Journal of the Energy Institute 113 (2024) 101529

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Journal of the Energy Institute

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Interpretation of interactions between low rank coal and polyethylene

during co-pyrolysis from the bond cleavage perspective
Tingting Zhang a, b, Wei Feng 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
Breeding Base for Shanxi Key Laboratory of Biomass-based Green Methanol Conversion and Hydrogen Utilization, 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

Handling Editor: Dr. Paul Williams Co-pyrolysis of low rank coal and plastic to extract oil is one of effective methods for solving the white pollution.
The interactions between coal and plastic during the co-pyrolysis process significantly improve the yield and
Keywords: quality of tar. However, the understanding of the interactions during co-pyrolysis from microscopic perspective is
Low rank coal still scarce. The effect of polyethylene on the cleavage of covalent bonds during Hami coal pyrolysis was
Plastic
investigated by combining TG-MS, Py-TOF-MS and ReaxFF MD simulations. The results showed that derivative
Co-pyrolysis
DTG curves can be decoupled into 6 sets of covalent bonds. The addition of PE had no effect on the breakage of
Interactions
Bond cleavage Cal-O bonds in HM from the chemical perspective, but it promoted the breakage of Cal-Cal bonds in both HM and
PE. Furthermore, after the addition of PE, the breakage peak temperature of Car-Cal in HM to shift towards a
higher temperature (from 532 to 545 ◦ C), and the peak area decreased from 13.12 % to 9.22 %. According to in-
situ Py-TOF-MS analysis, the addition of PE can promote the breaking of Cal-Cal bonds, resulting in the increase of
alkene products and radicals such as alkene, alkadienes and alkane radicals. Meantime, the long-chain alkenes
produced by PE cracking coats on the surface of HM during co-pyrolysis, which hinders the pyrolysis of the
broken Cal-Car bonds in its structure and leads to the reduction of aromatics. Moreover, the results of ReaxFF MD
simulations further confirmed that the results of experimental.

1. Introduction [3–6]. As a non-degradable synthetic material, waste plastics bring

Energy is the driving force of national economic development, and
the issue of energy supply is related to national strategic security. China
is short on oil and natural gas resources and highly dependent on foreign
countries. Compared with the oil and gas resources, China’s coal re­
sources are relatively rich, especially low rank coal, which accounts for
55 % of China’s proven coal reserves [1,2]. Pyrolysis at medium and low
temperature is an important technology for the direct conversion of low
rank coal. However, the practical application of low rank coal is still
limited due to the high oxygen content and heavy fraction content in the
pyrolysis tar, which restricts the subsequent processing and utilization.
Co-pyrolysis of low rank coal and hydrogen-rich waste materials is a
feasible method, which can not only improve the quality of pyrolysis tar,
but also effectively promote the resource treatment of waste resources
convenience to our life while also greatly challenges the environmental.
Polyethylene (PE) is one of the most common type waste plastics. China
is the largest consumer of PE in the world, accounting for 30 % of the
global PE consumption [7]. The high H/C in PE enables effective
hydrogen supply to coal during co-pyrolysis [8]. Numerous studies have
confirmed that there are obvious interactions between coal and PE
during co-pyrolysis [9–11]. Saha et al. observed that co-pyrolysis of PE
with coal can remarkably increase the calorific value of tar [12]. Qin
et al. found that the active intermediates formed by the pyrolysis of
waste plastic contributed to the interactions with coal [13], thus
increasing the quality and yield of tar. Additionally, our previous
research has also confirmed that co-pyrolysis of coal and PE reduces the
content of heavy fraction in tar effectively [14]. However, due to the
limitations of detection methods, many studies have been conducted to

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

https://doi.org/10.1016/j.joei.2024.101529
Received 28 November 2023; Received in revised form 4 January 2024; Accepted 8 January 2024
Available online 9 January 2024
1743-9671/© 2024 Energy Institute. Published by Elsevier Ltd. All rights reserved.
T. Zhang et al.
prepare pyrolysis products and analyze their properties using fixed beds.
The pyrolysis products inevitably undergo secondary reactions during
their formation and are collected as the final products after reaching the
target temperature and cooling.
In principle, the essence of pyrolysis is the breaking and reorgani­
zation of covalent bonds. The structure of coal is complex and the
products are enormous during pyrolysis. However, coal only consists of
limited types of major chemical bonds and fewer types of chemical
bonds are broken during pyrolysis process. The structure of plastic is
simple, which contains fewer types of covalent bonds compared to coal.
Besides, there are no new chemical bonds present in the structure of
plastic. Thus, the co-pyrolysis mechanism of coal and waste plastic can
be interpreted from the perspective of covalent bonds breakage. Ther­
mogravimetry (TG) is a common method to study the pyrolysis and co-
pyrolysis of coal and plastic, which measures the weight loss behavior of
the volatiles at different temperatures. It has been demonstrated that the
derivative thermogravimetric (DTG) data obtained from coal pyrolysis
can reflect the information of chemical bonds breakage in coal [15].
Peak splitting is a common method to analyze the integrated process
consisting of multiple seeds, and has been widely used in the analysis of
XPS, FTIR, NMR and other spectra. Some scholars have applied the
method of “peak splitting” to the analysis of DTG curve and obtained
more information from it [16–18]. Arenillas et al. analyzed the pyrolysis
characteristics of phenol formaldehyde (PFR) based on the “peak split­
ting” method [16]. They divided the DTG curve of PFR into 5 sub-peaks
and combined the information obtained from FTIR to clarify the
breakdown of covalent bonds during PFR pyrolysis. Shi et al. examined
the thermogravimetric process of coal with the “peak splitting” method,
and correlated the covalent bonds breaking information with the ther­
mogravimetric temperature [17]. Feng et al. determined the information
of covalent bonds in liquefied residue by fitting a certain number of
sub-peaks to the DTG curve [18]. Zhao et al. applied the method to the
pyrolysis process of oil shale and their results showed that the volatili­
zation of organic matter was primarily attributed to the cleavage of
Cal-Cal over 420 ◦ C [19]. This approach provides a new way of thinking
about the exploration of co-pyrolytic interactions between coal and
plastics.
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. The understanding of primary volatiles at the
molecular level helps to further elucidate the pyrolysis mechanism of
carbon-containing resources. Yang et al. [15] used Py-TOF-MS that
equipped with double ionization sources (PI and EI) to capture primary
volatiles from pyrolysis of PVC, revealing the Cl evolution and aroma­
tization mechanism. Zhu et al. [14] performed Py-TOF-MS experiments
on the primary volatiles fraction during lignin pyrolysis, and found that
the cleavage of β-O-4 linkages is the dominant contributor to the
depolymerization of lignin at the range of 100–300 ◦ C. As mentioned,
in-situ Py-TOF-MS has been successfully utilized to explore the mecha­
nism of pyrolysis. Undeniably, the production of primary volatile com­
ponents is intricately linked to the breaking of covalent bonds. Hence,
the in-situ Py-TOF-MS technique is also expected to be used to explore
the in-depth interactions from the bond cleavage perspective during
co-pyrolysis of coal and plastics.
With the continuous improvement of computers, molecular dy­
namics simulation has been proven to be an effective tool to augment
experimental results. The reactive molecular dynamics (ReaxFF MD)
method can simulate both the evolution of bond breakage and formation
with time and has been widely used in complex coal pyrolysis process
[20,21]. Castro Marcano et al. [22] explored the effect of sulfur on coal
pyrolysis with ReaxFF MD simulation, and discussed the role of different
types of sulfur functional groups in the pyrolysis process. Xu et al.
investigated the initial pyrolysis mechanism of lignite with ReaxFF MD
isothermal simulation method [23]. It was found that the pyrolysis
process of lignite begins with the dissociation of the weaker bridging
bonds Cal-O and Cal-Cal. He et al. investigated the synergistic effect
2
Journal of the Energy Institute 113 (2024) 101529
between biomass and municipal sewage sludge (MS) using ReaxFF [24].
They found that the free radicals produced by MS and biomass increased
the degree of biomass decomposition, while also resulting in an earlier
decomposition time for MS. Feng et al. [25] investigated the co-pyrolysis
behavior of coal and plastic using the ReaxFF MD simulation method.
They discovered that the inclusion of PE could enhance the cleavage of
C-C and C-H bonds, resulting in an increased production of tars.
Regrettably, most of the current ReaxFF MD simulation studies mainly
focus on the overall evolution trends of C-C, C-O, and C-H bonds without
distinguishing between aromatic carbon (Car) and aliphatic carbon (Cal).
On the other hand, the model scale directly affects the pyrolysis reaction
process, product distribution, and pyrolysis reaction diversity. The
ReaxFF model becomes computationally time-consuming when used on
a scale that is too large (over 100000 atoms), while a scale that is too
small (below 10000 atoms) is not suitable for studying the properties of
polymers. Therefore, the model should be constructed with both scal­
ability and diversity, as long as the cost is appropriate.
Co-pyrolysis of coal and plastics is a free radical-driven process in
which multiple reaction pathways, including cleavage, polymerization,
and recombination, occur simultaneously, which is challenging to ach­
ieve using separate experimental methods. The present research aims to
examine the interactions between coal and plastic during co-pyrolysis
from the perspective of covalent bonds cracking by combining experi­
ments and ReaxFF MD. In this study, the DTG curves of coal and plastic
co-pyrolysis were decoupled by the “peak splitting” method in order to
link the covalent bonds with similar bond energy in the coal structure to
the thermogravimetric temperature. The DTG curves of co-pyrolysis of
coal with different ratios of PE were analyzed to further clarify the effect
of plastic on covalent bonds cleavage. At the same time, the main pri­
mary volatiles produced from the pyrolysis of Hami coal (HM), PE, and
their mixtures were online capture during pyrolysis with the high
sensitivity through in-situ Py-TOF-MS. In addition, the ReaxFF MD was
used for simulation research. A model consisting of approximately
30,000 atoms has been established in order to obtain the trend of typical
covalent bonds with temperature during pyrolysis and co-pyrolysis. This
model is capable of accurately capturing the evolutionary trend of gas-
liquid products and can also observe the formation of solid products
by extending the simulation time appropriately. The obtained results
can be used as a reference to explore the mechanism of coal and plastic
co-pyrolysis, and provide new perspectives on the study of coal and
carbon-containing waste co-pyrolysis.
2. Experimental
2.1. Materials
Hami (HM) coal, a low rank coal, from Xinjiang and polyethylene
(PE) powder purchased from Macklin company were used in this work.
The HM coal was crushed and sieved to less than 74 μm. In addition, five
model compounds, PE, polyphenylene ether (PPO), lignin, poly­
phenylene sulfide (PPS) and calcium carbonate (CaCO3), were selected
for the types of covalent bonds present in coal structural and were py­
rolyzed under the same experimental conditions. All the model com­
pounds were obtained from the Macklin company. The proximate and
ultimate analyses of samples were provided in Table 1.
2.2. Thermogravimetric analysis
A thermogravimetric analyzer (Setsys Evolution, SETARAM, France)
coupled with mass spectrometry (Omnistar, Switzerland) (TG-MS) was
used to investigate the thermal decomposition properties of the samples.
Approximately 10 mg of sample was used for each test, with different
proportions of PE (0, 5 %, 10 %, 15 % and 100 %). The sample was
loaded into an alumina container and gradually warmed at a rate of 10
◦
C/min in high purity Ar (100 mL/min), reaching 900 ◦ C from 25 ◦ C.
T. Zhang et al.
Table 1
The ultimate analysis of samples.
Sample Proximate analysis (wt/%)
Mad Ad Vdaf
HM 7.46 9.93 53.01
PE – – 100.00
ad, air dried basis; St, ad, total sulfur (air dried basis); *, by difference; -, not detected.
2.3. Morphological evolution of samples
A heating stage coupled with microscope (HTSM) was used to
observe the morphology of samples during co-pyrolysis process. The
sample was placed in a crucible under argon atmosphere and warmed
from 25 ◦ C to 600 ◦ C with the rate of 10 ◦ C/min.
2.4. Py-TOF-MS analysis
The main primary volatiles produced from the pyrolysis of HM, PE,
and their mixtures were analyzed using an in-situ Py-TOF-MS (Quan­
Tang Science Instruments, China). The device consists of a vacuum
system, a programmed pyrolysis module, an ion source, a mass analyzer,
and an ion detector, and is schematically shown in Fig. S1(supplemen­
tary material). The pyrolysis and ionization zones are maintained in a
high vacuum (≤10− 5 Pa), with a distance of only 20 mm between them,
which helps to prevent the secondary reactions between primary vola­
tiles and can been considered an in-situ detector means [26,27].
For each test, approximately 5 mg of the sample was loaded into a
sample tube. After the vacuum conditions necessary for the experiment
were achieved, the sample was heated from room temperature to 700 ◦ C
at a rate of 10 ◦ C/min. The relative content of volatiles was obtained
through semi-quantitative analysis [27,28], as described by Eq. (1).
Sumi
Y(%) = ∑n × 100%
1 Sumi
where, Y is the relative content for species i, sumi represents the sum of
∑ found to be consistent with the MS results during the PE pyrolysis. Thus,
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 ) × 100%
where, Y1, Y2 are the experimental content of HM coal and PE pyrolysis
alone.
2.5. ReaxFF MD simulation
Eight different molecular weights of single molecules were con­
structed for simulation in order to make the simulation results closer to
the real coal. A coal model eventually containing 29583 atoms was
obtained through a series of optimizations with the chemical formula
C15650H10653O3079N159S42. Five long chains of polymerization from 100
to 300, a large-scale PE model containing 53,488 atoms, with the mo­
lecular formula C17800H35688 were constructed in order to make the PE
model more similar to plastic products. The simulation steps have been
described in more detail in our previous work [29]. Additionally, two
co-pyrolysis systems consisting of 9 coal molecules/1 PE molecules (9:1)
and 7 coal molecules/3 PE (7:3) molecules were constructed using the
same method. The effect of PE on covalent bond breaking during coal
pyrolysis was investigated by four constructed models using ReaxFF MD
from 300 K to 3000 K at 1 K/ps (Corresponding experimental temper­
ature from 230 to 500 ◦ C).
Journal of the Energy Institute 113 (2024) 101529
Ultimate analysis (daf, wt/%) St, ad
C H O* N
74.36 5.46 17.86 0.92 1.40
83.09 16.90 – – <0.01
3. Results and discussion
3.1. Pyrolysis of model compounds
To evaluate the cleavage rules of typical covalent bonds in coal and
to correlate the cleavage of different types of covalent bonds with the
thermal weight loss behavior of coal, five model compounds were
selected for pyrolysis. The structures of the model compounds are shown
in Fig. 1. The main covalent bond types contained in the five model
compounds were listed in Table 2.
The structure of PE is a simple long-chain aliphatic hydrocarbon,
which mainly undergoes breakage of Cal-Cal bonds during pyrolysis [30].
As shown in Fig. 2 (a), the cracking of PE begins at 400 ◦ C and is
completely pyrolysis before 500 ◦ C. Fragmentation peaks of CH4, C2H4,
C2H6 and C4H8 are detected in MS in the same temperature range (Fig. 2
(b)), which is caused by the random fracture of the main skeleton of PE.
In addition, a sharp DTG peak of PE pyrolysis can be found, indicating
that its pyrolysis process is relatively single.
Typical Car-O and benzene ring structures are contained in PPO. The
Car-O bonds in PPO break to form the corresponding monomer or
polymorph during the progress of PPO pyrolysis. Simultaneously, the
methyl groups on the side chain of PPO breaks to form methyl, phenol
and methyl phenol [31]. As shown in Fig. 3(a), the weight loss rate of
PPO reaches 92.84 % at 500 ◦ C. Strangely, only the signal of CH4 is
(1) detected in MS. Comparing Fig. 2(b) and Fig. 3(b), the temperature
corresponding to the thermal weight loss interval of PPO is inconsistent
with that of the signal interval detected on MS. The pyrolysis interval is
the effect of signal transmission lag can be excluded. This may be due to
the fact that the volatile fragments of large molecules generated by Car-O
(2) fracture cannot enter the MS detection system due to their large mo­
lecular weight, but cause significant thermal weight loss [15]. This in­
dicates that the cleavage of Car-O bonds occurs at 400–500 ◦ C.
Additionally, a large amount of CH4 is detected in MS between 500 and
650 ◦ C, which is caused by the cleavage of the Car-Cal bonds in PPO. The
results of Shi et al. also confirmed that methane mainly originated from
the breakage of the Car-CH3 bond when the pyrolysis temperature is
above 500 ◦ C [32].
The pyrolysis properties of other model compounds are explored in
the same way. We describe them in detail in Section S1.1-1.3.
Based on the analysis above, the thermal weight loss intervals were
calculated for the five model compounds with initial and termination
temperature corresponding to thermal weight loss rates of 20 % and 80
%, respectively [33]. The temperature information corresponding to the
break covalent bonds in model compounds is shown in Table 3.
3.2. Pyrolysis of HM coal
As seen from Fig. 4 that the pyrolysis process of HM can be divided
into three pyrolysis stages. The first stage is between 25 and 300 ◦ C, with
a weight loss of 10.73 %, which is dominated by decarboxylation re­
actions. Additionally, it includes the removal of small amounts of free
water, gas desorption, and the breaking of weak bonds on the fatty side
chains in the coal structure [17]. The second stage is between 300 and
600 ◦ C, which is the main pyrolysis stage of HM, and the weight loss in
this stage accounts for 73.67 % of the total weight loss. The major co­
valent bonds in the coal are broken during the process, producing large
3
T. Zhang et al. Journal of the Energy Institute 113 (2024) 101529

Fig. 1. Chemical structure of model compounds.

amounts of volatile matter. The weight loss rate of HM reaches its

Table 2
maximum at 446 ◦ C. The third stage is between 600 and 800 ◦ C, with a
The bond types contained in the five model compounds.
weight loss of 15.60 %, which mainly occurs in char polycondensation
Sample Lignin PE PPO PPS CaCO3 and mineral decomposition reactions. It is well known that the cleavage
Bond types Cal-O Cal-Cal Car-O/Cal Car-S Carbonates in coal of covalent bonds in the structure of coal is closely related to tempera­
ture [34]. Chemical bonds with similar bond energies break

Fig. 2. TG and DTG curves (a), evolution curves of gases (b) of PE pyrolysis.

Fig. 3. TG and DTG curves (a), evolution curve of gas (b) of PPO pyrolysis.

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T. Zhang et al. Journal of the Energy Institute 113 (2024) 101529

Table 3 CCO indicates a higher overlap of the two peaks, which means a poorer
Assignment of peaks from DTG curve of model compounds. fitting result.
Sample Bond cleavage Peak temperature (◦ C) Pyrolysis range (◦ C) Table 4 shows the results of R2 and CCO results using 6,7 and 8 sub-
peaks. It can be seen that the DTG curve is best fitted for 8 sub-peaks,
Tmax Ti Tf
with the smallest CCO and highest R2, and the fitting results are
Lignin Cal-O 338 305 386 shown in Fig. 5.
PE Cal- Cal 475 452 479
PPO Car-O 447 426 456
Car- Cal 546 500 600 3.2.2. Chemical bonding information of HM coal pyrolysis
PPS Car-S 546 505 565 Various volatiles over a temperature range are produced by the
CaCO3 Generation of CO2 740 675 750 breaking of a set of covalent bonds with similar bond energies [35]. The
main pyrolysis temperature of HM coal is between 300 and 600 ◦ C.
Based on the analysis of the pyrolysis characteristics of model com­
pounds in Section 3.1, the stage of HM is divided into three parts,
including 300–400 ◦ C, 400–500 ◦ C, and 500–600 ◦ C. The three stages
correspond to the breaking temperature of three groups of covalent
bonds with similar bond energies, which are Cal-O, Cal-Cal/Cal-H/Car-O,
and Car-Cal/Car-S. It can be seen from the DTG curve of HM pyrolysis that
an obvious weight loss peak appears below 150 ◦ C, which is attributed to
the removal of free water from HM coal. Based on the temperature
corresponding to H2 in MS (Fig. S5), it can be judged that the conden­
sation of the aromatic ring in HM occurs at higher temperature. A clear
weight loss peak is observed when the temperature is above 700 ◦ C,
which corresponds to the decomposition of inorganic carbonates in HM
coal [17]. The DTG curve of HM pyrolysis is decoupled, and the chem­
ical bond information of each sub-peak is shown in Table 5.

3.3. Effect of PE addition on covalent bonds breakage in HM

Based on the above analysis, it can be seen that correlating weight

loss of HM coal with changes in chemical bonds through the peak fitting
method can interpret the coal pyrolysis properties from the perspective
Fig. 4. TG and DTG curves of HM coal.
of bond cleavage. Different proportions of PE and HM were mixed uni­
formly and co-pyrolyzed to explore the effect of PE on the breakage of
simultaneously within a certain temperature range. As a consequence,
covalent bonds in HM. It should be noted that the breakage of Cal-Cal in
the weight loss process of HM coal can be analyzed using the “peak
HM and PE is unsynchronized. Therefore, the Cal-Cal bond between 400
splitting” method. ◦
C and 500 ◦ C is divided into two sub-peaks, representing the Cal-Cal
bond in HM and PE, respectively.
3.2.1. The number of sub-peaks of DTG curve
Fig. 6 shows the DTG fitting curves of the co-pyrolysis of HM and PE.
The main chemical bonds, including Cal-O, Cal-Cal, Car-Cal, Car-O, Car-
The peak temperature and peak area are important parameters for
Car, Car = Car, Car-H, and Cal-H, break during coal pyrolysis. Among
examining the pyrolysis interactions. The peak temperature indicates
them, Car-Car, Car = Car and Car-H bonds reside in the aromatic core of
the bond energy of various types of bonds (or a collection of bonds of
the coal molecule, which are more difficult to break than the other five
similar energy) in the samples, and the peak area can be used as a
covalent bonds due to their higher bond energy [17]. Thus, they are not
reference for the amounts of volatile fragments produced during co-
considered in this study. According to previous studies, the Cal-H and
pyrolysis process [17,35]. Fig. 6 and Table 6 show the changes in the
Cal-Cal bond energies are similar [17], and the decomposition of inor­
peak positions and peak areas of each sub-peak of the DTG curve from
ganic carbonates and removal of free water exist during coal pyrolysis.
co-pyrolysis of HM and PE at different proportions.
Thus, the DTG curve for coal pyrolysis alone contains at least six
As shown in Table 6, the peak temperature of sub-peak 1 does not
sub-peaks. In order to find the optimal peak separation result and
change because it is a weight loss peak caused by the removal of free
determine the number of sub-peaks, we tried to fit the DTG curve of HM
water from HM and does not involve the breakage of chemical bonds.
coal pyrolysis into 6, 7, and 8 sub-peaks. Detailed fitting parameters are
The peak temperature of sub-peaks 2 and 3 increases with the increase of
listed in Table S1.
the PE addition ratio. As can be seen from Fig. 2, PE hardly undergoes
Generally, better fitting results tend to be accompanied by a higher
cracking before 400 ◦ C. PE has a low softening point, which melts and
number of sub-peaks. From the perspective of correlating covalent
transforming into fluid at about 110 ◦ C (as shown in Fig. 7(with the ratio
bonds and pyrolysis behavior of coal, a high degree of overlap between
of 1:1)). With the temperature increases further, the PE begins to expand
the two sub-peaks indicates that two subpeaks originate from the same
and form a fluid and wrap the nearby HM particle. The molten PE is not
type of covalent bond or a covalent bond with similar bonding energy.
conducive to heat transfer [37], resulting in a shift of the peak tem­
Therefore, the fitting results should take the overlapping degree of
perature of sub-peaks 2 and 3 toward a higher temperature. The inhib­
adjacent sub-peaks into account. The coefficient of curve overlapping
itory effect increases with the increase of PE ratio.
(CCO) [17] is defined by Eq. (3):
The peak temperature of sub-peak 4 in the co-pyrolysis DTG shifts
( ) ( )
1∑ n
Ti− 1,f − Ti,i + Ti,f − Ti+1,i
CCO = ( ) (3)
n i=1 Ti,f − Ti,i Table 4
Comparison of fitting results by 6,7 and 8 sub-peaks.
where n represents the number of sub-peaks; Ti,1 and Ti,f are the initial Number of sub-curves 6 7 8
and ending temperature of sub-peak i, respectively. It should be noted CCO 2.03 2.38 1.33
that T1− 1 or Tn+1 of sub-peak 1 and n are noted as 0. A larger value of R2 0.9747 0.9975 0.9976

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T. Zhang et al. Journal of the Energy Institute 113 (2024) 101529

Fig. 5. DTG curve of HM coal and the fitting results by 8 sub-peaks through
multiple Gaussian functions.
Table 5
Assignment of peaks from DTG curve of HM coal [17,36].
Peak Origin
1 Release of bonded water
2 Decomposition of carboxylic acid
3 Breakage of Cal-O
4 Breakage of bonds between Cal-Cal, Cal-H, and
Car-O
5 Breakage of bonds between Car-Cal, Car-S
6 Condensation of aromatic rings
7 Decomposition of carbonates
8 Condensation of aromatic rings
toward the high temperature region compared to HM pyrolysis alone.
For the individual pyrolysis of HM, the peak temperature of sub-peak 4 is
449.32 ◦ C. At the same temperature, the weight loss of PE is 22.72 %,
and its main body still exists in a molten state. The Cal-Cal bonds in the
PE start to break when the temperature is higher than 400 ◦ C, but the
molten PE wraps the surrounding HM particles, which is not conducive
to heat transfer to HM particles. On the other hand, the molten PE in­
hibits the escape and diffusion of volatiles from HM pyrolysis, resulting
in an increase in the peak temperature of the weight loss detected in
DTG. With the increase of PE ratio, the breaking temperature of Cal-Cal
bonds in HM further increase. Compared to PE pyrolysis alone, the peak
temperature of sub-peak 5 during co-pyrolysis shifts toward a lower
temperature. The volatiles generated at lower temperature from the
matter are absorbed by the material that pyrolysis later, thus inducing
early cleavage of the post-pyrolyzed material [38]. Besides, we can find
that the peak temperature of sub-peak 6 in the co-pyrolysis DTG curve
moves toward a higher temperature compared to that of HM pyrolysis
alone. The long-chain olefin produced by PE cracking wraps around the
coal surface and inhibits the breakage of Car-Cal bonds in HM [10]. The
fragments wrapped around the HM surface are gradually decomposed
with the further increase of temperature. Meanwhile, the char begins to
condense and the cleavage of bonds is almost unaffected.
The peak areas of sub-peaks 1, 2 and 3 are not discussed since the
variation of their peak areas can be easily influenced by the heat transfer
of the molten PE. The PE has been completely converted into volatiles
after 500 ◦ C, which hardly affects the subsequent breaking of covalent
bonds in HM. Therefore, only the changes in peak area for sub-peaks 4, 5
and 6 are discussed and compared with the theoretical value.
As can be seen from Fig. 8, the peak area of sub-peak 4 is significantly
Peak temperature range
(◦ C)
higher than the theoretical value, indicating that PE as an H-donor
significantly promotes the breakage of Cal-Cal bonds in HM and signifi­
cantly improves the tar yield. The peak area of sub-peak 5 is also higher
<150
150–300
300–400 than the theoretical value, which is due to the induced effect during the
400–500 co-pyrolysis of HM and PE. The free radicals generated by HM pyrolysis
induce further cleavage of PE pyrolysis macromolecular fragments,
500–600 which contributes to the formation of active free radicals such as alkenyl
600–650
650–750
and alkyl radicals [10]. Additionally, the peak area of sub-peak 6 is
>750 significantly lower than the theoretical value and decreases further with
the increase in PE proportion. On the one hand, there are no Car-Cal
bonds in PE. On the other hand, the long chain olefins produced by PE
cracking wrap around the HM surface and inhibit the breakage of the
Car-Cal bonds in HM. In summary, the fundamental reason for the sig­
nificant increase in tar yield by co-pyrolysis of HM and PE can be

Fig. 6. DTG curves and fitted sub-peaks of HM and PE at different proportions: (a) 5 %, (b) 10 %, (c) 15 %.

Table 6
Fitting results of DTG curves.
Peak (◦ C) H2O COOH Cal-O Cal-Cal (HM) Cal-Cal (PE) Car-Cal Condensation of aromatic rings CO2 Condensation of aromatic rings
Sample

HM 95.00 263.02 385.78 449.32 – 532.22 627.84 720.00 771.84

HM+5%PE 95.00 265.00 387.63 450.40 467.19 538.36 635.25 720.00 778.85
HM+10%PE 95.00 270.95 389.00 451.09 473.67 544.01 640.65 720.00 779.03
HM+15%PE 95.00 274.97 392.00 454.68 474.17 544.48 638.94 720.00 777.26

6
T. Zhang et al.
Fig. 7. Evolution of the morphology of HM and PE during co-pyrolysis (1:1).
Fig. 8. Peak areas of sub-peaks 4, 5 and 6 of HM and PE co-pyrolysis.
attributed to the fact that co-pyrolysis promotes the cleavage of Cal-Cal
bonds in the samples.
3.4. In-situ Py-TOF-MS analyses
The volatiles released during the co-pyrolysis of coal and different
proportions of PE were detected in-situ using Py-TOF-MS. The spectra
are shown in Fig. 9, and were identified based on the m/z ratio in the
mass spectra and literature reports. Detailed assignments are listed in
Table S2. To analyze the interactions during co-pyrolysis quantitatively,
a semi-quantitative method was employed to calculate the relative
contents of the main volatiles. The calculated values of primary volatiles
during co-pyrolysis process were also determined.
The relative contents of the main primary volatile fractions from the
pyrolysis of HM and PE alone are presented in Fig. 10. It can be seen that
PE pyrolysis produces a significant amount of alkene products, which
are dominated by C4-C8, with relative contents of 1.11 %, 1.80 %, 1.44
%, 1.34 %, and 1.16 %, respectively. In addition, several radicals were
7
Journal of the Energy Institute 113 (2024) 101529
detected, including alkane radicals, alkene radicals, and some alka­
dienyl radicals. A large number of diolefins were also detected, such as
hexadiene and heptadiene, with contents of 1.39 % and 1.70 %,
respectively. This indicates that the olefinic intermediates generated
from PE pyrolysis were re-polymerized during the pyrolysis process.
Compared to PE, the structure of HM coal is much more complex,
resulting in a significant increase in the types of pyrolysis products. It
can be observed that pyrolysis of HM coal produces a large number of
phenolic compounds, including methylphenol and dimethylphenol with
relative contents of 1.02 % and 0.78 %, respectively. At the same time, it
is accompanied by the generation of various aromatic products such as
toluene (0.43 %), ethylbenzene (0.50 %), trimethylnaphthalene (0.49
%), dimethylanthracene (0.41 %). In addition, a minor quantity of
alkene products such as propylene (0.53 %), butene (0.51 %), and
pentene (0.40 %) are also generated.
No new substances were found to be generated in the HM coal and PE
co-pyrolysis spectra. However, the relative contents of the pyrolyzed
major volatile fractions exhibited significant differences compared to
the theoretical values (Fig. 11). As can be seen, co-pyrolysis significantly
promotes the generation of alkene products. For example, the relative
contents of pentene, hexene, pentadiene, hexadiene, and heptadiene
have significantly increased compared to calculated values, and are
closely related to the proportion of PE added. The production of alkenes
during coal pyrolysis mainly originates from the breaking of Cal-Cal
bonds [18], which further confirms that the co-pyrolysis of the two
promotes the breaking of Cal-Cal bonds in the HM coal and PE structures.
Although the barrier formed by the molten PE hinders the escape of
primary volatiles from HM coal pyrolysis, it also enhances the interac­
tion between the primary volatiles and PE, thereby promoting the
further breakage of Cal-Cal bonds in PE. The relative content of toluene,
dimethylbenzene, dimethylnaphthalene and methylanthracene in the
aromatic products is lower than the calculated value. This observation is
consistent with the results reported by Wu [8]. This may be attributed to
the fact that the long-chain alkenes produced by PE cracking coats on the
surface of the HM coal and hinders the pyrolysis of the broken Cal-Car
bonds in its structure [39], which leads to a reduction of aromatics. For
phenolic products, it can be observed that their relative content is
slightly higher than the calculated value. The excessive presence of PE
forms a melting layer that hinders the release of volatiles from HM py­
rolysis, causing the phenoxy radicals reacting with the hydrogen
T. Zhang et al.
Fig. 9. PI-MS spectra of volatiles from (a) HM coal, (b) PE, and their mixtures pyrolysis: (c) HM+5%PE, (d) HM+10%PE, (e) HM+15%PE.
radicals released by PE cracking [8]. In addition, the relative content of
alkene radicals, alkadienes radicals, and alkane radicals is significantly
higher than the calculated value. This indicates that the co-pyrolysis of
the HM and PE contributes to the formation of alkene and alkadienes
products, but also facilitates the fracture of Cal-Cal bonds, thereby pro­
moting the release of radicals.
3.5. ReaxFF MD simulation
The evolution trend of covalent bonds breakage and formation with
time during low rank coal and PE co-pyrolysis process can be intuitively
obtained by ReaxFF MD simulation [29]. The effect of PE addition on the
cleavage of Cal-Cal, Cal-O and Car-Cal bonds in the volatile fraction
(C1-C40) system during low rank coal pyrolysis is analyzed through
ReaxFF MD simulations, as shown in Fig. 12. It should be noted that the
breakage and formation of covalent bonds in the pyrolysis system occur
simultaneously, and the changes of their content are a comprehensive
result at a certain temperature.
The higher number of functional groups containing a type of cova­
lent bonds in the system indicates a higher content of that covalent
bonds. At low temperatures, samples in the system do not begin to
8
Journal of the Energy Institute 113 (2024) 101529
decompose, therefore no volatile fraction (C1-C40) can be detected. With
the increase of temperature, volatiles containing specific covalent bonds
appear in system. The number of covalent bonds formed is greater than
that of broken, which shows an increasing trend. With the further in­
crease of temperature, these covalent bonds in volatiles also begin to
break, and the rate of breakage is higher than the rate of generation,
showing a decreasing trend as a whole. The higher temperature of peak
indicates the harder break of bonds. As shown in Fig. 12 (a), the peak
temperature of the Cal-O bonds almost does not move with the addition
of PE, which further indicates that the addition of PE does not have
chemical impact on the breakage of the Cal-O bonds in the coal structure.
The variation of the number of Cal-Cal bonds in the simulated system
with temperature is shown in Fig. 12 (b). The Cal-Cal bonds in PE do not
show any change in the early stage of pyrolysis due to the fact that PE
only undergoes softening and melting at lower temperature. It is
consistent with our pyrolysis results in Fig. 2. With the increase of
temperature, the number of Cal-Cal bonds in PE increases sharply, which
is attributed to the major chain of PE starts to break irregularly and
generates large numbers of olefins and alkanes fragments. In the py­
rolysis system of coal, the Cal-O bonds cleave at low temperature, pro­
ducing volatile fragments that contain Cal-Cal bonds. The Cal-Cal bonds in
T. Zhang et al. Journal of the Energy Institute 113 (2024) 101529

Fig. 10. Relative content of main primary volatiles from (a) HM coal, (b) PE.

Fig. 11. Relative content of main volatiles and their synergistic values during co-pyrolysis of HM coal and PE: (a, e) alkenes, (b, f) aromatics, (c, g) phenols, and (d, h)
free radicals.

the coal begin to break with the temperature increases and a large
number of C5-C40 fragments are released [29]. As the temperature rises
further, the polycondensation reaction in the system dominates the
pyrolysis and the fragmentation of C40+ increases, leading to a gradual
decrease in the Cal-Cal bonds content in volatiles. The content of Cal-Cal
bonds in the co-pyrolysis system is lower than that of coal pyrolysis
alone when the temperature is below 2000K, which is related to the fact
that the major chain of PE does not break at lower temperature. As the
temperature increases, the cleavage of the Cal-Cal bonds in PE produces a
large number of volatiles that combine with volatiles from coal pyrolysis

9
T. Zhang et al.
Fig. 12. Number evolution of functional groups with temperature: (a) Cal-O,
(b) Cal-Cal, (c) Car-Cal bonds.
to form tar, which prevents the condensation between macromolecular
fragments to form char. This results in a higher content of Cal-Cal bonds
in the co-pyrolysis system than that of coal pyrolysis alone. However, the
peak temperature of Cal-Cal shifts toward higher temperature due to the
higher cracking temperature of PE (2458 K) compared to coal (2200 K).
This is consistent with the experimental results. As shown in Fig. 12 (c),
the breakage temperature of Car-Cal moves toward a higher temperature
with the addition of PE. This indicates that the addition of PE is unfa­
vorable to the breakage of Car-Cal in coal, which is consistent with our
experimental results in Table 6.
4. Conclusions
In this paper, the effect of PE on the breakage of covalent bonds
during coal pyrolysis was conducted by splitting the DTG curve of py­
rolysis and co-pyrolysis process. Simultaneously, in-situ Py-TOF-MS was
used to detect the release of primary volatiles from co-pyrolysis of HM
and PE, and the volatiles content and deviation values of primary vol­
atiles were compared to further in-depth study of covalent bond
breaking during the co-pyrolysis. Besides, the trends of typical covalent
bonds with temperature during the co-pyrolysis of coal and PE were
obtained by combining the ReaxFF MD simulation method to corrobo­
rate with experimental results.
The results show that the DTG curve of co-pyrolysis of HM with PE
can be fitted by 9 sub-peaks, which correspond to the breakage of 6 sets
of covalent bonds. The addition of PE results in a shift of the breakage
temperature of carboxyl and Cal-O in HM to a higher temperature. The
peak areas of the Cal-Cal bonds in HM and PE during co-pyrolysis are
significantly higher than the theoretical value, indicating that co-
pyrolysis significantly promotes the breakage of the Cal-Cal bonds in
10
Journal of the Energy Institute 113 (2024) 101529
both of HM and PE. Besides, the addition of PE causes the breakage peak
temperature of Car-Cal in HM to shift towards a higher temperature (from
532 to 545 ◦ C), and the peak area decreases from 13.12 % to 9.22 %. The
fundamental reason for the significant increase in tar yield by co-
pyrolysis of HM and PE is that co-pyrolysis promotes the cleavage of
Cal-Cal bonds in HM and PE. According to in-situ Py-TOF-MS analysis,
the addition of PE promotes the Cal-Cal bonds both of PE and HM to form
more alkene and alkadienes products, and also facilitate the transfer of
hydrogen (H) to react with the phenoxy group from HM to form phenolic
products. Meanwhile, ReaxFF MD simulation results also show that the
number of breaking reactions for Cal-Cal bonds in the co-pyrolysis system
is higher than that of coal pyrolysis alone. It further confirmed that the
addition of PE can promote the breakage of Cal-Cal bonds in the system.
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.
Acknowledgements
The research was financially supported by National Natural Science
Foundation of China (22078353, 22178371), Key Research and Devel­
opment project of Shanxi Province (202102090301004), Strategic Pri­
ority Research Program of the Chinese Academy of Sciences (Grant No.
XDA21020100).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.joei.2024.101529.
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