracene (m/z: 234)
increases to relative values compared to the theoretical values, namely
0.08 % and 0.11 %, respectively. This result suggests that co-pyrolysis of
coal with mixed plastic can promote the further cracking of the
macromolecular structure of coal and generate more PAHs. Beyond that,
it can be observed that the content of radicals reduces substantially
compared to the pyrolysis of HP. For example, hexane radicals (m/z: 85),
hexene radicals (m/z: 83), and hexadiene radicals (m/z: 81) decrease
from 0.93 % to 0.40 %, 0.99 % to 0.50 %, and 0.32 % to 0.25 %,
respectively. It is caused by the long-chain alkenes produced by LDPE
pyrolysis are easily trapped in the carbon matrix [31].
Pyrolysis of PS results in the formation of massive amounts of styrene
monomers and their homologous series, dimers or multimers, and
various free radicals, which have not been detected in systems that do
not contain PS. It can be observed that the relative content of alkenyl
benzenes exhibits an increasing trend compared to the theoretical values
in case of HPES (Fig. 6(c)). Among them, the contents of styrene (m/z:
104), 1-ethenyl-3-methyl benzene (m/z: 118), 2,3-diphenyl-1-propene
(m/z: 194), 1-butene-2,4-diphenyl (m/z: 208) and 1,2,6-triphenyl-3-
8
Fuel 359 (2024) 130519
hexene (m/z: 312) increased by 2.87 %, 0.30 %, 0.49 %, 0.63 % and
0.28 %, respectively. This suggests that the co-pyrolysis of HM and PS
promotes the Cβ-Car cleavage in PS to generate styrene monomers [16].
On the other hand, large amounts of benzene ring-containing radicals
are generated in initial chain reaction of PS, which are involved in that
of PP and LDPE, thereby affecting β-cleavage and increasing the benzene
ring-containing radicals [28]. There is also a growing trend in the con­
tent of alkyl phenyl radicals, alkenyl phenyl radicals, and dienyl benzene
radicals, leading to an increase in their derivatives, such as phenylethyl
(m/z: 105), 2,3-diphenyl-1-propenyl radical (m/z: 193), 1-butene-2,4-
diphenyl radical (m/z: 207) and 1,4-diethylbenzene (m/z: 130). Unlike
in the case of HP or HPE, the content of ethylbenzene (m/z: 106) is
higher than the theoretical value for HPES. PS forms phenethyl radicals
during the pyrolysis process. It can be concluded that the addition of PS
to the mixture promotes the intramolecular and intermolecular
hydrogen transfer in the system [32].
To further explore the co-pyrolysis interaction between HM and
mixed plastic, the temperature-evolved profiles of the primary volatiles
was also examined (Fig. 7). During the co-pyrolysis of HM and mixed
plastic, the volatiles are released in the range of 300–550 ◦ C, accom­
panied by different peak temperatures.
In the case of HPES, styrene monomers and their homologous series,
dimers or polymers, as well as various free radicals, all originate from
the cracking of PS. The peak value of them is 453 ◦ C, which is signifi­
cantly higher than that of PS pyrolysis alone (403 ◦ C). It due to that the
molten PP and LDPE inhibit the release of primary volatiles during PS
pyrolysis. Furthermore, it can be seen that the peak temperatures of
phenolic compounds in the evolution curves of HP, HPE, and HPES shift
T. Zhang et al.
Fig. 6. Relative content of main volatiles of (a) HP, (b) HPE and (c) HPES pyrolysis.
towards a higher temperature region compared to HM pyrolysis alone.
The order of peak temperatures is as follows: HPES (456 ◦ C) > HPE
(443 ◦ C) > HP (437 ◦ C) > HM (430 ◦ C). This is attributed to the molten
plastic hinders the release of HM volatiles. Molten plastic has the
characteristics of high viscosity and low thermal conductivity [19],
which are unfavorable for the transfer of mass and heat during pyrolysis.
3.3.4. In-suit Py-EI-TOF-MS analysis of primary volatiles during the co-
pyrolysis of HM and mixed plastic
Small molecule gases such as H2, CO, CO2 and CH4 are produced
during the pyrolysis of coal. However, due to their high ionization en­
ergies of 15.43, 12.61, 14.01 and 13.78 eV, they cannot be ionized and
captured by VUVPI-MS (10.6 eV). Thus, an EI (70 eV) source was
configured on an in-situ Py-TOF-MS to detect the release behavior of
those small molecule gaseous products. The EI-MS (a) and evolution-
curves (b) of main volatiles as a function of temperature from pyroly­
sis of HM is shown in Fig. 8 as an example. And the evolution-curves of
main volatiles from pyrolysis of HP, HPE, and HPES is shown in Fig. S4.
As can be observed, the vast majority of CO2 is released before 500 ◦ C
9
Fuel 359 (2024) 130519
during HM pyrolysis, which from the decomposition of aliphatic and
aromatic carboxylic and carboxylic acids. Higher temperatures result
from the thermal dissociation of ether structures, quinones and
oxygenated heterocycles [33]. CO has a broad escape peak, mainly from
the decomposition of ethers and carbonyls up to 550 ◦ C, at higher
temperatures it is derived from the decomposition of oxygen-containing
heterocycles [34].
The semiquantitative method was also used to calculate the relative
content of volatile products detected based on EI-MS, as shown in Fig. 9.
It can be seen that co-pyrolysis with plastics significantly reduces the
yields of CO and CO2, as evidenced by the fact that the actual content of
them are lower than the expected value. This is due to the fact that the
molten plastics at the early stage of pyrolysis hinder the pyrolysis pro­
cess of carboxyl groups in the coal structure [16]. It should be noted that
the content of CO is not significantly affected by the addition of different
types of plastic, but that of CO2 follows the order: HP < HPE < HPES. It
means that the addition of mixed plastics promotes the decomposition of
aliphatic and aromatic carboxylic acids in coal at lower temperatures.
T. Zhang et al. Fuel 359 (2024) 130519

Fig. 7. Temperature-evolved curves of main volatiles from pyrolysis of (a) HP, (b) HPE and (c) HPES.

10
T. Zhang et al.
Fig. 8. EI-MS (a) and evolution-curves (b) of main volatiles as a function of temperature from pyrolysis of HM.
Fig. 9. Relative content of primary volatiles from pyrolysis of HM, HP, HPE and HPES.
3.4. Co-pyrolysis mechanisms of HM and mixed plastic
Based on the results of the in-situ Py-TOF-MS analysis presented
above, a possible interaction mechanism during the co-pyrolysis of HM
coal and mixed plastic is proposed in Fig. 10. During the co-pyrolysis
process of HM and plastic (whether single or mixed), the plastic first
undergoes softening and melting at low temperatures, and then wraps
around the HM particles, which has been confirmed in our previous
work [35]. Long-chain alkenes produced from PP cracking coat the
surface of HM during the co-pyrolysis process, inhibiting the release of
volatiles, such as aromatics, alkenes and phenols. As the pyrolysis
temperature increases, the cracking of PP intensifies, leading to the
degradation of H radicals, alkenyl radicals, and alkyl radicals. These
radicals react with the phenoxy from HM pyrolysis, which promotes the
formation of diphenol compounds.
More long-chain alkene radicals are present in the system in case of
11
Fuel 359 (2024) 130519
HPE. Moreover, the enhanced inhibitory effect of molten plastic on HM
pyrolysis results in a reduction in the content of diphenol products.
Radicals are also trapped in the carbon matrix, leading to a decrease in
their relative content. With the further addition of PS after PP and LDPE,
numbers of styrene and its homologous series, as well as dimer or
multimer radicals, appear in the system. Co-pyrolysis with HM further
facilitates the cleavage of the Cβ-Car bond in PS, resulting in an increase
in the content of alkenyl benzene compounds. Moreover, the significant
quantity of radicals containing benzene produced during the cracking of
PS at lower temperatures participate in the initial chain reaction of PP
and LDPE, thereby affecting β-cleavage and increasing the benzene ring-
containing radicals. In addition, the peak temperatures of the HP, HPE,
and HPES evolution curves shift towards a higher-temperature region
compared to HM pyrolysis alone, which is due to the molten plastic
hinders transfer of heat and mass during the pyrolysis process. Mean­
time, the molten plastics hinder the pyrolysis process of carboxyl groups
T. Zhang et al.
Fig. 10. The proposed co-pyrolysis mechanisms between coal and mixed plastic.
in the coal structure, leading to a decrease in the yields of CO and CO2.
4. Conclusion
The in-situ Py-TOF-MS technique was used to obtain information on
the release of primary volatiles during the co-pyrolysis of HM coal and
mixed plastic. The mechanism of plastic pyrolysis and its interaction
with coal during co-pyrolysis were further discussed at the molecular
level by comparing the volatile content, deviation values, and volatile
evolution curves. The TIC results indicate that during the co-pyrolysis of
HM coal and mixed plastic, the molten plastic wraps around the surface
of the HM, hindering the release of volatiles from HM, causing the peak
pyrolysis temperature to shift to higher temperatures. The co-pyrolysis
of HM and PP promotes the C–C cracking of long-chain PP into
shorter chain products, as well as the hydrogen transfer reactions with
phenoxy in HM to generate more diphenol products. The further addi­
tion of LDPE after PP enhances the inhibitory effect of molten plastic on
HM pyrolysis, resulting in a decrease in the content of diphenol prod­
ucts. Meantime, long-chain radicals are trapped in the carbon matrix,
leading to a decrease in the content of radicals. Regarding the pyrolysis
of HPES, the production of aromatic products increases significantly.
Moreover, the inclusion of PS in the mixture enhances both the intra­
molecular and intermolecular hydrogen transfer within the system.
Regarding inorganic gases, co-pyrolysis of coal and plastic reduces the
content of CO and CO2 due to the molten plastic hinders the decompo­
sition of carboxyl groups in the coal structure at the early stage of
pyrolysis.
CRediT authorship contribution statement
Tingting Zhang: Writing – original draft, Methodology, Investiga­
tion. Zongqing Bai: Writing – review & editing, Formal analysis,
Conceptualization. Hongyan Zheng: Writing – review & editing. Haoyu
Dou: Investigation. Zhenxing Guo: Validation, Software. Lingxue
Kong: Resources, Data curation. Jin Bai: Supervision, Project admin­
istration. Wen Li: Supervision, Project administration.
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.
Data availability
Data will be made available on request.
12
Fuel 359 (2024) 130519
Acknowledgements
The authors gratefully acknowledge the financial support from the
National Natural Science Foundation of China (22078353, 22178371),
Key Research and Development project of Shanxi Province
(202102090301004), Strategic Priority Research Program of the Chi­
nese Academy of Sciences (Grant No. XDA21020100).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.fuel.2023.130519.
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