Chemical Engineering Journal 474 (2023) 145900

Contents lists available at ScienceDirect

Chemical Engineering Journal

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

Review

Free-radical behaviors of co-pyrolysis of low-rank coal and different solid

hydrogen-rich donors: A critical review
Lei Wu a, Yining Guan a, Changcong Li a, Lei Shi b, Sasha Yang c, B. Rajasekhar Reddy d, Gan Ye a,
Qiuli Zhang a, Rock Keey Liew e, Jun Zhou a, *, R. Vinu f, *, Su Shiung Lam g, h, *
a
School of Chemistry and Chemical Engineering, Xi’an University of Architecture and Technology, Xi’an 710055, China
b
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
c
Department of Chemical Engineering, Monash University, Victoria 3800, Australia
d
Department of Fuel, Minerals and Metallurgical Engineering, Indian Institute of Technology (Indian School of Mines), Dhanbad 826004, India
e
NV Western PLT, No. 208B, Second Floor, Macalister Road, 10400 Georgetown, Penang, Malaysia
f
Department of Chemical Engineering, Indian Institute of Technology Madras, Chennai 600036, India
g
Higher Institution Centre of Excellence (HICoE), Institute of Tropical Aquaculture and Fisheries (AKUATROP), Universiti Malaysia Terengganu, 21030 Kuala Nerus,
Terengganu, Malaysia
h
Department of Chemical Engineering and Materials Science, Yuan Ze University, Taoyuan, Taiwan

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

Keywords: Low-cost and accessible “hydrogen source” are the key to reducing the cost of coal hydropyrolysis technology.
Free radical behaviors The mechanism of hydrogen supply is a crucial scientific issue in this technology. Solid “hydrogen-rich” donors,
Co-pyrolysis such as biomass, waste plastics, oil shale, and coal liquefaction residue, possess favorable characteristics such as
Low-rank coal
affordability, abundant availability, high volatility and a high H/C ratio, which are considered ideal solid
Hydrogen-rich donors
Detection technology
“hydrogen sources” for coal hydropyrolysis. The co-pyrolysis reactions between low-rank coal and solid
“hydrogen donor” follow the mechanism of free radical reactions. Moreover, a clear investigation of the free-
radical behaviors and synergistic interactions between them can clarify the hydrogen supply mechanism in
the co-pyrolysis process of solid “hydrogen-rich” donors, resulting in the controlled production of high-quality oil
and gas products. This review systematically summarizes the free-radical behaviors during the co-pyrolysis of
low-rank coal and solid “hydrogen-rich” donors: Three detection methods of free radicals and their applications
are first introduced. Then, the factors influencing the free-radical behaviors during the co-pyrolysis are discussed,
and the influences of the free-radical behaviors on the products obtained by the co-pyrolysis are analyzed.
Finally, the results and challenges of free-radical behaviors are outlined. This work is intended to provide a
comprehensive and scientific basis for completing the mechanism of free-radical reactions in the co-pyrolysis of
low-rank coal and solid “hydrogen-rich” donors.

1. Introduction
Pyrolysis is one of the most mature technologies for clean and effi­
cient conversion and utilization of coal. It can achieve thermal conver­
sion of coal under mild conditions to produce high-value products such
as coke/semi-coke, tar, and gas [1,2]. However, because of the low H/C
ratio in coal, the low yield and poor quality of pyrolysis tar, and the low
yield of valuable gas components such as H2 and CH4 in the pyrolysis
gas, coal pyrolysis is economically inefficient [3–6]. The coal hydro­
pyrolysis technology can produce pyrolysis gas with a high calorific
value and tar with a high yield and quality; however, the costs of
“hydrogen rich” gases such as H2, CH4, and syngas are high, resulting in
the high cost of the coal hydropyrolysis technology [7,8]. Therefore, a
low-cost and accessible “hydrogen source” would be the key to reducing
the cost of coal hydropyrolysis, and the mechanism of hydrogen supply
during coal pyrolysis is a key scientific issue in this technology [9].
Common solid “hydrogen-rich” donors such as biomass, waste plastics,
oil shale and coal liquefaction residues are cheap, resource-rich, high
volatile and high H/C ratio [10–13]. For example, the total amount of
biomass resources that can be used as an energy source in China is
approximately 10 billion tons of standard coal annually [14]. However,
there is a lack of reasonable and effective use of biomass resources,

* Corresponding authors at: School of Chemistry and Chemical Engineering, Xi’an University of Architecture and Technology, Xi’an 710055, China.
E-mail addresses: zhoujun@xauat.edu.cn (J. Zhou), vinu@iitm.ac.in (R. Vinu), lam@umt.edu.my (S.S. Lam).

https://doi.org/10.1016/j.cej.2023.145900
Received 9 July 2023; Received in revised form 19 August 2023; Accepted 4 September 2023
Available online 6 September 2023
1385-8947/© 2023 Elsevier B.V. All rights reserved.
L. Wu et al.
resulting in the consumption of large amounts of hydrogen components
in the biomass at the low-end, which causes an unnecessary wastage of
resources [15]. Owing to the above characteristics of solid “hydrogen-
rich” donors, they are used in the hydropyrolysis of low rank coal to
achieve low-cost hydropyrolysis, which is ideal as a solid “hydrogen
source.” Regarding the radical reactions in pyrolysis, the hydrogen
radicals provided by the “hydrogen-rich” donors in the pyrolysis re­
actions can stabilize the intermediate radical fragments and promote the
generation of light components, thus enhancing the distribution and
quality of the pyrolysis products. In addition, the co-pyrolysis of low-
rank coal and solid “hydrogen-rich” donors not only enhance the utili­
zation value of “hydrogen-rich” donors but also realizes clean and effi­
cient conversion and graded utilization of low-rank coal resources due to
it is cheap and high H/C ratio [16,17]. The advantages and disadvan­
tages of the co-pyrolysis of low-rank coal and different solid “hydrogen-
rich” donors are presented in Fig. 1.
Considering the significant advantages of solid “hydrogen-rich” do­
nors in the field of coal pyrolysis, the study of the co-pyrolysis of low-
rank coal has received considerable attention in recent years. As
depicted in the Web of Science statistics (Fig. 2a), the number of aca­
demic papers with the subject terms “Coal,” “Co-pyrolysis,” and “Free
radical” is increasing each year and more researchers are focusing on the
importance of free-radical behaviors during the co-pyrolysis of coal. The
co-pyrolysis process of coal has been extensively studied and summa­
rized in the literature. Generally, this process follows the free-radical
mechanism, involving the formation of free-radical fragments from the
breakage of covalent bonds and the subsequent condensation reaction
between these fragments. The solid products, namely semi-coke and
coke, are produced through the coupled polycondensation of large free
radical fragments, while the liquid and gas products are formed through
the coupled formation of smaller free radical fragments. However, it is
imperative to note that the co-pyrolysis process requires consideration
of the unique interaction between different pyrolysis feedstocks and the
impact of free-radical behavior on the final products. In particular, low-
rank coal has a hydrogen-poor composition, and other added pyrolysis
feedstocks typically serve as hydrogen-rich donors during co-pyrolysis
[9,12,13]. Furthermore, high-frequency keyword analysis of academic
papers related to the above-mentioned subject terms was conducted
using the VOSviewer visual analysis software. As shown in Fig. 2b, when
Fig. 1. Comparison of different “hydrogen-rich” donors during low-rank coal co-pyrolysis.
2
Chemical Engineering Journal 474 (2023) 145900
“Radical” is used as the node, it shows strong correlations with the
keywords “Content,” “Structure,” “Interaction,” “Reaction,” and “Tar”,
indicating the importance of radical behaviors in the study of the dis­
tribution and properties of the co-pyrolysis products. Furthermore, it is
evident that co-pyrolysis studies and product analysis employ a wider
range of addition and pyrolysis techniques and product analysis tech­
niques. Researchers are utilizing more comprehensive analytical
methods to investigate the co-pyrolysis behavior and product distribu­
tion mechanisms of various pyrolysis feedstocks. Hence, conducting a
comprehensive investigation into the co-pyrolysis characteristics of coal
and the solid “hydrogen-rich” donors by analyzing free-radical behav­
iors becomes imperative. Such an approach helps unravel the hydrogen
supply/hydrogenation mechanism of solid “hydrogen-rich” donors
during the coal pyrolysis process. Ultimately, this research aims to
enhance the production capacity and improve the quality of pyrolysis
products.
It is well-established that the co-pyrolysis reactions of the low-rank
coal and different solid “hydrogen-rich” donors have significant differ­
ences. These differences arise from variances in the free-radical re­
actions during co-pyrolysis, which can be attributed to the variations in
the components of the solid “hydrogen-rich” donors [18,19]. However,
the current studies on coal co-pyrolysis have mostly focused on the in­
fluence of raw materials and experimental parameters on the co-
pyrolysis properties (temperature-increasing characteristics and prod­
uct properties) and rarely systematically summarized the influence of
different solid “hydrogen-rich” donors as hydrogen donors on the co-
pyrolysis reaction from a microscopic radical perspective. The co-
pyrolysis of low-rank coal and solid “hydrogen-rich” donors similarly
follow the mechanism of radical reactions. However, the mechanism is
more complex than coal alone since the synergistic reactions between
the free radicals generated by each of the low-rank coal and “hydrogen-
rich” donors should be considered [20]. Therefore, it is necessary to
analyze the radical behaviors during the co-pyrolysis of low-rank coal
and solid “hydrogen-rich” donors to enhance the understanding of their
synergistic interactions to provide a theoretical basis for controlling and
regulating the co-pyrolysis products derived from low-rank coal.
Since the discovery of free radicals in coal by Ubersfeld in 1954 [21],
the free-radical behaviors during the transformation process of coal have
been extensively reported [18,22–24]. Electron paramagnetic resonance
L. Wu et al. Chemical Engineering Journal 474 (2023) 145900

Fig. 2. (a) Statistical diagram of publication volumes in different years, and (b) keyword co-occurrence network.

3
L. Wu et al.
(EPR) provides accurate and reliable information for analyzing free-
radical behaviors during this process. The team, under the supervision
of Prof. Zhenyu Liu, conducted an informative study on free-radical
behaviors during coal pyrolysis and coal solvent extraction, provided
an in-depth and comprehensive explanation of the free-radical behav­
iors reflected in the EPR spectrum, and proposed new methods to cap­
ture and quantify the free-radical behaviors using the EPR spectrum
[25]. These findings are expected to improve further the understanding
of the free-radical mechanism of the thermal transformation of coal. The
limitations of active radicals with ultra-high reactivities make detecting
active radicals (intermediates) during coal pyrolysis through the EPR
spectra is difficult. The capture technology of free radicals is a good way
to resolve this technical deficiency. The reaction of the trapping agent
with the active radicals at room or high-temperature forms adducts, and
the active radicals can be inferred from the analysis of the EPR or gas/
liquid chromatography-mass (GC/LC-MS) spectra of the adducts
[26,27]. Therefore, the combination of the EPR spectrum technology
and capture technology can address the free-radical behaviors during
the co-pyrolysis of low-rank coal and solid “hydrogen-rich” donors and
clarify the effects of free-radical behaviors on the pyrolysis products
(coke, tar, pyrolysis gas and pyrolysis water). This is beneficial for the
understanding of the hydrogen supply/hydrogenation reaction path­
ways of the solid “hydrogen-rich” donors during the pyrolysis of low-
rank coal.
Although the above technologies provide the technical support
required for analyzing free-radical behaviors during the co-pyrolysis of
low-rank coal and solid “hydrogen-rich” donors, most of the co-pyrolysis
studies still focus on the co-pyrolysis behaviors of low-rank coal,
particularly the influence of the pyrolysis conditions (such as type of
hydrogen donor, heating temperature and rate, feedstock mixing ratio,
feedstock mixing method) on the pyrolysis [28–30], and the free-radical
behaviors during the co-pyrolysis have rarely been summarized. Hence,
this work focuses on an in-depth and systematic summary of the free-
radical behaviors during the co-pyrolysis of low-rank coal and solid
“hydrogen-rich” donors, with detailed investigation and analyses of the
following four aspects to provide a comprehensive and scientific liter­
ature basis for improving the mechanism of free-radical reactions during
the co-pyrolysis of low-rank coal and solid “hydrogen-rich” donors.
(1) Detection of free radicals and their applications in co-pyrolysis.
(2) Free-radical behaviors during co-pyrolysis.
(3) Factors influencing free-radical behaviors during co-pyrolysis.
(4) Effects of free-radical behaviors on the co-pyrolysis products.
2. Detection methods of free radicals and their application in co-
pyrolysis
During the co-pyrolysis process, the covalent bonds in the low-rank
coal and solid “hydrogen-rich” donors are broken, forming large
numbers of active radicals, which can be coupled and polymerized to
produce pyrolysis products. However, some of the unreacted active
radicals are preserved in the pyrolysis products and form stable radicals
confined to a limited space because of the large steric hindrance and
electron delocalization [19,27,31]. The EPR spectrum detection tech­
nology can detect and analyze stable radicals in the pyrolysis products;
however, obtaining information about the active radicals is difficult
because they are extremely active and have a short lifetime of only a few
nanoseconds [32,33]. Thus, they are often indirectly detected and
analyzed using capture detection technology.
2.1. EPR spectra detection technology
The EPR spectra detection technology can obtain relevant informa­
tion on stable radicals through the interaction between an external
magnetic field and a magnetic dipole in a system under electromagnetic
radiation with a suitable wavelength, coupled with the capture of the
4
Chemical Engineering Journal 474 (2023) 145900
Zeeman transition of unpaired electrons in paramagnetic substances.
The characteristic parameters of the EPR spectra (hyperfine coupling
constant, g value, peak area, line width, and line shape) can be used to
determine the radical species and concentration [34]. Particularly, the
EPR spectra of the co-pyrolysis products derived from the low-rank coal
and solid “hydrogen-rich” donors often demonstrate a single spectral
peak due to the presence of several non-magnetic nuclear center radicals
such as C, O and S in the co-pyrolysis products. This results in the
coupling and superposition of various absorption peaks to form a single
absorption peak. Therefore, it is challenging to determine the properties
of the co-pyrolysis products using hyperfine coupling constants when
analyzing the EPR spectra.
2.1.1. Parameters analysis
(1) g value
The characteristic g value of the EPR spectrum is determined by the
position of the magnetic field intensity from the EPR spectral focus to the
baseline, and the species of the measured radical can be obtained from
its classification. As early as the 1980 s, Petrakis and Grandy summa­
rized the g values of the EPR spectra for several typical compounds in
coal [35–37]. When the g value exceeded 2.0040, the radicals were
identified as oxygen-centered radicals. Conversely, when the g value fell
below 2.0030, the radicals were categorized as carbon-centered radicals.
A g value between 2.0030 and 2.0040 indicated the existence of a
compound system containing both oxygen- and carbon-centered radi­
cals. Abdelsayed et al. found that the pyrolysis and co-pyrolysis of both
the coal and biomass yielded coke with free-radical g values between
2.0027 and 2.0034 and classified coke free-radical g values more finely
[38,39]. They found that coke with radical g values between 2.0027 and
2.0029 could be classified as carbon-centered radicals, and those with g
values between 2.0026 and 2.0028 belonged to the polycyclic aromatic
radicals (1–5 rings) with low carbon-centered radical content. The
polycyclic aromatic radical g values of the coke obtained by co-pyrolysis
were lower than those of coal pyrolysis alone, indicating that the com­
plex aromatic hydrocarbons in the coke obtained by the co-pyrolysis of
the coal and biomass were transformed into fewer cyclic aromatic hy­
drocarbons, which made the coke lighter. In addition, oxygen-centered
radicals with the g values of 2.0040 or more were not found in the coke
obtained by co-pyrolysis. This was due to the large numbers of oxygen-
containing groups that caused thermal decomposition with decarbox­
ylation, dehydration, and ether bond breakage reactions in the pyrolysis
process.
(2) Peak area
The peak areas in the EPR spectra were obtained by the second
integration of the first-order derivatives of the absorption curves. It is
also necessary to use a standard sample (the radical concentration of
which is known) for concentration calibration to obtain the relationship
between the radical concentration and the peak area function under test
conditions, such that the radical concentration of the test sample can be
calculated [39]. Thus, the spin concentration (Ns.spin) of the sample
(proportional to the absorption area under the ESR curve) was obtained
by comparing the quadratic integration area of the sample (Asample)
signal with that of the standard (Astandard) signal with the corresponding
Q-factor of the sample and the standard, as shown in Eq. (1):
Nstandard ⋅Asample ⋅Qstandard
Ns.spin = (1)
Astandard ⋅Qsample
where Nstandard is the spin concentration of a known standard sample
(spins/g); A is the integrated quadratic area of the sample and standard;
and Q is the quality factor of the sample and standard in the EPR test.
L. Wu et al.
(3) Linewidth
The linewidth in the EPR spectrum is represented by the half-width
value (G) at the half-height of the absorption peak, which reflects the
electron spin relaxation time, that is, the time required for the electron
to return from the spin-excited state to the ground state [40,41]. The
linewidth is mainly influenced by the “lifetime broadening” and “long-
term broadening”, which correspond to spin–lattice and spin–spin in­
teractions, respectively. During coal pyrolysis, oxygen affects the line­
width, and its paramagnetic effect increases the linewidth of the
pyrolysis products. Therefore, the co-pyrolysis of the coal and solid
“hydrogen-rich” donors can reduce the effect of oxygen on the linewidth
because the “hydrogen-rich” environment can greatly reduce the
oxidation ability of the oxygen-containing compounds or oxygen-
containing functional groups on the intermediates of the pyrolysis re­
actions [42]. During the co-pyrolysis process, removing heteroatoms
from the coal by hydrogen radicals enhanced the aromaticity of coke and
narrowed the EPR spectral line width [43–45]. Therefore, the hydrogen
content of the coke was positively correlated with the line width of the
EPR spectrum. Wu et al. [46] found that the line width of the O-centered
radicals decreased and that of π-type radicals increased in the EPR
spectrum of coke derived from the co-pyrolysis of the low-rank coal and
high-density polyethylene (HDPE) at different pyrolysis temperatures,
indicating that the oxygen radicals were restricted in the co-pyrolysis
process. In addition, they found that the line widths of the O-centered
radicals in the EPR spectrum of coke derived from the co-pyrolysis of the
low-rank coal and black polyethylene plastic (BPE) containing organic
additives (OPAs) with higher H/C ratio were significantly reduced
compared with those of white polyethylene (WPE) without the OPAs.
(4) Line shape
Similar to the g value, the line shape of EPR spectrum can be used to
determine the radical type. Uniformly broadened line shapes are mainly
EPR signals generated by the exchange effects or spin–lattice in­
teractions, which are usually Lorentzian in shape, whereas non-
uniformly broadened line shapes are overlapping EPR signals due to
radicals with different g values or hyperfine splitting, and their line
shapes are closer to Gaussian shapes [47,48]. The co-pyrolysis of the
coal and solid “hydrogen-rich” donors is a complex mixture, which
inevitably leads to a wide variety of radicals and complex reactions in
the system, and their line shapes appear as Gaussian or near-Gaussian
line shapes or a combination of both superimposed [49]. The Gaussian
line shapes are considered to be generated by individual non-interacting
radicals, indicating that there are few or almost no coupling reactions
with other radicals in the system. The narrow Lorentzian line shapes
result from the electron spin exchange processes. For instance, the EPR
spectra of coke derived from the co-pyrolysis of the low-rank coal and
HDPE showed a significant change in the Lorentzian/Gaussian ratio (L/
G). This indicates that the new radicals generated by the pyrolysis of
HDPE induce the transfer of unpaired electrons from the original radi­
cals among the aromatic clusters of coke, thus enhancing the radical
exchange effect [46].
2.1.2. EPR spectral application in co-pyrolysis
As mentioned above, the EPR spectrum of the co-pyrolysis products
of coal and solid “hydrogen-rich” donors often show a single spectral
peak, which is a composite curve formed by superimposing the EPR
signals of the paramagnetic components in the pyrolysis products, and it
is difficult to grasp the information about individual radicals directly
from the composite curve [50]. Therefore, the composite curve must be
resolved by spectral fitting. Because it is not a simple signal super­
position, the composite curve is resolved by fitting Gaussian or Lor­
entzian functions. The most commonly used functions are the Gaussian-
Lorentzian sum area functions, (Eq. (2)) [51–53].
5
Chemical Engineering Journal 474 (2023) 145900
a
y= [ ]2 [(0 [ ]2 ] (2)
1+ a3 x−a2a1 exp 1 − a3 ) 12 x−a2a1
where a0 is the area under the absorption curve, a1 is the center of the
curve, and a2 is the full width at half maximum. Parameter a3 is a shape
indicator and takes values in the range of 0–1 (0 is a pure Lorentzian line
and 1 is a pure Gaussian line).
Further, EPR spectral fitting methods have been widely used to
analyze coal pyrolysis products with more accurate results. Liu et al.
[54] fitted the EPR spectra of coal with deconvolution calculations, and
the free radicals in coal were fitted with one Gaussian line and three
Lorentz lines to obtain the highest correlation coefficients. Combined
with the g value classification of the free radicals of coal, the Gaussian
line is a simple aromatic cluster; the Lorentz 1, 2, and 3 lines belong to
oxygen-containing radicals (such as ethers and quinones), hydrocarbon
radicals, and σ oxygen-containing radicals, respectively. This method
also applies to the EPR spectra of the co-pyrolysis products of the coal
and solid “hydrogen-rich” donors. Wu et al. [46] performed a decon­
volution fitting calculation of the EPR spectra of the co-pyrolysis prod­
ucts of low-order coal and waste plastics. As shown in Fig. 3, the fitted
sub-curves were attributed to the C-centered with oxygen radicals (g =
2.0373–2.000382), 1–3 rings π-type quinone radicals or mono-, di-, tri-
methoxybenzene ethers radicals (g = 2.0387–2.00401), nitroxide radi­
cals (g = 2.0640–2.00776), and peroxide radicals (g =
2.01172–2.012551). This was followed by the quantification of the spin
concentration (Ng) for each radical using the area normalization method
to obtain the evolution of stable radicals during co-pyrolysis under
different conditions, such as the increase in the addition of waste plastic
and the increase in the area of C-centered with oxygen radicals, implying
the increase in the radical concentration in the system. In contrast, the
decrease in the integral area of the nitroxide radicals indicated a sub­
sequent reduction in the spin concentration of the nitroxide radicals.
Although several studies have confirmed the efficiency of the radical
parameters and evolution results obtained by deconvolution fitting
calculations, the reliability of the deconvolution technology for the
radical behaviors during co-pyrolysis has not yet been confirmed [55]. It
still has the following problems: (1) it is difficult to determine the radical
species due to the variety of hydrogen donors and the complexity of
radical reactions during co-pyrolysis; (2) it is affected by changes in the
surrounding chemical structure, such as other electron-giving or
electron-absorbing substituents during co-pyrolysis, resulting in
abnormal changes in the characteristic parameters obtained by the
fitting.
In-situ EPR technology has emerged as an advanced detection
methodology with several advantages over ex-situ EPR, which is often
challenging. While many studies have relied on ex-situ EPR to provide
information on stable free radicals at the beginning and end of a reac­
tion, this method only provides limited insight into the continuous
process of free-radical reactions [56]. In contrast, in-situ EPR allows for
real-time observation of the evolution of stable free radicals, directly
reflecting the reaction process. Moreover, in-situ EPR has been
employed to measure free radicals generated from covalent bond
breakage during thermal transformations, such as co-pyrolysis [57,58].
Seehra et al. [59] used the in-situ EPR technique to determine the
change in radical concentration during the pyrolysis and found that the
radical concentration during the coal pyrolysis showed differences at
different temperature stages. Specifically, the N-centered radical con­
centration first increased, decreased and then increased again with the
increase of temperature in the three stages of 300–500 K, 500–700 K and
700–900 K. Fowler et al. [60] used in situ EPR to confirm that desorp­
tion, free-radical recombination induced by low-temperature migration,
and thermal bond breaking are common processes in the pyrolysis of
low-rank coal.
L. Wu et al.
Fig. 3. EPR spectrum and fitted sub-curves of the coke sample: (a)coal coke, (b-g) coke obtained from coal and two kinds of waste plastics under varied mixing
ratios [46].
2.2. Capture detection technology
Common radical capture techniques include spin-trapping and
hydrogen donor solvent capture techniques. Spin-trapping is used to
capture active radicals under mild conditions; however, its application is
limited by high temperatures. Hydrogen-donor solvents compensate for
this shortcoming and can capture active radicals at high temperatures
during co-pyrolysis.
2.2.1. Spin-trapping technology
The spin-trapping technology involves the addition of an unsaturated
antimagnetic spin trap to a system that can trap free radicals under mild
conditions. When introducing a spin trap into the system, the originally
unstable active radicals react with it to form more stable or longer-lived
spin adducts [61,62]. The indirect detection of unstable active radicals
can be achieved by detecting and resolving the EPR spectra of spin ad­
ducts to invert the type of active radicals. For example, 5,5-dimethyl-1-
pyrroline-N-oxide (DMPO) can react rapidly with active radicals to form
new stable radicals or organics, thus achieving an extended active
radical lifetime, as shown in Fig. 4.
Fig. 4. Principle of the spin-trapping technology (with DMPO as an example).
6
Chemical Engineering Journal 474 (2023) 145900
The most widely used spin-trapping agents are mainly nitrone or
nitroso compounds, such as DMPO; 5-(diethoxyphosphoryl)-5-methyl-1-
pyrroline-N-oxide (DEPMPO); N-tertbutyl α-phenylnitrone (PBN); 5-
(1,1-dimethylethoxycarbonyl)-5-methyl-1-pyrroline N-Oxide (BMPO)
and 2-methyl-2-nitrosopropane dimer (MNP) [63–66], whose structures
and characteristics are shown in Fig. 5. The spin-trapping agents of
active radicals must meet the following three conditions: (1) the formed
spin adducts should be stable and long-lived; (2) the EPR spectra of the
formed spin adducts should be easy to distinguish, identify and resolve;
and (3) the spin-trapping agents should react easily with a variety of
active radicals and have no or simple side reactions.
2.2.2. Hydrogen-donor solvent capture technology
In addition to the EPR spectra used to determine the free-radical
species, the results were verified by the chemical removal of free radi­
cals. The hydrogen-donor solvent capture technique is typically used in
the presence of a hydrogen supply solvent; the radicals generated in the
pyrolysis process can be coupled or stabilized by obtaining H from the
solvent, while the solvent is converted to the corresponding aromatics.
In other words, when highly active hydrogen-donor solvents are present
L. Wu et al.
Fig. 5. Structure and characteristics of common spin traps.
in the reaction system, the active radicals are stabilized by combining
with H in the hydrogen-donor solvent, and the amount of hydrogen
supplied by the hydrogen-donor solvent is approximately equal to the
number of active radicals [67]. Compared to the spin-trapping tech­
nology, the high-temperature limitation is impervious to the hydrogen-
donor solvent capture technique, which is more suitable for detecting
active radicals during co-pyrolysis.
According to the above, the most suitable hydrogen-donor solvent in
the coal pyrolysis process should be the “hydrogen-rich” organic sub­
stances (such as dihydrophenanthrene, dihydroanthracene, and tetra­
hydronaphthalene), which provide not only sufficient hydrogen for the
active radicals in the coal thermochemical conversion but also provide
stable and easily measurable organic substances. Moreover, the side
reactions of “hydrogen-rich” organics are relatively simple, and the
content of “hydrogen-rich” organics and by-products can be used to
invert the number of active radicals [68–70]. Considering the 9,10-dihy­
drophenanthrene (DHP) hydrogen donor to capture the active radicals
generated during the coal pyrolysis as an example, the active radicals
were stabilized after capturing H in DHP, and DHP was converted into
the corresponding dehydrogenation product, phenanthrene (PHE), as
shown in Eq. (3). In addition, the ring-opening, disproportionation, and
dehydrogenation side reactions of DHP generate PHE under high-
7
Chemical Engineering Journal 474 (2023) 145900
temperature conditions, while 2-ethylbiphenyl (EBP), tetrahy­
drophenanthrene (THP) and H2 are produced, as shown in Eqs. (4)–(6).
Therefore, the number of active radicals (QH) can be accurately calcu­
lated by subtracting the amount of PHE generated (Qblank) from the side
reaction of DHP from the total amount of PHE generated (Qtotal).
(3)
(4)
(5)
(6)
The technology of hydrogen-donor solvent capture presents certain
difficulties regarding its widespread application in detecting free-radical
behavior during pyrolysis. This is mainly due to the limitations of its
capture agent itself. Moreover, the complexity of the pyrolysis system
and the diversity of reaction products in the process make it challenging
to determine the actual pathways for transferring H radicals from the
hydrogen-donor solvent to the coal radicals and their corresponding
products [71,72]. As a result, it remains difficult to analyze the types and
behaviors of free radicals in the technology, which instead focuses pri­
marily on tracking the trend of active radical concentrations during
coal’s thermochemical conversion. Researchers are investigating the
trapping behavior and free-radical types involved in the capture process.
They are utilizing various testing and computational techniques,
including the tracer method and Density Functional Theory (DFT), to
determine the hydrogen-donating activity and hydrogen-transfer
pathway of the hydrogen-donor solvents. These methods also infer the
possible free radical behaviors associated with the process [73–75].
L. Wu et al.
2.3. PLIF detection technology
The free-radical behavior can also be detected by other advanced
measurement technologies, such as planar laser-induced fluorescence
(PLIF), which can detect trace components (such as⋅OH, ⋅CH, ⋅CHO, and
NO) that induce fluorescence via thermal transformations. The product
molecules and free radicals have been excited to generate energy level
transitions and to fluoresce, and then the concentration and spatio­
temporal distribution of the free radicals have been analyzed based on
the measured visual images to determine the thermal transformations in
different environments [76]. This cutting-edge optical detection tech­
nology offers exceptional spatiotemporal resolution without altering the
reaction products during the analysis process. It is prevalent in thermal
conversion processes, particularly in steady-state combustion for flame
diagnostics. In pyrolysis research, the focus is on the conversion mech­
anisms and the generation of pyrolyzed polycyclic aromatic hydrocar­
bons (PAHs) [77,78].
Mosonik et al. [79] used in-situ PLIF to analyze the PAH PLIF signal
in the gas phase of biomass pyrolysis and found that the signal began to
appear at 275 ℃, the peak of the signal was located at about 400 ℃ and
almost disappeared at 550 ℃. They suggested that the initial formation
of PAHs was attributed to the increased rate of 3–5 rings PAHs formation
reaction when a large number of PAHs condensed in the lower tem­
perature region above the bed. The reduction in signal at the later stages
may be primarily related to the condensation of 3–5 rings PAHs into
heavier compounds (out of the detection range) or the breaking of 3–5
rings PAHs into lower ring compounds (also out of the detection range).
Additionally, the PAH PLIF signal change intensity was detected close to
the bed, indicating that the products released from the biomass under­
went rapid changes and emphasizing the importance of pyrolysis studies
using in-situ technology [80].
3. Free radical behaviors during co-pyrolysis
The generation of the pyrolysis products during coal pyrolysis fol­
lows the mechanism of free-radical reactions, which means that the
chemical bonds in coal are broken first to produce active radical frag­
ments, and these active radical fragments are broken, combined, and
condensed to produce different pyrolysis products [81–83]. These active
radical fragments also play the role of “clipping engineer” in the coal
pyrolysis process, which can “clip” and “trim” the unstable chemical
Fig. 6. Free-radical behaviors in coal pyrolysis under different temperatures [84].
8
Chemical Engineering Journal 474 (2023) 145900
bonds in the coal or tar macromolecule structure. This directly impacts
the conversion efficiency of coal and the yield and quality of oil and gas
products in the subsequent stages, as shown in Fig. 6 [84]. Compared to
coal pyrolysis, the co-pyrolysis of the low-rank coal and solid “hydrogen-
rich” donors involves interactions between the generated radicals. This
interaction has significant effects on the co-pyrolysis properties,
particularly on the properties of the pyrolysis product. Therefore, the
free-radical behaviors during the co-pyrolysis of low-rank coal and
different solid “hydrogen-rich” donors must be better understood and
explored.
3.1. Co-pyrolysis of low-rank coal and biomass
With pyrolytic properties similar to coal, biomass can be used to
produce bio-coke, bio-oil, and biogas by pyrolysis technology [85,86].
Owing to its high H/C ratio, high volatile fraction, and existing alkaline
earth metals, it can provide a “hydrogen source” and an alkali metal
catalyst for the coal pyrolysis reactions, thereby promoting the catalytic
hydropyrolysis reactions of coal and improving the properties of the coal
pyrolysis products [16,87]. Therefore, biomass is often used as a solid
“hydrogen-rich” donor to assist coal pyrolysis. However, some re­
searchers have found a large difference in the pyrolysis temperature
range between biomass and low-rank coal. The biomass completes the
pyrolysis reactions when the low-rank coal begins the pyrolysis re­
actions [88]. Based on this, they suggested that the active radicals
produced by biomass pyrolysis were difficult to utilize in the low-rank
coal pyrolysis reactions [89]. He et al. proposed a different perspec­
tive on this issue [67]. They found that the experimental values of the
free-radical concentrations of coke obtained by the co-pyrolysis of the
low-rank coal and biomass under the same conditions were lower than
the theoretically calculated values and believed that the interaction
between active and stable radicals and the escape of active radicals led
to a decrease in the free-radical concentrations of coke obtained by co-
pyrolysis, as shown in Fig. 7. In addition, they found that the σ radicals
(g = 2.0014) in coke caused by the hydrogen transfer reactions during
the co-pyrolysis increased with the increasing pyrolysis temperature,
particularly after 400 ℃. This indirectly proves that the active radicals
generated from the biomass could be involved in the low-rank coal py­
rolysis reactions. The mechanism of the co-pyrolysis of the low-rank coal
and biomass proposed by Gouws et al. [90] is consistent with the find­
ings of He et al. [67]. They suggested that free-radical reactions mainly
L. Wu et al.
Fig. 7. (a) Variations in the free-radical concentrations during pyrolysis of coal, walnut shell (WS), and pine.; (b) schematic diagram of interactions between free
radicals during co-pyrolysis [67].
occurred in the volatile fraction of coke or gas phase in the molten phase.
Moreover, with an increase in the pyrolysis temperature, the fragments
generated from the depolymerization of the low-rank coal and biomass
in the molten phase limited the diffusion and escape of free radicals,
which in turn promoted hydrogen transfer reactions in the liquid phase.
Moreover, it is difficult to accurately assess the effects of the biomass
on the co-pyrolysis reactions because of its wide variety and complex
composition. Therefore, researchers often choose a single biomass
fraction of cellulose, hemicellulose or lignin [91,92] (mostly cellulose
and lignin) as biomass model compounds to study the free radical be­
haviors during the co-pyrolysis. Enkhsaruul et al. [93] found that
increasing the amount of lignin reduced the soluble content of acetone in
the tar obtained from the co-pyrolysis of low-rank coal and lignin
because the agglomeration of active radicals during the co-pyrolysis led
to a decrease in the soluble matter content. This meant that the increase
in the lignin addition caused the agglomeration of many active radicals,
which played a negative role in tar quality. A study by Gouws et al. also
confirmed Enkhsaruul’s view that the O/C ratio of lignocellulosic
biomass is more than three times higher than that of coal [90,93]. Lignin
is generally linked by many C-C bonds and ether bonds, such as α-O-4
and β-O-4 bonds. It is thought that the α-O-4 and β-O-4 bonds break first
during the pyrolysis process, and then with the increase in temperature,
the other ether bonds and bridge bonds break in the next [94]. Zhang
et al. [95] performed quantum calculations for lignin pyrolysis and
concluded that active phenoxy free radicals were generated due to the
9
Chemical Engineering Journal 474 (2023) 145900
breakage of the adjacent bonds of α-O-4 and β-O-4, but the opening of
the monomer ring of β-O-4 was earlier than the breakage of the active
β-O-4 bond itself. At this stage, a large number of active free radicals
such as phenoxy intermediates formed with the breaking of the β-O-4
bond, resulting in the breakage of one of the stable bonds of the 4-O-5
ether bond or the formation of an O-inserted heterocyclic ring on one
of the benzene rings. Therefore, oxygen is a well-known crosslinking
agent that somewhat counteracts the depolymerizing effects of
hydrogen [96], leading to the formation of many oxygen-containing
functional group products in this process.
During the co-pyrolysis of biomass, it is crucial to consider the
migration of nitrogen (N) as it is a significant concern owing to the high
N content in the biomass [97], and the N-containing compounds pro­
duced may harm the environment. Biomass pyrolysis produces signifi­
cant amounts of NOx, with NH3 being the major precursor. However, it is
worth noting that HCN, a toxic pollutant, can also be generated during
rapid pyrolysis at high temperatures [98]. It is generally accepted that
nitrogen can be divided into two stages during the co-pyrolysis of
biomass: the primary pyrolysis is the decomposition of fuel-N (Amino-N
and Inorganic-N), which is converted to NH3 and heterocyclic-N sub­
stances in the tar. The intermediate products of tar and coke undergo
cracking at high temperatures and further conversion to NH3 and HCN.
Nitrogen-containing compounds and more stable nitrogen-containing
substances (such as Quaternary-N and N-oxides) in the tar remain in
the coke [99].
L. Wu et al.
3.2. Co-pyrolysis of low-rank coal and waste plastics
Plastics are polymers mainly composed of carbon and hydrogen.
They are non-degradable, and their reuse after waste is of great interest
[100]. Waste plastics with high H/C ratios can be used as hydrogen
donors to provide sufficient hydrogen sources for the low-rank coal
pyrolysis, and the overlapping pyrolysis temperature range (438–521
℃) is favorable for the hydrogen transfer from plastics to coal. In high-
temperature environments, the C-H bonds in waste plastics depoly­
merize to form small-molecule monomers of different sizes and active
radicals. Plastic monomers undergo molecular isomerization and
condensation via hydrogen transfer reactions, eventually forming par­
affins, diolefins, alkane and olefin isomers [101]. Similarly, hydrogen
transfer reactions involve hydrogenation and recombination of active
radicals, forming large amounts of “hydrogen-rich” gases and liquid
products. In the co-pyrolysis of low-rank coal and waste plastics, free-
radical behaviors are the key reason for the change in the properties
of their pyrolysis products; the •H radicals generated by the cracking of
waste plastics can inhibit the crosslinking and polymerization reactions
of the coal molecules, which directly affects the yield and quality of the
pyrolysis products [102]. Therefore, in contrast to coal and biomass co-
pyrolysis, the temperatures of coal and waste plastics co-pyrolysis are
relatively concentrated, the pyrolysis interval is narrow, and the in­
termediates and final products often depend on the polymerization
monomer of the plastics [103–105]. The thermal decomposition of
plastic monomers produces hydrocarbons and partial hydrogen radicals
from re-bonding, which can be used as inhibitors and stabilizers of the
free radicals produced from coal pyrolysis and inhibit the condensation
Fig. 8. (a) Distributions of the •OH radical and (b) •H radical during the co-pyrolysis of coal/PE and coal/PS; (c) concentration of the •H radicals during the PVC
pyrolysis, and H + OH radicals during the coal pyrolysis; and (d) formation pathway of C2H2 and C2H4 during ① PVC pyrolysis and ② PVC/coal co-
pyrolysis [108,109].
10
Chemical Engineering Journal 474 (2023) 145900
of the macromolecular radicals in coal [46,106,107]. Thus reduces the
yield of solid products and increases the yield of gas and liquid products.
Nevertheless, it is important to note that the free-radical behaviors
produced during the co-pyrolysis of low-rank coal and waste plastics can
vary significantly owing to disparities in the chemical structures of the
polymer backbones and side chains. Hong et al. [108] conducted a
simulation study of low-rank coal and Polyethylene (PE)/ Polystyrene
(PS) co-pyrolysis using molecular dynamics (ReaxFF MD), in which the
concentration distributions of the •OH and •H radicals were analyzed.
The •OH radical concentration shown in Fig. 8a increased with
increasing temperature, but the number of •OH radicals during coal/PS
co-pyrolysis was consistently smaller than that of coal/PE due to the
difficulty in destroying the aromatic structure of PS. The generation of
the •H radicals of both started at 2300 and 2500 K, respectively
(Fig. 8b), and it can be concluded that PE and PS had weak effects on the
low-temperature pyrolysis of coal without releasing the •H radicals. In
addition, they simulated the co-pyrolysis behavior of the low-rank coal
and polyvinyl chloride (PVC), as shown in Fig. 8c and Fig. 8d [109]. The
•Cl radicals generated from the cracking of PVC preferentially combined
with the •H radicals generated from the pyrolysis of coal to form HCl,
leaving the PVC substrate. The •H radicals preserved in the PVC
increased the C2H4 yield and decreased the C2H2 yield from the pyrolysis
products. In the co-pyrolysis, the •H radicals produced by the PVC py­
rolysis reacted with the •OH radicals produced from the coal pyrolysis,
resulting in a higher amount of pyrolysis water, whereas the tar yield
was not significantly affected. Therefore, the co-pyrolysis of the low-
rank coal and waste plastics does not necessarily promote tar produc­
tion; in contrast, it may be inhibited. For instance, polypropylene (PP) is
L. Wu et al.
a highly substituted plastic, and because of its severe spatial site resis­
tance, the free radicals from cracking reactions do not participate in the
formation of liquid products, leading to a decrease in the co-pyrolysis tar
yield [110–112].
3.3. Co-pyrolysis of low-rank coal and oil shale
Oil shale (OS), a high-ash solid fossil fuels, is a sedimentary rock in
which organic matter (kerogen and bitumen) is impregnated into an
inorganic matrix [113,114]. Organic matter is rich in aliphatic com­
pounds and contains small amounts of aromatic compounds. Similar to
low-rank coal, OS is rich in potential hydrocarbon resources and has low
cost, high volatility, and a high H/C ratio [115]. OS pyrolysis involves
decomposition and condensation processes and generates large amounts
of active radicals [116–118]. Li et al. [119] found that the free-radical
concentrations of coke from the co-pyrolysis of both were in the range
of 1015-1016 spins/g, which was significantly lower than the theoreti­
cally calculated values. This result indicates that the free radicals
generated during the co-pyrolysis had synergistic effects on each other
and changed the properties of the pyrolysis products. The co-pyrolysis
model for the biomass and OS established by Chen et al. was used to
explain the co-pyrolysis of the low-rank coal and OS [120–122]. When
the OS is at a high temperature, the breakage of the bridging bonds,
intact chains, and side chains of kerogen in the OS leads to the formation
of bitumen and small-molecule fragments. As shown in Fig. 9, the
continued occurrence of the co-pyrolysis reactions involving OS resulted
in reduced oxygen-containing functional groups and pore volume in the
coal, and the aromaticity was improved. The hydrogen-rich radicals
released from the OS during the co-pyrolysis act as hydrogen donors,
which help stabilize the hydrogen-poor radicals in the intermediates
produced by the coal pyrolysis.
Wang et al. [115] found that the free-radical spin concentration (Ng)
of shale oil increased from 0.7 × 1018 spins/g to 1.25 × 1018 spins/g
during the pyrolysis of OS from 370 ℃ to 550 ℃. With an increase in the
temperature, the strong bonds in OS molecules were broken, and the
formation of free radicals was accelerated, leading to an increase in the
Ng in hot bitumen. Meanwhile, many strong bonds in the low-rank coal
broke at this temperature, and strong synergistic effects occurred
Fig. 9. Generation mechanism for the solid product from the co-pyrolysis of coal and OS [122].
11
Chemical Engineering Journal 474 (2023) 145900
between different components, resulting in improved product yield and
quality [118]. Finally, a possible mechanistic model for the co-pyrolysis
of the low-rank coal and OS was obtained by combining the conclusions
of numerous studies. The bitumen produced by the decomposition of the
kerogen molecules was decoupled and adsorbed free radicals from the
low-rank coal to form oil, whereas other molecular fragments were more
likely to undergo further decomposition to produce coke and gas.
Meanwhile, Ye et al [123] used the DFT calculation method to predict
the possible hydrogen transfer mechanism of oil shale. It was found that
the aromatic chains generated during the pyrolysis process of oil shale
were more likely to react with •H radicals through the sites generated by
the breakage at the bridge bonds between their carbon chains and aro­
matic functional groups, and the generated functional group radicals
would also absorb the •H radicals to form the corresponding products
and new carbon chain radicals. Notably, OS introduces large amounts of
ash during the co-pyrolysis process, which leads to the deterioration of
the coke quality while improving the catalytic pyrolysis effect. This is a
crucial problem that cannot be ignored in the co-pyrolysis of both [124].
3.4. Co-pyrolysis of low-rank coal and coal conversion by-products
Coal conversion by-products (liquefaction residues, pyrolysis resi­
dues, heavy oil, etc.) as waste products obtained after clean and efficient
conversion and utilization of coal and graded upgrading contain large
amounts of organic matter, which can assist coal pyrolysis in improving
the tar yield and quality [125–128]. Direct coal liquefaction residue
(DCLR) is a very interesting coal conversion by-product with a low ox­
ygen content, which helps the hydrogen radicals generated from DCLR
to stabilize the more active radicals generated from coal molecules
during the co-pyrolysis, rather than interacting with •OH radicals to
generate water. The reaction behaviors of the low-rank coal and DCLR
can be explained using Eqs. (7)–(12) [108]. When the low-rank coal and
DCLR are co-pyrolyzed, the changes in the properties of the pyrolysis
products (particularly tar) are mainly focused on two aspects: the
enhancement of hydrogenation reactions and the reduction of the
condensation reactions. At high pyrolysis temperatures, weak bonds in
the DCLR are the first to break and generate active radicals and low-
boiling-point oils, which escape from the coal particles in the form of
L. Wu et al.
volatile oil and gas fractions. As the pyrolysis temperature increases,
some of the organic components (THFS) in the DCLR soften and melt
into liquid-like phases. The hydrogen radicals generated by the THFS
can combine with the radicals released from lignite during pyrolysis,
thus enhancing the occurrence of the hydrogenation reaction (Eq. (8))
and weakening of the condensation reaction (Eq. (9)). Additionally, the
molten liquid phase formed by the THFS was easily wrapped outside the
coal coke to hinder the emission of volatiles, leading to a decrease in the
reactions, as shown in Eqs. (8) and (11), and an increase in the reactions,
as shown in Eqs. (9) and (12), such that the tar yield decreases. There­
fore, there are two perspectives on the effect of DCLR on the tar pro­
duced from co-pyrolysis. The appropriate amount of DCLR promotes
hydrogenation reactions to increase light oil. The molten liquid phase
wraps around coke and leads to a reduction in tar production [126]. In
addition, it cannot be ignored that the FeS catalyst contained in the
DCLR transfers a part of the sulfur back into the tar, and the other will
exist in coke, whereas the addition of sulfur will degrade the pyrolysis
product quality and subsequent process utilization is more difficult.
Coal → R• + G ↑ + S (7)
R• +Coal-H → Tar + Coal*• (8)
R• → S + G ↑ (9)
DCLR → THFS• + THFS ↑ + G ↑ + S (10)
THFS• + THFS-H → Tar + THFS (11)
THFS• → S + G ↑ (12)
where R• is a free-radical fragment of lignite pyrolysis; S is solid coke; G
is pyrolysis gas and water; THFS is tetrahydrofuran soluble (heavy oil,
asphaltene, and asphaltene); THFS• is the free-radical fragment broken
by the DCLR.
Song et al. [130] investigated the co-pyrolysis behaviors of Sunjiacha
coal (SJC) and DCLR, and derived the free-radical reaction mechanism
by in situ analysis, as shown in Fig. 10. The presence of the DCLR pro­
motes the cleavage of SJC to generate more free-radical fragments,
which combine with the •H radicals to form tar. As the pyrolysis
Fig. 10. Formation mechanism of coke during the co-pyrolysis of SJC and DCLR [130].
12
Chemical Engineering Journal 474 (2023) 145900
temperature increases, the oxygen-containing functional groups and
•OH radicals in the coal are converted into phenols, aromatics, and
aliphatic groups. In the late stage of the pyrolysis, the concentration of
macromolecular radical fragments increased and condensed to form
coke, with the •H radicals approaching complete consumption. Zhang
et al. [131] analyzed the properties of the products obtained from the co-
pyrolysis of Hunan bituminous coal and pyrolysis residue (DRPT). The
free radical concentration of coke obtained from the co-pyrolysis was
significantly lower than that of coal pyrolysis alone. This was due to the
mutual coupling of small radical fragments from the residue pyrolysis
and larger radicals from the low-rank coal cracking. This resulted in a
lower free-radical concentration in coke.
Song et al. [132] investigated the co-pyrolysis process of long-flame
coal and low-temperature pyrolysis heavy oil (HS). They suggested that
the preferential combination of the •H radicals with the fragments
produced from the HS pyrolysis reduced the light fractions and
increased the intermediate fractions in the tar. The preferential combi­
nation of the •H radicals and HS led to incomplete hydrogenation con­
version of the free radicals produced from the SJC pyrolysis, and the tar
recombinant fractions subsequently increased. When the temperature
reached 655 ℃, the unconverted radicals condensed into
Fig. 11. Hydrogen distribution in pyrolysis products [133]. (Note: a-e: VR ratio
of 4, 7, 10, 13, 18 wt% in feed; E: experimental RCs of hydrogen in the prod­
ucts; T: theoretical RCs of hydrogen in products.).
L. Wu et al.
macromolecular compounds and eventually formed coke. In another
study by Li et al. [133], the hydrogen transfer mechanism occurred
during the co-pyrolysis of the low-rank coal and a vacuum residue (VR).
When the temperature exceeded the softening point of the VR, the coal
particles were wrapped by the melted VR, which increased the resis­
tance to releasing the volatiles from the coal and prolonged the contact
time between the coal and VR radical fragments. Because the H/C ratio
of the VR is higher than that of coal, VR can provide more low-
molecular-weight radicals (hydrogen and methyl), which combine
with the radical fragments produced from coal pyrolysis to form
medium-molecular-weight substances (tar). As shown in Fig. 11, during
the co-pyrolysis of the low-rank coal and VR, H was transferred more to
the solid coke product, followed by tar, pyrolysis water, and pyrolysis
gas. As the amount of VR increased, the RCs (the relative contents (RCs)
of each hydrogen proton type to the total hydrogen proton were calcu­
lated by the integral calculations) of hydrogen in the coke and pyrolysis
water decreased significantly, and the RCs of hydrogen in the tar
increased significantly, indicating that the addition of VR facilitated the
transfer of more hydrogen radicals to the tar and made the tar lighter.
4. Influence factors of free-radical behaviors during co-pyrolysis
Variations in the properties of the coal pyrolysis products are pri­
marily caused by diverse free-radical reactions occurring during the
pyrolysis process. The co-pyrolysis process conditions can also lead to
significant differences in the properties of the pyrolysis products, which
indicates that in addition to the influence of the low-rank coal and solid
“hydrogen-rich” donors on the free-radical behaviors during the co-
pyrolysis, the co-pyrolysis process conditions also affect the free-
radical behaviors [134]. Most studied on the co-pyrolysis process con­
ditions include pyrolysis temperature, residence time, heating rate,
feedstock mixing ratio, and mixing method, and the effects of these co-
pyrolysis process conditions on the radical behaviors during co-pyrolysis
are presented below [135–137].
Fig. 12. Spin concentrations of the pyrolysis residues at various pyrolysis temperatures, (a) total radicals, (b) C-centered radicals, (c) O-centered radicals, (d) N-
centered radicals [142].
13
Chemical Engineering Journal 474 (2023) 145900
4.1. Pyrolysis temperature
The pyrolysis temperature is a necessary condition for the occurrence
of the pyrolysis reactions and it is essential for the free-radical behaviors
during the pyrolysis. When the temperature increases to the required
temperature, the heat provided by the surrounding environment exceeds
the activation energy required to break the chemical bonds in the low-
rank coal and solid “hydrogen-rich” donors, and these bonds break
and depolymerize, generating large numbers of active radicals [138].
The differences in the properties of the co-pyrolysis products of the low-
rank coal and solid “hydrogen-rich” donors at different pyrolysis tem­
peratures indicate that different pyrolysis temperatures have various
effects on the free-radical behaviors in the co-pyrolysis process. Within a
specific temperature range, the improvement in the free-radical con­
centration with an increase in the pyrolysis temperature indicates that
high temperature favors the generation of free radicals during the py­
rolysis [119]. This finding is also supported by Srinivasan, Seehra and
Wang et al. [115,139]. The volatile product yield can determine the
optimal temperature for the pyrolysis reaction; however, the tempera­
ture often requires a balance between the amounts of volatile products
released at high temperatures and the secondary cracking reaction of the
volatile products under these conditions. If the pyrolysis temperature
increases above the optimal temperature range, the volatile products
shift to less liquid and more gaseous products [47,140,141].
The pyrolysis temperature directly affects the radical concentration
during the co-pyrolysis process. Wu et al. [142] found that the radical
spin concentrations in the Pingshuo coal (PC)/ HDPE (7:3) pyrolysis
residue were lower than those in the PC pyrolysis residue within 500 ℃
(Fig. 12a), indicating that the melt of HDPE hindered the transfer of
π-quinone radicals and O-centered radicals to semiquinone radicals.
With the increase in the pyrolysis temperature to 550 ℃, the free-radical
spin concentration of the pyrolysis residue showed an obvious
increasing trend, particularly for the O-centered radicals (Fig. 12a),
indicating that HDPE was favorable for stabilizing the O-centered
L. Wu et al.
radicals at high temperatures. The decrease in spin concentration of the
pyrolysis residue at higher temperatures was due to HDPE mixing,
which delayed coke formation, leading to the condensation reactions of
C- and O-centered radicals (Fig. 12b and Fig. 12c). A higher pyrolysis
temperature was not favorable for the N-centered radicals, and it
gradually shifted to lower temperatures with the addition of HDPE
(Fig. 12d). Yan et al [143] calculated the condensation of O- and C-
centered radicals during the pyrolysis with the use of ReaxFF MD. The O-
centered radicals can easily form peroxides at low temperatures in the
system and can be chemisorbed onto the C-centered radicals to form
carboxyl radicals and combined with other radicals to form oxygen-
containing compounds. In addition to the radical concentration, the
pyrolysis temperature affected the radical species. Chen et al. [144]
investigated the evolution of radicals in the coke obtained from co-
pyrolysis at different temperatures. At a pyrolysis temperature of 450
℃, the radical concentration in the coke was maximum. As the pyrolysis
temperature continued to increase, the interaction between the free
radicals in the system was enhanced, the g value of the coke decreased,
and the free radicals in the coke evolved from O-centered radicals to C-
and O-centered combined radicals. In addition, the radicals at low
temperatures are mostly non-interacting radicals, which are more
difficult to couple with other radicals in the system, whereas the radicals
at high temperatures are more likely to undergo coupling reactions and
are more active.
4.2. Residence time
Residence time is the constant heating time after pyrolysis reaches
the required control temperature. It directly determines whether the co-
pyrolysis reactions between the low-rank coal and solid “hydrogen-rich”
donors occur fully and directly affect the co-pyrolysis product charac­
teristics; however, its influence is also related to the pyrolysis temper­
ature [85,145–148]. Generally, the longer the co-pyrolysis residence
time at high temperatures, the higher the co-pyrolysis gas yield and the
lower the coke and tar yields gain. Wen et al. [149] analyzed the in­
termediate •H radicals in a simulated Rice Husk (RH) and oil shale (OS)
co-pyrolysis processes and found that the •H radicals were completely
consumed when the co-pyrolysis residence time was extended. This is
because many •H radicals are partially used in the dehydration and ring-
opening reactions of RH, which are the main reactions occurring in the
later stages of RH pyrolysis. Khan et al. [150] found that extending the
residence time stabilized the free-radical fragments produced by the co-
pyrolysis of the low-rank coal and waste rubber and promoted the
generation of stable residues. At high temperatures, extending the
residence time increases the reaction time for the cracking of the low-
rank coal and solid “hydrogen-rich” donors, and the intermediate
products are more fully cracked, resulting in large amounts of volatile
products. Mastral et al. [151] investigated the free radical behavior
during the co-pyrolysis of low-rank coal and tires at different residence
times. Unlike the shorter residence time, the longer residence time
resulted in a long co-pyrolysis reaction time, and the “hydrogen-rich”
radicals from the tire pyrolysis increased the hydrocracking reaction
time of the low-rank coal macromolecules, which reduced the difference
in the C1-C3 product production from the theoretical value. Meanwhile,
the long residence time also prolongs the interaction of volatile fractions
in the co-pyrolysis process, which increases the opportunity for volatile
fractions to react with organic and inorganic components on the internal
and external surfaces of the coke. This prompts the cracking reaction to
produce more radical fragments and produces more small-molecule
gases [152,153].
4.3. Heating rate
The product properties obtained from fast and slow pyrolysis differ,
particularly the tar properties. Fast pyrolysis has shown promise in
mitigating secondary reactions during pyrolysis and increasing tar yield.
14
Chemical Engineering Journal 474 (2023) 145900
However, the quality of the resulting tar may be inconsistent and contain
a significant proportion of heavy components. This can be attributed to
the significant effects of the heating rate on the free-radical behaviors
during the pyrolysis process [154,155]. Wen et al. [156] investigated
the synergistic effects of the co-pyrolysis of Yulin coal (YL) and waste
tires (WT). They found that increasing the heating rate could weaken the
asynchrony of the volatile fraction evolution of YL and WT and maxi­
mize the interaction of free radicals during the co-pyrolysis of YL and
WT. Victor et al. [39] found that rapid microwave pyrolysis shortened
the time required for secondary pyrolysis reactions of the low-rank coal
and pine wood. The free-radical concentration in coke from rapid mi­
crowave co-pyrolysis was lower, and the g value increased from 2.00273
to 2.00282, indicating that the carbon in coke tends to be more ordered,
and aromatic radicals with fewer rings evolved into graphitic carbon
aliphatic radicals. It is generally believed that during the slow pyrolysis
of coal, crosslinking reactions occur before tar evolution, and tar evo­
lution occurs simultaneously with the production of H2O and CO2. Fast
pyrolysis reduced the relative rate of low-temperature crosslinking of
macromolecular radicals during co-pyrolysis, and the relative rate of
bridge bond breaking occurred almost simultaneously with tar evolu­
tion. Rapid pyrolysis involves a quick transition from room temperature
to high temperature, resulting in incomplete bridge bond breakage
compared to slow pyrolysis due to the short time frame. However, the
heating rate minimises the types of free radicals produced from bridge
bond breakage. During fast pyrolysis, bridge bond breakage free radicals
from the early stage of slow pyrolysis may occur simultaneously with the
high-temperature tar evolution. This increases the likelihood of collision
coupling between the bridge bond breaking free radical and the inter­
mediate product of tar evolution [38,141,157]. Rapid pyrolysis is an
effective method to utilize solid “hydrogen-rich” donors for the hydro­
genation of low-rank coal [158]. Bozkurt et al. [159] suggested that
under the effects of rapid pyrolysis, the active •H radicals generated by
the hydrogen donor inhibit the condensation of the aromatic compounds
produced from the coal pyrolysis, and promoting the conversion of ar­
omatics to tar, consequently enhancing the yield and quality of tar.
Slow pyrolysis has the characteristics of uniform heat and mass
transfer, adequate cracking and more abundant secondary reactions. Li
et al. [129] demonstrates that slow pyrolysis can overcome spatial site
resistance limitations, thereby exposing more free-radical sites. This in
turn facilitates cross-linking reactions at later stages. The reactions that
lead to cracking and breakage are also more adequate during slow py­
rolysis, resulting in increased light tar yield with extended pyrolysis time
[87]. Moreover, it has been observed that during the slow pyrolysis
process, the hydrogen donor is partially softened in the preceding
heating phase, leading to the formation of active substances adsorbed on
the surface of coal particles. This results in the blocking of coal molecule
pore structures, thereby inhibiting volatile product escape. These vola­
tile components break through the restrictions only upon reaching the
pyrolysis temperature and pressure, thereby promoting secondary re­
actions and forming a stable large PAHs radical. [39].
4.4. Blend ratio
The addition of solid “hydrogen-rich” donors directly determines the
sufficiency of “hydrogen-rich” components in the co-pyrolysis reaction,
which further affects the adequacy of the hydropyrolysis of the low-rank
coal [160,161]. Therefore, in the co-pyrolysis studies, the blend ratio of
the low-rank coal and solid “hydrogen-rich” donors are often of great
interest, which can be used to regulate the characteristics of the co-
pyrolysis reactions. Zhang et al. [131] found that the free-radical con­
tent in the coke obtained from the co-pyrolysis of low-rank coal and
direct coal liquefaction residue (DCLR) first increased to a stable value
and then slowly decreased as the DCLR ratio increased. As shown in
Fig. 13a, the free-radical concentration in the coke obtained from the co-
pyrolysis was maximum when the blend ratio of the DCLR to low-rank
coal was 5:100. When the addition of the DCLR continued to increase,
L. Wu et al.
Fig. 13. (a) Free-radical concentration of coke at different DRPT ratios [131]; (b) spin concentrations of coke samples from co-pyrolysis of coal and PE mixtures at
550 ℃ [46].
more free-radical fragments were produced in contact with the large
free-radical fragments produced by the low-rank coal. Thus, the free
radicals were more likely to be quenched, resulting in the reduction of
free radicals in the coke. The effects of the solid “hydrogen-rich” donors
on the pyrolysis reactions of the low-rank coal depend mainly on the H/
C ratio of the solid “hydrogen-rich” donors. Wu et al. [46] studied the
characteristics of the co-pyrolysis products of low-rank coal and two
types of PE with different H/C ratios. As shown in Fig. 13b, the overall
changes in the concentrations of the three radicals in the coke obtained
from the co-pyrolysis of the low-rank coal and PEs with different H/C
ratios were similar to the increase of the two PE additions; however,
there were differences as well. The free-radical concentrations of PE
with higher H/C ratios were higher than those of PE with lower H/C
ratios, and PE hydrogen donors with high H/C ratios could better pro­
duce and condense C-O central radicals. This led to an overall trend in
which the free-radical concentrations in coke first increased to a stable
level and then slowly decreased. The effects of the blend ratio of coal and
PE on the radical behaviors of the coke obtained from the co-pyrolysis
were mainly manifested by the competition between the C- and O-
centered radicals and N-centered radicals. The addition of PE during the
co-pyrolysis of low-rank coal subtly impacts O-centered radicals. This is
due to the lower O content in PE compared to low-rank coal and the
conversion of phenolic substances into stable O-centered radicals during
Fig. 14. (a) Schematic diagram of three mixing modes of CS and NMH; (b) EPR spectra of coke from CS, NMH, and blends obtained at 600 ℃ using a variety of
mixing modes [165].
15
Chemical Engineering Journal 474 (2023) 145900
co-pyrolysis. Conversely, the concentration of N-centered radicals de­
creases significantly while C-centered radicals increases. It is hypothe­
sized that H radicals produced by the hydrogen donor PE react with N-
containing aromatics in coal to generate NH3, thus consuming N-
centered radicals. C-centered radicals are less coupled to H radicals,
leading to an increase in C-centered radical concentration [162,163].
4.5. Load mode
The effect of the sample loading mode on the co-pyrolysis of low-
rank coal and solid “hydrogen-rich” donors has received increasing
attention from researchers [164]. It is generally accepted that the
loading method of the low-rank coal and solid “hydrogen-rich” donors
affect the pyrolysis product properties, which is mainly attributed to the
presence of volatiles-coke interactions [5]. Zhu et al. [165] designed
three loading methods (U-type, L-type and M− type) for the co-pyrolysis
of the Naomaohu low-rank coal (NMH) and cedar sawdust (CS) to verify
the effects of the loading mode on co-pyrolysis, as shown in Fig. 14. The
g values of coke obtained from the pyrolysis of NMH and CS alone were
similar, indicating that the coke obtained from the pyrolysis alone had a
similar radical distribution and was mainly O-centered. Compared to the
g values of the coke obtained from pyrolysis alone, the g values of the
coke obtained by co-pyrolysis of NMH and CS with the three different
L. Wu et al.
Fig. 15. (a) Different cases of feedstock configurations for deconvolution of synergy in co-pyrolysis; and (b) spin concentration of coke samples obtained at different
co-pyrolysis cases [166].
loading modes were lower, and the free radicals of all three cokes were
dominated by the C-centered radicals. The coke obtained from the co-
pyrolysis in the L-type loading mode had the lowest free-radical con­
centration because the volatile radicals generated by CS failed to contact
with NMH effectively and escaped directly from the top, resulting in the
lowest free radicals in the coke.
Zhang et al. [166] investigated the effects of different loading modes
(Fig. 15a) on the properties of the co-pyrolysis products of low-rank coal
and PS. Their free-radical concentrations were obtained from the peak
areas of the EPR spectra (Fig. 15b). When the loading mode was changed
from case 6 to case 5, the increase in the loading height led to an increase
in the contact between the volatile fractions of PS and the low-rank coal.
Oxygen-containing components such as ether, hydroxyl and carbonyl
groups in the volatile fractions of PS were further decomposed to form
16
Chemical Engineering Journal 474 (2023) 145900
aromatic radicals [18]. The interaction between the volatile fractions of
PS and coke was determined by comparing loading mode cases 7 and 8.
Large numbers of aromatic ring groups generated by PS were partially
adsorbed on the coke surface when passing through the coke, thereby
increasing the number of aliphatic and aromatic structural radicals.
Compared with loading case 3, loading case 5 had a smaller physical
contact area and weaker spatial site resistance, resulting in a lower
concentration of C-centered radicals containing oxygen functional
groups in the coke [4].
5. Effects of free radical behaviors on co-pyrolysis products
During the co-pyrolysis of low-rank coal and solid “hydrogen-rich”
donors, free radical reactions caused by the breakage of the chemical
L. Wu et al.
bonds significantly affect the pyrolysis product properties; that is, the
free-radical behaviors during the co-pyrolysis are closely related to the
pyrolysis product properties. When the solid “hydrogen-rich” donors are
sufficient, the “hydrogen-rich” radicals in the volatile fractions of the
solid “hydrogen-rich” donors will react with the active radicals gener­
ated from the pyrolysis of low-rank coal macromolecules to promote the
generation of the low-molecular volatile fraction or the hydrogenation
of the coal macromolecules, which will improve the distribution and
quality of the pyrolysis products [167–169]. However, when the solid
“hydrogen-rich” donors are insufficient, the “hydrogen-rich” radicals
fail to stabilize the active radicals, resulting in condensation of the active
radicals and the formation of coke (semi-coke) or heavy oil [20].
5.1. Coke/semi-coke
Coke (semi-coke) is formed by the condensation of macromolecular
radicals during coal pyrolysis and is continuously subjected to redox
reactions with the pyrolysis radicals or intermediates at high tempera­
tures [54]. The coke obtained from the co-pyrolysis of low-rank coal and
solid “hydrogen-rich” donors is similar to the coke obtained from both
alone pyrolysis; however, the coke yield obtained from the co-pyrolysis
is usually lower than the theoretical yield, and the coke quality also
changes, which can be attributed to the hydrogenation mechanism
during the co-pyrolysis [170,171]. The “hydrogen-rich” radicals in the
volatile fractions of the solid “hydrogen-rich” donors combine with the
coal macromolecular radicals and inhibit the condensation reaction of
the coal macromolecular radicals, resulting in a low coke yield. The
reactions of the “hydrogen-rich” radicals with the heteroatomic func­
tional groups in the coal macromolecules reduce the heteroatomic
functional group content in the coke and generate more aromatic
structures, which result in changes in the coke quality. Hong et al. [172]
used the Reax FF MD method to simulate the formation of semi-coke
during the pyrolysis, confirming that tar reduction leads to coke for­
mation in two ways: (1) reactions between tar fragments lead to the
formation of semi-coke, and (2) free radicals from tar decomposition
erode the semi-coke, leading to the growth of semi-coke fragments and
the release of H2 and CO2. Victor et al. [39] demonstrated that the free
radicals produced by the biomass can react with coke and promote its
decomposition during the co-pyrolysis of the low-rank coal and biomass.
Meanwhile, the “hydrogen-rich” radicals in the volatile fractions of the
biomass and the hydrogen radicals produced from the coal pyrolysis
prevented the crosslinking of the low-rank coal macromolecules
resulting in further graphitization of coke. The changes in the coke
Fig. 16. Changes in g-factor values of free radicals produced during separate pyrolysis and co-pyrolysis of HLBE coal, walnut shell (WS), and pine [67].
17
Chemical Engineering Journal 474 (2023) 145900
properties obtained from the co-pyrolysis can be inferred from the
analysis of the radical behavior. For example, the molten coke is rich in
aliphatic branched chains and active radicals when the co-pyrolysis
temperature is 400–600 ℃; however, most of the aliphatic branched
chains and active radicals are lost in the solidified and contracted coke at
high temperatures [173].
The solid “hydrogen-rich” donors significantly affect the free-radical
concentration in the coke obtained from the co-pyrolysis, which is
generally considered to increase the concentration of the O-centered
radicals. The co-pyrolysis reactions inhibited the escape of phenolics and
converted them into stable O-centered radicals, whereas the concen­
tration of C- and N-centered radicals decreased. The •H radicals hy­
drogenate with carbon-containing aromatics and nitrogen-containing
aliphatic hydrocarbons in the coal during the co-pyrolysis to form NH3
and alkanes, resulting in the depletion of C- and N-centered radicals
[37,174,175]. However, He et al. [67] concluded that the soft residues
produced in the early stages of biomass pyrolysis would adhere to the
coal surface, causing pore plugging of the coal particles and inhibiting
thermal decomposition and the aromatic hydrocarbon formation. This
would result in an increase in the coke yield and free radicals in the coke.
This confirms that the co-pyrolysis of low-rank coal and solid “hydrogen-
rich” donors can increase the free-radical concentration in coke. In
addition, as shown in Fig. 16, the g values in the EPR spectra of the cokes
obtained from the co-pyrolysis of the low-rank coal and biomass
decreased with the increasing pyrolysis temperature, which may be
attributed to the presence of small- and medium-sized aromatic clusters
and oxygen in the structure of low-temperature cokes. The free radicals
in coke mainly exist in the stable aromatic system [176–178], while the
hydrogenation of the “hydrogen-rich” volatile fraction from biomass
destroys the aromatic system in coke and exposes the wrapped free
radicals to the pyrolysis system, resulting in the stepwise conversion of
the system from C-centered radicals to O-centered radicals
[175,179,180].
5.2. Tar
Tar is the most valuable product of coal pyrolysis, and its yield and
quality directly affect the economics of coal pyrolysis technology. With
the hydrogenation of the solid “hydrogen-rich” donors, the tar yield and
quality of the co-pyrolysis products are significantly improved
[181,182]. The changes in the tar yield and quality are mainly attributed
to the fact that the “hydrogen-rich” radicals in the volatile fractions of
the solid “hydrogen-rich” donors promote the production of light
L. Wu et al.
components such as short-chain alkanes and phenols while inhibiting
the production of heavy components such as long-chain alkanes,
aliphatic hydrocarbons, and heavy aromatics during the co-pyrolysis
process [183]. The condensation and hydrogenation reactions between
free radicals during the co-pyrolysis lead to the development of the
pyrolysis products in different directions, in which the former favoring
coke production and the latter mainly promoting tar production. Wen
et al. [156] found that the co-pyrolysis of Yulin coal (YL) and waste tires
(WT) produces more tar and pyrolysis gas than coal pyrolysis alone
because the rubber in WT readily cracked and produced large amounts
of “hydrogen-rich” radicals. These “hydrogen-rich” radicals could
effectively combine with the radicals generated from coal cracking and
participate in the formation of liquid or solid products. Particularly,
when the amount of WT addition was higher than that of YL, the
“hydrogen-rich” radicals produced by WT stabilized the active radicals
produced by YL and avoided further cracking into pyrolysis gas, which
improved the tar yield. Guo et al. [87] found that the synergistic effects
of coal and corn straw co-pyrolysis increased the tar yield and improved
the tar quality. This may be because the volatiles escaping from coal and
corn straw were cleaved at high temperatures, generating large numbers
of active radicals. The relatively small radicals in the corn straw volatile
fractions stabilized the large molecular radicals produced in the coal
volatile fractions and contributed to tar production rather than cross­
linking with each other to produce secondary coke and pyrolysis gas.
The quality of tar is also the focus of attention for the co-pyrolysis of
low-rank coal and solid “hydrogen-rich” donors [184]. He et al. [67]
found a significant increase in the light and monocyclic fractions in the
tar obtained from the co-pyrolysis of low-rank coal and walnut shell
(WS). During co-pyrolysis, some aromatic radicals are combined with
small volatile radicals (such as •H and •OH radicals) to prevent the
further condensation of aromatic hydrocarbons. The binding of aromatic
radicals to •H and •OH radicals may also lead to an increase in tar yield
and a decrease in the pyrolysis water rate [185]. The decrease in the
non-aromatic hydrocarbon fractions in the tar was caused by the com­
bination of radicals generated by the breakage of aliphatic bridge bonds
with volatile radicals to produce pyrolysis gas, water-soluble substances
and aromatic compounds. The free-radical concentration in the tar ob­
tained from co-pyrolysis is higher than that obtained from pyrolysis
alone, and these radicals are stable and mainly concentrated in the
heavy fractions of tar (tetrahydrofuran insoluble matter) [186]. There­
fore, a high concentration of free radicals implies a high content of the
heavy fraction (tetrahydrofuran insoluble matter) in the tar obtained
from co-pyrolysis [187]. The corresponding tar properties were ob­
tained by the co-pyrolysis of low-rank coal and high-ash DCLR [125].
The tar composition showed that the •H generated during the pyrolysis
preferentially combined with the large molecular radicals with carbon
atoms larger than 10 to produce small-molecule phenyls. Phenol and
aromatic hydrocarbons were formed due to the inability to combine
with •H in time [188]. The resulted in the phenol and aromatic hydro­
carbon in the light fractions of the tar significantly decreasing and the
alkanes increasing.
5.3. Pyrolysis gas
Pyrolysis gas is generated from the co-pyrolysis of the low-rank coal
and solid “hydrogen-rich” donors by breaking the large molecular side
chains or combining small molecular radicals [163]. According to the
chemical structure of low-rank coal or solid “hydrogen-rich” donors,
there are several sources for the components in pyrolysis gas [189–191]:
(1) CO2 mainly arises from the decarboxylation of carboxyl groups at
approximately 200 ℃; (2) CO mainly arises from the decomposition of
carbonyl and ether groups at around 400 ℃ and the cleavage of other
oxygen-containing heterocycles above 500 ℃; (3) CH4 is derived from
the breakage of alkyl side chains and aliphatic branched chains at high
temperatures; (4) H2 is mostly formed by the aromatization and
condensation of coal or solid “hydrogen-rich” macromolecules at a high
18
Chemical Engineering Journal 474 (2023) 145900
temperature. Zhang et al. [131] found that H2 and CH4 in the pyrolysis
gas obtained from the co-pyrolysis of the low-rank coal and DRPT were
higher than those in other pyrolysis gas fractions, indicating that large
amounts of •H and •CH3 radicals were produced during the co-pyrolysis
process. CH4 in the C1-C4 hydrocarbon gas fractions of the pyrolysis gas
obtained from co-pyrolysis decreases significantly with an increase in
the amount of DRPT, indicating that more •CH3 fragments were pro­
duced during the co-pyrolysis and stabilized to form light tar fractions.
In addition, He et al. [67] found that the CH4 in the pyrolysis gas ob­
tained from the co-pyrolysis of the low-rank coal and biomass at the
pyrolysis temperatures below 450 ℃ was significantly higher than the
theoretically calculated value, while C2 and above hydrocarbon gases
were lower than the theoretically calculated value. This can be attrib­
uted to the fact that •H radicals are more easily bound to small-molecule
radicals; this result is supported by a study by Li et al. [192].
More studies have found that the synergistic effects of the co-
pyrolysis of the low-rank coal and solid “hydrogen-rich” donors
inhibit the production of almost all gases, where the experimental values
of the gas yields are lower than the theoretically calculated values
because H2, CH4 and C2-C3 are mainly formed by the •H, •CH3,
•CH2CH3 or •CH2CH2CH3 radicals. These radicals are more likely to
combine with active radicals to produce more light tar components, such
as short-chain aliphatic hydrocarbons, monocyclic aromatic hydrocar­
bons [193–196].
5.4. Pyrolysis water
Pyrolysis water is considered a by-product of the co-pyrolysis re­
actions of the low-rank coal and solid “hydrogen-rich” donors, which
mainly consist of two parts: Combined water and reaction water [197].
In the early stage of co-pyrolysis (from room temperature to approxi­
mately 200 ℃), the adsorbed bound water in the low-rank coal and solid
“hydrogen-rich” donors vaporizes and escapes, and it condenses into
liquid water outside the reaction system. As the pyrolysis temperature
increases, the thermal decomposition of the low-rank coal and the solid
“hydrogen-rich” donors produce large numbers of radical fragments,
including •OH and •H, which interact with each other to produce re­
action water. The reaction water aids in the decomposition of oxygen-
containing functional groups that can transfer H from water to pyroly­
sis intermediates, leading to an increase in the concentration of free
radicals during the co-pyrolysis [20,190,198,199]. In terms of macro­
scopic reactions, the reaction water in pyrolysis water was mostly pro­
duced by the reactions of the components in the pyrolysis gas, as shown
in Eqs. (13)–(16). Wen et al. [156] investigated the possible relationship
between the pyrolysis water yield and the mixing ratio or pyrolysis
temperature. With an increase in the amount WT, the pyrolysis water
yield tended to decrease significantly, which was mainly related to the
reduction of oxygen-containing functional group in the co-pyrolysis
system. There was no obvious regularity of the pyrolysis temperature
on the pyrolysis water yield, but all of them reached the maximum yield
in the range of 500–550 ℃. This temperature interval was exactly at the
window temperature for the generation of tar, indicating the “hydrogen-
rich” volatile fractions from the WT pyrolysis combined with the
oxygen-containing radicals from the cracking of the low-rank coal pro­
moted the production of pyrolysis water. This may also have affected tar
production.
Water-gas shift reaction:
CO2 + H2 ↔ CO + H2 O ΔH = 41.2kJ/mol (13)
Methanation reaction:
CO2 + 4H2 ↔ CH4 + 2H2 O ΔH = − 165kJ/mol (14)
Water-gas reaction:
C + H2 O ↔ CO + H2 ΔH = 41.2kJ/mol (15)
L. Wu et al.
C + 2H2 O ↔ CO2 + 2H2 ΔH = 41.2kJ/mol (16)
6. Summary and challenges
Clean and efficient conversion and utilization of coal resources and
graded utilization are important ways to utilize coal resources in the
future. Among these, the low-rank coal hydropyrolysis technology
stands out as it produces high-calorific-value pyrolysis gas and high-
yield tar, which holds great potential for enhancing the economic
viability of coal resource utilization. However, the high cost associated
with hydropyrolysis poses a significant barrier to the widespread
adoption and development of this technology. The cheap “hydrogen
source” becomes the key to reducing the cost of the coal hydropyrolysis
technology, and the mechanism of its hydrogen supply in the process of
coal pyrolysis also becomes a key scientific problem of this technology.
Solid “hydrogen-rich” donors, characterized by their low cost, abundant
availability, high volatiles, and high H/C ratio, can be effectively
employed in the pyrolysis of the low-rank coal, enabling low-cost hy­
drogenation of this resource.
(1) EPR spectroscopy can resolve the radical behavior during the co-
pyrolysis of low-order coal and solid “hydrogen-rich” donors, and
its characteristic parameters such as radical spin concentration,
g-value, line width and line shape can be correlated with the
radical behavior. However, the reliability of the radical species
and spin concentrations corresponding to the deconvolution of
EPR spectra needs to be improved further, and it remains chal­
lenging to resolve the effects of different radicals in the co-
pyrolysis process accurately.
(2) The presence of various solid “hydrogen-rich” donors with
diverse compositions adds complexity to the behavior of the co-
pyrolysis radicals, making it challenging to establish universal
rules for the properties of the co-pyrolysis products when com­
bined with low-rank coal. The influence of hydrogen radicals on
the co-pyrolysis reactions plays a pivotal role in determining the
distribution of co-pyrolysis products. A comprehensive explora­
tion of the hydrogen radical behaviors in different solid
“hydrogen-rich” donors during the co-pyrolysis process, as well
as simplifying the complex system of different radical reactions,
may provide insights into the underlying reasons and patterns
behind changes in the properties of co-pyrolysis products derived
from the low-rank coal and solid “ hydrogen-rich ” donors.
(3) The influence of pyrolysis process conditions on the free radical
behaviors during co-pyrolysis has not been uniformly established;
however, certain effects have been acknowledged within the ac­
ademic community. High temperatures affect the secondary re­
actions during the co-pyrolysis, leading to the formation of more
reactive radicals that exhibit a greater tendency to couple. A
rapid increase in the temperature can cause active hydrogen
radicals to inhibit the condensation of the aromatic compounds
produced by coal pyrolysis and promote the conversion of aro­
matics to oils. The feedstock blend ratio and blending method can
change the contact coupling behavior of radicals, however, the
effect of contact coupling on radical behavior has not been
directly proven and mostly relies on inferences drawn from other
analytical test results.
(4) The free radical behaviors during the co-pyrolysis impact the
properties of pyrolysis products. The free radicals generated by
solid “hydrogen-rich” donors can react with the coke and
improve its aromaticity. The spatial site resistance of coke is a key
factor causing differences in the concentration of free radicals.
The tar fraction is associated with the hydrogen radicals pro­
duced by the solid “hydrogen-rich” donors, which prevent further
condensation of aromatic or aliphatic hydrocarbons in the tar.
Pyrolysis gas is produced by the breakage of large molecular side
19
Chemical Engineering Journal 474 (2023) 145900
chains or the binding of small molecular radicals during co-
pyrolysis, whereas pyrolysis water is associated with the hydro­
genation breakage behavior of oxygen-containing radicals.
7. Authors’ contributions
All of authors contributed to the research. Dr. Lei Wu and Mr. Yining
Guan: Investigation, data analysis, writing manuscript, and revision; Mr.
Changcong Li: Collecting literatures; Prof. Dr. Lei Shi, Dr. Sasha Yang,
Dr. B. Rajasekhar Reddy, Dr. Gan Ye, and Dr. Rock Keey Liew: Sugges­
tion and revision; Prof. Dr. Qiuli Zhang: Data support; Prof. Dr. Jun
Zhou, Prof. Dr. R. Vinu, and Prof. Dr. Su Shiung Lam: Methodology,
financial support, and supervision.
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.
Acknowledgements
This work was supported by the Innovation Capability Support
Program of Shaanxi (No. 2020TD-028), the Service Local Special Project
of Education Department of Shaanxi Provincial Government (No.
22JC045), the Special Scientific Research Project of Education Depart­
ment of Shaanxi Provincial Government (No. 22JK0432), the Science
and Technology Plan Project of Yulin City (No. CXY-2020-058), and the
Science and Technology Foundation Project of XAUAT (No. ZR21065).
References
[1] S. Sun, D. Xu, Y.a. Wei, Y. Zhi, G. Jiang, Y. Guo, Influence laws of operating
parameters on coal pyrolysis characteristics, J. Anal. Appl. Pyrol. 167 (2022),
105684, https://doi.org/10.1016/j.jaap.2022.105684.
[2] B. Sardi, H. Rachmawati, T.F. Maulana, E. Setiawati, N. Indrawan, M. Mahfud,
Advanced bio-oil production from a mixture of microalgae and low rank coal
using microwave assisted pyrolysis, Bioresour. Technol. Rep. 21 (2023), 101367,
https://doi.org/10.1016/j.biteb.2023.101367.
[3] L. Shi, Q. Liu, B. Zhou, X. Guo, Z. Li, X. Cheng, R.u. Yang, Z. Liu, Interpretation of
methane and hydrogen evolution in coal pyrolysis from the bond cleavage
perspective, Energy Fuel 31 (1) (2017) 429–437.
[4] L. Shi, Q. Liu, X. Guo, W. Wu, Z. Liu, Pyrolysis behavior and bonding information
of coal — a TGA study, Fuel Process. Technol. 108 (2013) 125–132.
[5] L. Wu, Y. Guan, J. Zhou, X.u. Jiang, T. Liu, J. Pan, Effects of variable amounts of
volatiles in corncob on microwave co-pyrolysis of low-rank coal and corncob,
Fuel 332 (2023), 126133, https://doi.org/10.1016/j.fuel.2022.126133.
[6] C. Ma, Y. Zhao, T. Lang, C. Zou, J. Zhao, Z. Miao, Pyrolysis characteristics of low-
rank coal in a low-nitrogen pyrolysis atmosphere and properties of the prepared
chars, Energy 277 (2023), 127524, https://doi.org/10.1016/j.
energy.2023.127524.
[7] L. Wu, Y. Guan, C. Li, J. Zhou, T. Liu, G. Ye, Q. Zhang, Y. Song, R. Zhu, Insight
into product characteristics from microwave co-pyrolysis of low-rank coal and
corncob: unraveling the effects of metal catalysts, Fuel 342 (2023), 127860,
https://doi.org/10.1016/j.fuel.2023.127860.
[8] B. Rajasekhar Reddy, R. Vinu, Microwave-assisted co-pyrolysis of high ash Indian
coal and rice husk: product characterization and evidence of interactions, Fuel
Process. Technol. 178 (2018) 41–52.
[9] H. Hassan, J.K. Lim, B.H. Hameed, Recent progress on biomass co-pyrolysis
conversion into high-quality bio-oil, Bioresour. Technol. 221 (2016) 645–655,
https://doi.org/10.1016/j.biortech.2016.09.026.
[10] M. Al-Asadi, N. Miskolczi, Hydrogen rich products from waste HDPE/LDPE/PP/
PET over Me/Ni-ZSM-5 catalysts combined with dolomite, J. Energy Inst. 96
(2021) 251–259, https://doi.org/10.1016/j.joei.2021.03.004.
[11] L. Wu, J. Liu, P. Xu, J. Zhou, F.u. Yang, Biomass hydrogen donor assisted
microwave pyrolysis of low-rank pulverized coal: optimization, product upgrade
and synergistic mechanism, Waste Manag. 143 (2022) 177–185.
[12] Y. Fan, B. Yang, B.o. Zhang, Z. Wu, Z. Sun, J. Shang, Synergistic effects from fast
co-pyrolysis of lignin with low-rank coal: on-line analysis of products distribution
and fractal analysis on co-pyrolysis char, J. Energy Inst. 97 (2021) 152–160.
L. Wu et al.
[13] H. Zhou, H. Li, R. Duan, Q. Yang, An integrated scheme of coal-assisted oil shale
efficient pyrolysis and high-value conversion of pyrolysis oil, Energy 196 (2020),
117106, https://doi.org/10.1016/j.energy.2020.117106.
[14] T. Zhang, X. Sun, X. Li, H. Liu, J. Hong, Drivers of spatiotemporal variations in
traditional heating under carbon neutrality commitment: evidence from China at
city-level, J. Clean. Prod. 406 (2023), 137142, https://doi.org/10.1016/j.
jclepro.2023.137142.
[15] W.-J. Liu, W.-W. Li, H. Jiang, H.-Q. Yu, Fates of chemical elements in biomass
during its pyrolysis, Chem. Rev. 117 (9) (2017) 6367–6398.
[16] X. Chen, L.i. Liu, L. Zhang, Y. Zhao, P. Qiu, Pyrolysis characteristics and kinetics
of coal-biomass blends during co-pyrolysis, Energy Fuel 33 (2) (2019)
1267–1278.
[17] P.R. Bhoi, A.S. Ouedraogo, V. Soloiu, R. Quirino, Recent advances on catalysts for
improving hydrocarbon compounds in bio-oil of biomass catalytic pyrolysis,
Renew. Sustain. Energy Rev. 121 (2020), 109676, https://doi.org/10.1016/j.
rser.2019.109676.
[18] Y. Zhao, Y. Wei, Q.i. Wang, S. He, Y. Wang, Y. Zhang, The behavior of free
radicals during the carbonization of anthracite briquette, Fuel 284 (2021),
118856, https://doi.org/10.1016/j.fuel.2020.118856.
[19] X. Jiang, S. Yang, B. Zhou, Z. Hou, C. Zhang, Effect of gas atmosphere change on
radical reaction and indicator gas release during coal oxidation, Fuel 312 (2022),
122960, https://doi.org/10.1016/j.fuel.2021.122960.
[20] S. Zhong, B.o. Zhang, C. Liu, A. Shujaa aldeen, Mechanism of synergistic effects
and kinetics analysis in catalytic co-pyrolysis of water hyacinth and HDPE, Energ.
Conver. Manage. 228 (2021), 113717, https://doi.org/10.1016/j.
enconman.2020.113717.
[21] J. Uebersfeld, A. Étienne, J. Combrisson, Paramagnetic resonance, a new property
of coal-like materials, Nature 174 (4430) (1954) 614.
[22] L. Wu, H. Wu, Q. Wen, et al., Gas stripping coupled with in-situ oxidation assisted
microwave remediation of contaminated soil for efficient removal of polycyclic
aromatic hydrocarbons (PAHs), Chem. Eng. J. 473 (2023), 145411, https://doi.
org/10.1016/j. cej. 2023.145411.
[23] X. Qin, Q. Liu, J. Yu, L. Shi, Z. Liu, Study on structure and properties of remained
solids from liquefaction of Naomaohu coal in tetrahydronaphthalene, Fuel 339
(2023), 127348, https://doi.org/10.1016/j.fuel.2022.127348.
[24] S. Tian, Y. Liu, Y. Wang, J. Qi, L. Tian, J. Ma, G. Wen, L.u. Wang, Comparative
study on heterogeneous activation of peroxydisulfate and peroxymonosulfate
with black carbon derived from coal tar residues: contribution of free radical, 1O2
and surface-bound radicals, J. Hazard. Mater. 433 (2022), 128819, https://doi.
org/10.1016/j.jhazmat.2022.128819.
[25] B. Zhou, Q. Liu, L. Shi, Z. Liu, Electron spin resonance studies of coals and coal
conversion processes: a review, Fuel Process. Technol. 188 (2019) 212–227.
[26] T.A. Nguyen, S. Ichise, K. Kinashi, W. Sakai, N. Tsutsumi, S. Okubayashi, Spin
trapping analysis of the thermal degradation of polypropylene, Polym. Degrad.
Stab. 197 (2022), 109871, https://doi.org/10.1016/j.
polymdegradstab.2022.109871.
[27] Q. Zhou, Z. Luo, G. Li, S. Li, EPR detection of key radicals during coking process of
lignin monomer pyrolysis, J. Anal. Appl. Pyrol. 152 (2020), 104948, https://doi.
org/10.1016/j.jaap.2020.104948.
[28] J. Wei, M. Wang, F. Wang, X. Song, G. Yu, Y. Liu, H. Vuthaluru, J. Xu, Y. Xu,
H. Zhang, S. Zhang, A review on reactivity characteristics and synergy behavior of
biomass and coal co-gasification, Int. J. Hydrogen Energy 46 (33) (2021)
17116–17132.
[29] S.M. Gouws, M. Carrier, J.R. Bunt, H.W.J.P. Neomagus, Co-pyrolysis of coal and
raw/torrefied biomass: a review on chemistry, kinetics and implementation,
Renew. Sustain. Energy Rev. 135 (2021), 110189, https://doi.org/10.1016/j.
rser.2020.110189.
[30] W. Wang, R. Lemaire, A. Bensakhria, D. Luart, Review on the catalytic effects of
alkali and alkaline earth metals (AAEMs) including sodium, potassium, calcium
and magnesium on the pyrolysis of lignocellulosic biomass and on the co-
pyrolysis of coal with biomass, J. Anal. Appl. Pyrol. 163 (2022), 105479, https://
doi.org/10.1016/j.jaap.2022.105479.
[31] S.V. Krasnovyd, A.A. Konchits, B.D. Shanina, A.N. Molchanov, A.A. Kamchatnyj,
Adsorption processes on a carbonaceous surface: Electron spin resonance study,
Phys. B Condens. Matter 651 (2023), 414571, https://doi.org/10.1016/j.
physb.2022.414571.
[32] Z. Lei, Z. Cheng, Q. Ling, X. Liu, P. Cui, Z. Zhao, Investigating the trigger
mechanism of Shenfu bituminous coal pyrolysis, Fuel 313 (2022), 122995,
https://doi.org/10.1016/j.fuel.2021.122995.
[33] M. Liu, J. Yang, Y. Li, Z. Liu, Q. Liu, L. Shi, Radical reactions and two-step kinetics
of sub-bituminous coal liquefaction in various solvents, Energy Fuel 33 (3) (2019)
2090–2098.
[34] Q. Xu, S. Yang, W. Yang, Z. Tang, X. Hu, W. Song, B. Zhou, Micro-structure of
crushed coal with different metamorphic degrees and its low-temperature
oxidation, Process Saf. Environ. Prot. 140 (2020) 330–338.
[35] Y. Ban, L. Jin, Y. Li, H.e. Yang, H. Hu, Pyrolysis behaviors and product
distributions of coal flotation sample separated by float and sink test, Fuel 312
(2022), 122923, https://doi.org/10.1016/j.fuel.2021.122923.
[36] L. Petrakis, D.W. Grandy, Formation and behaviour of coal free radicals in
pyrolysis and liquefaction conditions, Nature 289 (5797) (1981) 476–477,
https://doi.org/10.1038/289476a0.
[37] P.E.T.R.A.K.I.S. Leon, Grandy d w., Electron spin resonance spectrometric study
of free radicals in coals, Anal. Chem. 50 (2) (1978) 303–308, https://doi.org/
10.1021/ac50024a034.
[38] A. Trubetskaya, P.A. Jensen, A.D. Jensen, P. Glarborg, F.H. Larsen, M.
L. Andersen, Characterization of free radicals by electron spin resonance
20
Chemical Engineering Journal 474 (2023) 145900
spectroscopy in biochars from pyrolysis at high heating rates and at high
temperatures, Biomass Bioenergy 94 (2016) 117–129.
[39] V. Abdelsayed, C.R. Ellison, A. Trubetskaya, M.W. Smith, D. Shekhawat, Effect of
microwave and thermal co-pyrolysis of low-rank coal and pine wood on product
distributions and char structure, Energy Fuel 33 (8) (2019) 7069–7082.
[40] B. Huang, L. Mao, X. Shi, H.-B. Yang, Recent advances and perspectives on
supramolecular radical cages, Chem. Sci. 12 (41) (2021) 13648–13663.
[41] Y. Ban, L. Jin, J. Zhu, F. Liu, H. Hu, Insights into effect of Ca(OH)2 on pyrolysis
behaviors and products distribution of Hongshaquan coal, Fuel 307 (2022),
121791, https://doi.org/10.1016/j.fuel.2021.121791.
[42] H. Uchiyama, K. Ishikawa, Q.-L. Zhao, G. Andocs, N. Nojima, K. Takeda, M.
C. Krishna, T. Ishijima, Y. Matsuya, M. Hori, K. Noguchi, T. Kondo, Free radical
generation by non-equilibrium atmospheric pressure plasma in alcohol-water
mixtures: an EPR-spin trapping study, J. Phys. D Appl. Phys. 51 (9) (2018),
095202, https://doi.org/10.1088/1361-6463/aaa885.
[43] Q. Zheng, Z. Li, T. Guo, Q. Fan, S. Hu, J. Xiang, P. Fu, Unraveling the synergistic
development of carbon skeleton and pore networks involved in lignin pyrolysis,
J. Anal. Appl. Pyrol. 170 (2023), 105912, https://doi.org/10.1016/j.
jaap.2023.105912.
[44] S. Duber, A.B.E.P.R. Wiekowski, study of molecular phases in coal, Fuel 61 (5)
(1982) 433–436, https://doi.org/10.1016/0016-2361(82)90067-9.
[45] B. Pilawa, A.B. Wie, Oxidation of demineralized coal and coal free of pyrite
examined by EPR spectroscopy, Fuel 81 (2002) 1925–1931.
[46] Y. Wu, G. Wang, J. Zhu, Y. Wang, H.e. Yang, L. Jin, H. Hu, Insight into synergistic
effect of co-pyrolysis of low-rank coal and waste polyethylene with or without
additives using rapid infrared heating, J. Energy Inst. 102 (2022) 384–394.
[47] X. Cheng, L. Shi, Q. Liu, Z. Liu, A study on vitrinite and inertinite interaction in
pyrolysis of 3 coals, J. Anal. Appl. Pyrol. 156 (2021), 105134, https://doi.org/
10.1016/j.jaap.2021.105134.
[48] X. Zhang, Z. Liu, Z. Chen, T. Xu, Q. Liu, Bond cleavage and reactive radical
intermediates in heavy tar thermal cracking, Fuel 233 (2018) 420–426.
[49] J. Cai, S. Yang, W. Zheng, W. Song, R. Gupta, Dissect the capacity of low-
temperature oxidation of coal with different metamorphic degrees, Fuel 292
(2021), 120256, https://doi.org/10.1016/j.fuel.2021.120256.
[50] L. Ma, S.S.A. Syed-Hassan, Y. Tong, Z. Xiong, Y. Chen, J. Xu, L. Jiang, S. Su, S. Hu,
Y.i. Wang, J. Xiang, Interactions of cellulose- and lignin-derived radicals during
pyrolysis: an in-situ electron paramagnetic resonance (EPR) study, Fuel Process.
Technol. 239 (2023), 107536, https://doi.org/10.1016/j.fuproc.2022.107536.
[51] B. Sun, J. Huo, H. Liu, D. Che, S. Guo, Elucidation of synergistic effects in straw/
sludge co-pyrolysis through gaseous product monitoring and biochar analysis,
J. Energy Inst. 106 (2023), 101151, https://doi.org/10.1016/j.joei.2022.11.011.
[52] G.P. Słowik, A.B. Więckowski, Influence of microwave power on EPR spectra of
coal macerals, Appl. Magn. Reson. 24 (3–4) (2003) 437–445, https://doi.org/
10.1007/BF03166947.
[53] O.Y. Grinberg, B.B. Williams, A.E. Ruuge, et al., Oxygen effects on the EPR signals
from wood charcoals: experimental results and the development of a model,
J. Phys. Chem. B 111 (46) (2007) 13316–13324, https://doi.org/10.1021/
jp072656l.
[54] J. Liu, X. Jiang, J. Shen, H. Zhang, Influences of particle size, ultraviolet
irradiation and pyrolysis temperature on stable free radicals in coal, Powder
Technol. 272 (2015) 64–74.
[55] J. Zhu, H.e. Yang, H. Hu, Y. Zhou, J. Li, L. Jin, Novel insight into pyrolysis
behaviors of lignin using in-situ pyrolysis-double ionization time-of-flight mass
spectrometry combined with electron paramagnetic resonance spectroscopy,
Bioresour. Technol. 312 (2020), 123555, https://doi.org/10.1016/j.
biortech.2020.123555.
[56] X. Guo, Y. Xiao, L. Zhao, L. Shi, X. Xue, X. Li, Z. Liu, Combustion behaviors of
various coals and chars: From covalent bonds’ and radicals’ perspective, Fuel 297
(2021), 120749, https://doi.org/10.1016/j.fuel.2021.120749.
[57] L. Ma, S.S.A. Syed-Hassan, J. Zhou, W. Deng, Y. Xiong, X. Wang, X. Hu, J. Xu,
L. Jiang, S. Su, S. Hu, Y.i. Wang, J. Xiang, Effect of alkali and alkali earth metals
on reactions of stable free radicals during biomass pyrolysis: an in-situ EPR study,
Fuel Process. Technol. 250 (2023), 107916, https://doi.org/10.1016/j.
fuproc.2023.107916.
[58] M. Toybenshlak, R. Carmieli, A new and robust method for in-situ EPR
electrochemistry, Isr. J. Chem. 59 (11–12) (2019) 1020–1026, https://doi.org/
10.1002/ijch.201900074.
[59] M.S. Seehra, B. Ghosh, S.E. Mulins, Evidence for different temperature stages in
coal pyrolysis from in situ E.S.R. spectroscopy, Fuel 65 (9) (1986) 1315–1316,
https://doi.org/10.1016/0016-2361(86)90249-8.
[60] T.G. Fowler, K.D. Bartle, R. Kandiyoti, C.E. Snape, Pyrolysis of coals as a function
of rank as studied by in situ electron spin resonance spectroscopy, Carbon 27 (2)
(1989) 197–208.
[61] L. Wang, Y. Fu, Q. Li, et al., EPR evidence for mechanistic diversity of Cu(II)/
Peroxygen oxidation systems by tracing the origin of DMPO spin adducts,
Environ. Sci. Tech. 56 (12) (2022) 8796–8806, https://doi.org/10.1021/acs.
est.2c00459.
[62] Y. Zheng, D. Li, T. Pei, J. Wang, C. Liu, Y.i. Lu, X.u. Lin, J. Li, Z. Zheng,
Mechanism of synergistic effects and kinetic analysis in bamboo-LDPE waste ex-
situ catalytic co-pyrolysis for enhanced aromatic hydrocarbon production via
CeZrAl and HZSM-5 dual catalyst, J. Environ. Chem. Eng. 10 (3) (2022), 107479,
https://doi.org/10.1016/j.jece.2022.107479.
[63] D. Ma, J. Wang, K. Feng, B. Liu, G. Xie, D. Xing, A green strategy from waste red
mud to fe0-based biochar for sulfadiazine treatment by peroxydisulfate
activation, Chem. Eng. J. 446 (2022), 136944, https://doi.org/10.1016/j.
cej.2022.136944.
L. Wu et al.
[64] F. Tang, Y. Jin, Y. Chi, Z. Zhu, J. Cai, Z. Li, M. Li, Effect of steam on the
homogeneous conversion of tar contained from the co-pyrolysis of biomass and
plastics, Environ. Sci. Pollut. Res. 28 (48) (2021) 68909–68919.
[65] F. Huang, D. Bi, S. Liu, W. Yi, J. Zhang, D.i. Yao, Formation and regulation of
environmentally persistent free radicals in biochar and removal of diethyl-
phthalate in water, J. Anal. Appl. Pyrol. 168 (2022), 105770, https://doi.org/
10.1016/j.jaap.2022.105770.
[66] L. Li, G. Liu, Y. Li, Z. Zhu, H. Xu, J. Chen, X. Ren, Release of sulfur and nitrogen
during co-pyrolysis of coal and biomass under inert atmosphere, ACS Omega 5
(46) (2020) 30001–30010.
[67] W. He, G. Yin, Y. Zhao, L. Zhang, S. Xu, T. Huang, L.u. Chang, H. Lu, Interactions
between free radicals during co-pyrolysis of lignite and biomass, Fuel 302 (2021),
121098, https://doi.org/10.1016/j.fuel.2021.121098.
[68] S. Jayaswal, N. Vidyarthi, Multiple allocation hub location with service level
constraints for two shipment classes, Eur. J. Oper. Res. 309 (2) (2023) 634–655,
https://doi.org/10.1016/j.ejor.2023.01.066.
[69] X. Liu, K.G. Burra, Z. Wang, J. Li, D. Che, A.K. Gupta, On deconvolution for
understanding synergistic effects in co-pyrolysis of pinewood and polypropylene,
Appl. Energy 279 (2020), 115811, https://doi.org/10.1016/j.
apenergy.2020.115811.
[70] P. Zhang, Z. Chen, Q. Zhang, S. Zhang, X. Ning, J. Zhou, Co-pyrolysis
characteristics and kinetics of low metamorphic coal and pine sawdust, RSC Adv.
12 (34) (2022) 21725–21735.
[71] M. Liu, J. Yang, Y. Yang, Z. Liu, L. Shi, W. He, Q. Liu, The radical and bond
cleavage behaviors of 14 coals during pyrolysis with 9,10-dihydrophenanthrene,
Fuel 182 (2016) 480–486.
[72] B. Niu, L. Jin, Y. Li, Z. Shi, H. Hu, Isotope analysis for understanding the hydrogen
transfer mechanism in direct liquefaction of Bulianta coal, Fuel 203 (2017)
82–89.
[73] S. Vasireddy, B. Morreale, A. Cugini, C. Song, J.J. Spivey, Clean liquid fuels from
direct coal liquefaction: chemistry, catalysis, technological status and challenges,
Energ. Environ. Sci. 4 (2) (2011) 311–345.
[74] H. Hao, T. Chang, L. Cui, R. Sun, R. Gao, Theoretical study on the mechanism of
hydrogen donation and transfer for hydrogen-donor solvents during direct coal
liquefaction, Catalysts 8 (12) (2018) 648.
[75] J.-K. Bai, X.-B. Zhang, W. Li, X.-B. Wang, Z.-Y. Du, W.-Y. Li, Rate constant of
hydrogen transfer from h-donor solvents to coal radicals, Fuel 318 (2022),
123621, https://doi.org/10.1016/j.fuel.2022.123621.
[76] X. Jiang, B. Yu, J. Xu, S. Chen, X. Tu, L. Wang, Study on the deflagration reaction
process of oil gas in long-narrow confined space based on PLIF and flame spectra,
J. Loss Prev. Process Ind. 64 (2020), 104088, https://doi.org/10.1016/j.
jlp.2020.104088.
[77] W. Zhu, X. Li, J. Peng, Z. Wang, R. Sun, L. Zhang, X. Yu, Y. Yu, Study on the
combustion behaviours of two high-volatile coal particle streams with high-speed
OH-PLIF, Fuel 265 (2020), 116956, https://doi.org/10.1016/j.fuel.2019.116956.
[78] C. Shao, G. Kukkadapu, S.W. Wagnon, W.J. Pitz, S.M. Sarathy, PAH formation
from jet stirred reactor pyrolysis of gasoline surrogates, Combust. Flame 219
(2020) 312–326.
[79] M. Chelang’at Mosonik, R. Volpe, C. Ezenwajiaku, M. Talibi, R. Balachandran, In
situ observation of the evolution of polyaromatic tar precursors in packed-bed
biomass pyrolysis, React. Chem. Eng. 6 (9) (2021) 1538–1547.
[80] N. Bie, J. Wang, P. Lv, Y. Zhang, Y. Bai, X. Song, W. Su, G. Yu, In-situ release
characteristic of alkali metals during co-pyrolysis of coal and biomass in a visual
fixed bed combined with laser-induced breakdown spectroscopy, Fuel 331
(2023), 125868, https://doi.org/10.1016/j.fuel.2022.125868.
[81] Q. Yang, Q. Yao, D. Ma, Y. Liu, L. He, R. Zhou, M. Sun, X. Ma, Investigation of the
(catalytic) co-pyrolysis of Shendong coal and coal tar based on rapid pyrolysis
and ANN modelling, J. Anal. Appl. Pyrol. 163 (2022), 105486, https://doi.org/
10.1016/j.jaap.2022.105486.
[82] W. He, Z. Liu, Q. Liu, D. Ci, C. Lievens, X. Guo, Behaviors of radical fragments in
tar generated from pyrolysis of 4 coals, Fuel 134 (2014) 375–380.
[83] W. He, Q. Liu, L. Shi, Z. Liu, D. Ci, C. Lievens, X. Guo, M. Liu, Understanding the
stability of pyrolysis tars from biomass in a view point of free radicals, Bioresour.
Technol. 156 (2014) 372–375.
[84] P. Liu, J. Le, L. Wang, T. Pan, X. Lu, D. Zhang, Relevance of carbon structure to
formation of tar and liquid alkane during coal pyrolysis, Appl. Energy 183 (2016)
470–477.
[85] S. Li, J. Li, H. Chen, J. Xu, Understanding the release behavior of biomass model
components and coal in the co-pyrolysis process, J. Energy Inst. 101 (2022)
122–130.
[86] S. Babu, S. Singh Rathore, R. Singh, S. Kumar, V.K. Singh, S.K. Yadav, V. Yadav,
R. Raj, D. Yadav, K. Shekhawat, O. Ali Wani, Exploring agricultural waste
biomass for energy, food and feed production and pollution mitigation: a review,
Bioresour. Technol. 360 (2022), 127566, https://doi.org/10.1016/j.
biortech.2022.127566.
[87] Z. Wu, J. Zhang, B.o. Zhang, W. Guo, G. Yang, B. Yang, Synergistic effects from
co-pyrolysis of lignocellulosic biomass main component with low-rank coal:
online and offline analysis on products distribution and kinetic characteristics,
Appl. Energy 276 (2020), 115461, https://doi.org/10.1016/j.
apenergy.2020.115461.
[88] N. Thibanyane, P. Agachi, G. Danha, Effects of biomass/coal copyrolysis
parameters on the product yield: a review, Procedia Manuf. 35 (2019) 477–487,
https://doi.org/10.1016/j.promfg.2019.07.007.
[89] B.R. Reddy, R. Vinu, Microwave assisted pyrolysis of Indian and Indonesian coals
and product characterization, Fuel Process. Technol. 154 (2016) 96–103, https://
doi.org/10.1016/j.fuproc.2016.08.016.
21
Chemical Engineering Journal 474 (2023) 145900
[90] S.M. Gouws, M. Carrier, J.R. Bunt, H.W.J.P. Neomagus, Co-pyrolysis of torrefied
biomass and coal: effect of pressure on synergistic reactions, J. Anal. Appl. Pyrol.
161 (2022), 105363, https://doi.org/10.1016/j.jaap.2021.105363.
[91] Z. Ni, H. Bi, C. Jiang, H. Sun, W. Zhou, Z. Qiu, Q. Lin, Research on the co-pyrolysis
of coal slime and cellulose based on TG-FTIR-MS, artificial neural network, and
principal component analysis, Fuel 320 (2022), 123960, https://doi.org/
10.1016/j.fuel.2022.123960.
[92] S. Zhao, P. Yang, X. Liu, Q. Zhang, J. Hu, Synergistic effect of mixing wheat straw
and lignite in co-pyrolysis and steam co-gasification, Bioresour. Technol. 302
(2020), 122876, https://doi.org/10.1016/j.biortech.2020.122876.
[93] E. Byambajav, H. Paysepar, L. Nazari, C.(. Xu, Co-pyrolysis of lignin and low rank
coal for the production of aromatic oils, Fuel Process. Technol. 181 (2018) 1–7.
[94] G. Li, F. Zheng, Q. Huang, J. Wang, B.o. Niu, Y. Zhang, D. Long, Molecular insight
into pyrolysis processes via reactive force field molecular dynamics: a state-of-
the-art review, J. Anal. Appl. Pyrol. 166 (2022), 105620, https://doi.org/
10.1016/j.jaap.2022.105620.
[95] T. Zhang, X. Li, L. Guo, Initial reactivity of linkages and monomer rings in lignin
pyrolysis revealed by ReaxFF molecular dynamics, Langmuir 33 (42) (2017)
11646–11657, https://doi.org/10.1021/acs.langmuir.7b02053.
[96] Z. Wu, W. Yang, L. Chen, H. Meng, J. Zhao, S. Wang, Morphology and
microstructure of co-pyrolysis char from bituminous coal blended with
lignocellulosic biomass: effects of cellulose, hemicellulose and lignin, Appl.
Therm. Eng. 116 (2017) 24–32.
[97] H. Zhu, M. Cheng, J. Xu, S. Chen, F. Niu, D. Yu, Nitrogen migration and
transformation from ammonia to char during ammonia-coal/char co-pyrolysis,
Int. J. Hydrogen Energy (2023), https://doi.org/10.1016/j.
ijhydene.2023.07.004.
[98] M. Yu, X. Yu, D. Yu, X.i. Jiang, Molecular dynamics investigation of the effect of
ammonia on coal pyrolysis and the nitrogen transformation, Energ. Conver.
Manage. 285 (2023), 117006, https://doi.org/10.1016/j.
enconman.2023.117006.
[99] H. Chen, R. Shan, F. Zhao, J. Gu, Y. Zhang, H. Yuan, Y. Chen, A review on the NOx
precursors release during biomass pyrolysis, Chem. Eng. J. 451 (2023), 138979,
https://doi.org/10.1016/j.cej.2022.138979.
[100] D.V. Suriapparao, B. Boruah, D. Raja, R. Vinu, Microwave assisted co-pyrolysis of
biomasses with polypropylene and polystyrene for high quality bio-oil
production, Fuel Process. Technol. 175 (2018) 64–75.
[101] X. He, D. Chen, ReaxFF MD study on the early stage co-pyrolysis of mixed PE/PP/
PS plastic waste, J. Fuel Chem. Technol. 50 (3) (2022) 346–356, https://doi.org/
10.1016/S1872-5813(21)60161-5.
[102] K. Wang, Y. Ban, Y. Wu, L. Jin, H. Hu, Synergistic effect and chlorine migration
behavior in co-pyrolysis of Pingshuo coal and polyvinyl chloride and directional
chlorine enrichment using calcium oxide, Fuel 349 (2023), 128749, https://doi.
org/10.1016/j.fuel.2023.128749.
[103] S.B. Engamba Esso, Z. Xiong, W. Chaiwat, M.F. Kamara, X.u. Longfei, J. Xu,
J. Ebako, L. Jiang, S. Su, S. Hu, Y.i. Wang, J. Xiang, Review on synergistic effects
during co-pyrolysis of biomass and plastic waste: significance of operating
conditions and interaction mechanism, Biomass Bioenergy 159 (2022), 106415,
https://doi.org/10.1016/j.biombioe.2022.106415.
[104] N. Phetyim, S. Pivsa-Art, Prototype co-pyrolysis of used lubricant oil and mixed
plastic waste to produce a diesel-like fuel, Energies 11 (11) (2018) 2973, https://
doi.org/10.3390/en11112973.
[105] W.A. Wan Mahari, S. Awang, N.A.Z. Zahariman, W. Peng, M. Man, Y.-K. Park,
J. Lee, C. Sonne, S.S. Lam, Microwave co-pyrolysis for simultaneous disposal of
environmentally hazardous hospital plastic waste, lignocellulosic, and
triglyceride biowaste, J. Hazard. Mater. 423 (2022), 127096, https://doi.org/
10.1016/j.jhazmat.2021.127096.
[106] J. Wang, J. Cui, P. Lv, X. Song, Y. Bai, W. Su, G. Yu, Y. Ma, Study on pyrolysis
characteristic of iron-based waste catalyst containing wax from Fisher-Tropsch
synthesis by TG and Py-GCMS, Thermochim Acta 710 (2022), 179173, https://
doi.org/10.1016/j.tca.2022.179173.
[107] S.S. Lam, W.A. Wan Mahari, Y.S. Ok, W. Peng, C.T. Chong, N.L. Ma, H.A. Chase,
Z. Liew, S. Yusup, E.E. Kwon, D.C.W. Tsang, Microwave vacuum pyrolysis of
waste plastic and used cooking oil for simultaneous waste reduction and
sustainable energy conversion: recovery of cleaner liquid fuel and techno-
economic analysis, Renew. Sustain. Energy Rev. 115 (2019), 109359, https://doi.
org/10.1016/j.rser.2019.109359.
[108] D. Hong, P. Li, T. Si, X. Guo, ReaxFF simulations of the synergistic effect
mechanisms during co-pyrolysis of coal and polyethylene/polystyrene, Energy
218 (2021), 119553, https://doi.org/10.1016/j.energy.2020.119553.
[109] D. Hong, P. Gao, C. Wang, A comprehensive understanding of the synergistic
effect during co-pyrolysis of polyvinyl chloride (PVC) and coal, Energy 239
(2022), 122258, https://doi.org/10.1016/j.energy.2021.122258.
[110] T. Wang, Q. Liu, W. Zhong, X. Tang, Production of light aromatics by co-pyrolysis
of lignite and plastics: effect of metal loaded hzsm-5, J. Anal. Appl. Pyrol. 170
(2023), 105927, https://doi.org/10.1016/j.jaap.2023.105927.
[111] H. Meng, M. Wang, Z. Wu, J. Zhao, J. Li, S. Wang, Physico-chemical structure and
gasification performance of co-pyrolytic char produced by the pyrolysis of
polyvinyl chloride blends with two rank coals, ACS Omega 7 (36) (2022)
32280–32291.
[112] Y. Peng, Y. Wang, L. Ke, L. Dai, Q. Wu, K. Cobb, Y. Zeng, R. Zou, Y. Liu, R. Ruan,
A review on catalytic pyrolysis of plastic wastes to high-value products, Energ.
Conver. Manage. 254 (2022), 115243, https://doi.org/10.1016/j.
enconman.2022.115243.
[113] Z. Lu, X. Zhao, Z. Liu, Q. Liu, Mutual influences between organic matter and
minerals during oil shale pyrolysis, Energy Fuel 33 (3) (2019) 1850–1858.
L. Wu et al.
[114] B. Chen, Y. Li, M. Yuan, J. Shen, S. Wang, J. Tong, Y. Guo, Study of the co-
pyrolysis characteristics of oil shale with wheat straw based on the hierarchical
collection, Energy 239 (2022), 122144, https://doi.org/10.1016/j.
energy.2021.122144.
[115] S. Cui, T. Yang, Y. Zhai, Y. Zhu, Z. Yu, X. Kai, Investigation on the characteristics
and interaction of co-pyrolysis of oil shale and peanut shell, Fuel 340 (2023),
127502, https://doi.org/10.1016/j.fuel.2023.127502.
[116] Y. Zhai, Y. Zhu, S. Cui, Y. Tao, X. Kai, T. Yang, Study on the co-pyrolysis of oil
shale and corn stalk: pyrolysis characteristics, kinetic and gaseous product
analysis, J. Anal. Appl. Pyrol. 163 (2022), 105456, https://doi.org/10.1016/j.
jaap.2022.105456.
[117] B. Baruah, P. Tiwari, Investigation of co-pyrolysis mechanism of oil shale and
rubber seed shell, product yield and optimization of pyrolysis parameter using
response surface methodology, Fuel 317 (2022), 123441, https://doi.org/
10.1016/j.fuel.2022.123441.
[118] X. Liu, P. Cui, Q. Ling, Z. Zhao, R. Xie, A review on co-pyrolysis of coal and oil
shale to produce coke, Front. Chem. Sci. Eng. 14 (4) (2020) 504–512.
[119] X. Liu, J. Hu, R. Xie, B. Fang, P. Cui, Formation mechanism of solid product
produced from co-pyrolysis of Pingdingshan lean coal with organic matter in
Huadian oil shale, Front. Chem. Sci. Eng. 15 (2) (2021) 363–372.
[120] B. Chen, X. Han, J. Tong, M. Mu, X. Jiang, S. Wang, J. Shen, X. Ye, Studies of fast
co-pyrolysis of oil shale and wood in a bubbling fluidized bed, Energ. Conver.
Manage. 205 (2020), 112356, https://doi.org/10.1016/j.
enconman.2019.112356.
[121] B. Chen, X. Han, M. Mu, X. Jiang, Studies of the co-pyrolysis of oil shale and
wheat straw, Energy Fuel 31 (7) (2017) 6941–6950.
[122] Z. Chang, X. Wang, C. Hao, W. Kuang, C. Wang, L. Zhou, M.o. Chu, Non-catalytic
and in-situ catalytic co-pyrolysis of Huadian oil shale and microalgae using
several additives as catalyst, J. Anal. Appl. Pyrol. 172 (2023), 106012, https://
doi.org/10.1016/j.jaap.2023.106012.
[123] X. Ye, A. Jiao, H. Zhang, B. Chen, S. Wang, J. Shen, Z. Yan, S. Deng, X. Han,
X. Jiang, M. Yuan, Quantum chemical calculations for the h free radical
chemisorption with different chain models during oil shale pyrolysis, Fuel 290
(2021), 119999, https://doi.org/10.1016/j.fuel.2020.119999.
[124] Y. Lu, Y. Wang, J. Zhang, Q.i. Wang, Y. Zhao, Y. Zhang, Investigation on the
characteristics of pyrolysates during co-pyrolysis of Zhundong coal and Changji
oil shale and its kinetics, Energy 200 (2020), 117529, https://doi.org/10.1016/j.
energy.2020.117529.
[125] Y. Song, N. Yin, D.i. Yao, Q. Ma, J. Zhou, X. Lan, Co-pyrolysis characteristics and
synergistic mechanism of low-rank coal and direct liquefaction residue, Energy
Sources Part A 41 (21) (2019) 2675–2689.
[126] Z. Feng, Z. Bai, R. Hou, Z. Guo, L. Kong, J. Bai, W. Li, Co-pyrolysis of mild
liquefaction solid product and low rank coals: products distributions, products
properties and interactions, Fuel 306 (2021), 121719, https://doi.org/10.1016/j.
fuel.2021.121719.
[127] Y. Yin, Y. Zhang, Z. Huang, X. Hu, Y. Gao, Z. Shao, X. Qi, Y. Yang, Influence of
temperature change on the change law of free radicals in coal, ACS Omega 6 (49)
(2021) 33685–33693.
[128] S. Gu, Z. Xu, Y. Ren, Y. Tu, D. Lu, H. Wang, Microwave co-pyrolysis of lignite with
direct coal liquefaction residue: synergistic effects and product combustion
characteristics, J. Clean. Prod. 325 (2021), 129293, https://doi.org/10.1016/j.
jclepro.2021.129293.
[129] X. Li, Y. Xue, J. Feng, Q. Yi, W. Li, X. Guo, K.e. Liu, Co-pyrolysis of lignite and
Shendong coal direct liquefaction residue, Fuel 144 (2015) 342–348.
[130] Y. Song, S. Lei, J. Li, N. Yin, J. Zhou, X. Lan, In situ FT-IR analysis of coke
formation mechanism during co-pyrolysis of low-rank coal and direct coal
liquefaction residue, Renew. Energy 179 (2021) 2048–2062.
[131] D. Zhang, S. Wang, X. Ma, Y. Tian, Interaction between coal and distillation
residues of coal tar during co-pyrolysis, Fuel Process. Technol. 138 (2015)
221–227.
[132] Y. Song, Q. Ma, W. He, Co-pyrolysis properties and product composition of low-
rank coal and heavy oil, Energy Fuel 31 (1) (2017) 217–223, https://doi.org/
10.1021/acs.energyfuels.6b02106.
[133] Y. Li, S. Huang, S. Wu, Y. Wu, J. Gao, Co-pyrolysis of lignite and vacuum residue:
product distribution and hydrogen transfer, Fuel 263 (2020), 116703, https://
doi.org/10.1016/j.fuel.2019.116703.
[134] O.A. Fakayode, H. Wahia, L. Zhang, C. Zhou, H. Ma, State-of-the-art co-pyrolysis
of lignocellulosic and macroalgae biomass feedstocks for improved bio-oil
production- a review, Fuel 332 (2023), 126071, https://doi.org/10.1016/j.
fuel.2022.126071.
[135] B.B. Uzoejinwa, X. He, S. Wang, A.-F. Abomohra, Y. Hu, Z. He, Q. Wang, Co-
pyrolysis of seaweeds with waste plastics: modeling and simulation of effects of
co-pyrolysis parameters on yields, and optimization studies for maximum yield of
enhanced biofuels, Energy Sources Part A 42 (8) (2020) 954–978.
[136] B.S. Adeboye, B.Z. Adewole, A.M. Adedoja, S.O. Obayopo, A.A. Asere, O. Kayode,
M.O. Idris, I.K. Okediran, Optimization and modeling of process parameters on
the yield of enhanced pyrolysis oil during co-pyrolysis of cassava peel with
polystyrene, Environmental Challenges 5 (2021), 100347, https://doi.org/
10.1016/j.envc.2021.100347.
[137] M. Tauseef, A.A. Ansari, A.H. Khoja, S.R. Naqvi, R. Liaquat, W. Nimmo, S.
S. Daood, Thermokinetics synergistic effects on co-pyrolysis of coal and rice husk
blends for bioenergy production, Fuel 318 (2022), 123685, https://doi.org/
10.1016/j.fuel.2022.123685.
[138] P. Wang, C. Wang, C. Wang, M. Yuan, Y. Du, J. Zhang, D. Che, Synergistic effects
in rapid co-pyrolysis of semi-coke and coal at high temperature, Fuel 282 (2020),
118795, https://doi.org/10.1016/j.fuel.2020.118795.
22
Chemical Engineering Journal 474 (2023) 145900
[139] G. Srinivasan, M.S. Seehra, Effect of pyrite and pyrrhotite on free radical
formation in coal, Fuel 62 (7) (1983) 792–794, https://doi.org/10.1016/0016-
2361(83)90029-7.
[140] H. Merdun, Z.B. Laougé, Kinetic and thermodynamic analyses during co-pyrolysis
of greenhouse wastes and coal by TGA, Renew. Energy 163 (2021) 453–464,
https://doi.org/10.1016/j.renene.2020.08.120.
[141] F. Yang, A. Zhou, W. Zhao, Z. Yang, H. Li, Thermochemical behaviors, kinetics
and gas emission analyses during co-pyrolysis of walnut shell and coal,
Thermochim Acta 673 (2019) 26–33.
[142] Y. Wu, J. Zhu, Y. Wang, H.e. Yang, L. Jin, H. Hu, Insight into co-pyrolysis
interactions of Pingshuo coal and high-density polyethylene via in-situ PY-TOF-
MS and EPR, Fuel 303 (2021), 121199, https://doi.org/10.1016/j.
fuel.2021.121199.
[143] G. Yan, Z. Zhang, K. Yan, Reactive molecular dynamics simulations of the initial
stage of brown coal oxidation at high temperatures, Mol. Phys. 111 (1) (2013)
147–156, https://doi.org/10.1080/00268976.2012.708443.
[144] W. Chen, S. Shi, T. Nguyen, et al., Effect of temperature on the evolution of
physical structure and chemical properties of bio-char derived from co-pyrolysis
of lignin with high-density polyethylene, BioResources 11 (2) (2016) 3923–3936,
https://doi.org/10.15376/biores.11.2.3923-3936.
[145] T. Schubert, M. Lehner, T. Karner, W. Hofer, A. Lechleitner, Influence of reaction
pressure on co-pyrolysis of LDPE and a heavy petroleum fraction, Fuel Process.
Technol. 193 (2019) 204–211.
[146] X. Zhuang, Z. Gan, K. Cen, Y. Ba, F. Chen, D. Chen, Upgrading biochar by co-
pyrolysis of heavy bio-oil and apricot shell using response surface methodology,
Fuel 310 (2022), 122447, https://doi.org/10.1016/j.fuel.2021.122447.
[147] M. Ma, J. Wang, Y. Bai, P. Lv, X. Song, W. Su, J. Wei, G. Yu, Decoupling of
volatile-char interaction in co-pyrolysis of cow manure and bituminous coal and
deactivation mechanism of coal char reactivity, Energy 251 (2022), 123891,
https://doi.org/10.1016/j.energy.2022.123891.
[148] X. Guo, X. Xu, X. Tang, X. Xue, X. Li, Investigation of co-pyrolysis of coals and
biomass by Boltzmann-Monte Carlo-Percolation (BMCP) model, J. Anal. Appl.
Pyrol. 155 (2021), 105083, https://doi.org/10.1016/j.jaap.2021.105083.
[149] Y. Wen, Y. Xie, C. Jiang, W. Li, Y. Hou, Products distribution and interaction
mechanism during co-pyrolysis of rice husk and oily sludge by experiments and
reaction force field simulation, Bioresour. Technol. 329 (2021), 124822, https://
doi.org/10.1016/j.biortech.2021.124822.
[150] A. Khan, J. Akhtar, K. Shahzad, N. Sheikh, S. Munir, Co-pyrolysis and
hyrdogenation of waste tires and thar coal blends, Energy Sources Part A (2017)
1–7.
[151] A.M. Mastral, R. Murillo, M.S. Callén, T. Garcı́a, Evidence of coal and tire
interactions in coal-tire coprocessing for short residence times, Fuel Process.
Technol. 69 (2) (2001) 127–140.
[152] L. Zhou, G. Zhang, M. Reinmöller, B. Meyer, Effect of inherent mineral matter on
the co-pyrolysis of highly reactive brown coal and wheat straw, Fuel 239 (2019)
1194–1203.
[153] B. Nyoni, S.P. Hlangothi, Co-pyrolysis of low-grade bituminous coal and algal
biomass in a rotary kiln: effect of coal/algae ratio and kiln temperature on the
yield and composition of the resultant oils, J. Anal. Appl. Pyrol. 171 (2023),
105950, https://doi.org/10.1016/j.jaap.2023.105950.
[154] J. Zhu, L. Jin, Y. Luo, H. Hu, Y. Xiong, B. Wei, D. Wang, Fast co-pyrolysis of a
massive Naomaohu coal and cedar mixture using rapid infrared heating, Energ.
Conver. Manage. 205 (2020), 112442, https://doi.org/10.1016/j.
enconman.2019.112442.
[155] Z.B. Laougé, H. Merdun, Investigation of thermal behavior of pine sawdust and
coal during co-pyrolysis and co-combustion, Energy 231 (2021), 120895, https://
doi.org/10.1016/j.energy.2021.120895.
[156] Y. Wen, S. Liu, S. Fu, Z. Wang, H. Hu, L. Jin, Insight into influence of process
parameters on co-pyrolysis interaction between Yulin coal and waste tire via
rapid infrared heating, Fuel 337 (2023), 127161, https://doi.org/10.1016/j.
fuel.2022.127161.
[157] C. Tang, D. Zhang, X. Lu, Improving the yield and quality of tar during co-
pyrolysis of coal and cotton stalk, BioResources 10 (4) (2015) 7667–7680,
https://doi.org/10.15376/biores.10.4.7667-7680.
[158] S. Krerkkaiwan, C. Fushimi, A. Tsutsumi, P. Kuchonthara, Synergetic effect during
co-pyrolysis/gasification of biomass and sub-bituminous coal, Fuel Process.
Technol. 115 (2013) 11–18.
[159] P.A. Bozkurt, O. Tosun, M. Canel, The synergistic effect of co-pyrolysis of oil shale
and low-density polyethylene mixtures and characterization of pyrolysis liquid,
J. Energy Inst. 90 (3) (2017) 355–362, https://doi.org/10.1016/j.
joei.2016.04.007.
[160] H. Gohar, A.H. Khoja, A.A. Ansari, S.R. Naqvi, R. Liaquat, M. Hassan, K. Hasni, U.
Y. Qazi, I. Ali, Investigating the characterisation, kinetic mechanism, and
thermodynamic behaviour of coal-biomass blends in co-pyrolysis process, Process
Saf. Environ. Prot. 163 (2022) 645–658.
[161] Z. Ni, H. Bi, C. Jiang, C. Wang, J. Tian, W. Zhou, H. Sun, Q. Lin, Investigation of
the co-pyrolysis of coal slime and coffee industry residue based on machine
learning methods and TG-FTIR: synergistic effect, kinetics and thermodynamic,
Fuel 305 (2021), 121527, https://doi.org/10.1016/j.fuel.2021.121527.
[162] D. Hong, Y. Guo, C. Wang, R. Wei, Coal/NH3 interactions during co-pyrolysis and
their effects on the char reactivity for no-reduction: a ReaxFF MD study, Fuel 346
(2023), 128415, https://doi.org/10.1016/j.fuel.2023.128415.
[163] J. Hongrapipat, W.L. Saw, S. Pang, Co-gasification of blended lignite and wood
pellets in a dual fluidized bed steam gasifier: the influence of lignite to fuel ratio
on NH3 and H2 s concentrations in the producer gas, Fuel 139 (2015) 494–501,
https://doi.org/10.1016/j.fuel.2014.09.030.
L. Wu et al.
[164] J. Li, J. Zhu, H. Hu, L. Jin, D. Wang, G. Wang, Co-pyrolysis of Baiyinhua lignite
and pine in an infrared-heated fixed bed to improve tar yield, Fuel 272 (2020),
117739, https://doi.org/10.1016/j.fuel.2020.117739.
[165] J. Zhu, S. Zhao, B. Wei, J.i. Xu, H. Hu, L. Jin, Enhanced co-pyrolysis synergies
between cedar and Naomaohu coal volatiles for tar production, J. Anal. Appl.
Pyrol. 160 (2021), 105355, https://doi.org/10.1016/j.jaap.2021.105355.
[166] T. Zhang, Z. Bai, Z. Guo, L. Kong, H. Dou, J. Bai, W. Li, Synergistic effect of Hami
coal and polystyrene on products properties during co-pyrolysis: evaluation on
the contribution of different interaction sources, Fuel 338 (2023), 127209,
https://doi.org/10.1016/j.fuel.2022.127209.
[167] W. Chen, K. Li, M. Xia, H. Yang, Y. Chen, X.u. Chen, Q. Che, H. Chen, Catalytic
deoxygenation co-pyrolysis of bamboo wastes and microalgae with biochar
catalyst, Energy 157 (2018) 472–482.
[168] S. Huang, L. Pan, Y. Li, S. Wu, Y. Wu, J. Gao, Investigation on hydrogen migration
and redistribution characteristics during co-pyrolysis of lignite with hydrogen-
rich carbonaceous matters, Fuel 303 (2021), 121268, https://doi.org/10.1016/j.
fuel.2021.121268.
[169] M. Mu, X. Han, X. Jiang, Interactions between oil shale and hydrogen-rich wastes
during co-pyrolysis: 1. co-pyrolysis of oil shale and polyolefins, Fuel 265 (2020),
116994, https://doi.org/10.1016/j.fuel.2019.116994.
[170] B. Wu, X. Guo, X. Qian, B.o. Liu, Insight into the influence of calcium on the co-
pyrolysis of coal and polystyrene, Fuel 329 (2022), 125471, https://doi.org/
10.1016/j.fuel.2022.125471.
[171] H. Meng, M. Wang, Z. Wu, S. Wang, J. Zhao, Z. Wang, D. Wang, H. Wang, J. Li,
H. Li, Co-pyrolysis of platanus wood and bituminous coal: product distributions,
char pore analysis and synergistic effects, J. Anal. Appl. Pyrol. 167 (2022),
105703, https://doi.org/10.1016/j.jaap.2022.105703.
[172] D. Hong, X. Guo, Molecular dynamics simulations of Zhundong coal pyrolysis
using reactive force field, Fuel 210 (2017) 58–66, https://doi.org/10.1016/j.
fuel.2017.08.061.
[173] C.Y. Cha, B.I. Kim, R.E. Lumpkin, E.M.Y. Quinga, Electromagnetic enhancement
of chemical reactions (devolatilization of char and coal), Fuel Sci. Technol. Int. 11
(9) (1993) 1175–1202.
[174] L.L. Tan, Li c-z., Formation of NOx and SOx precursors during the pyrolysis of coal
and biomass. part I. effects of reactor configuration on the determined yields of
HCN and NH3 during pyrolysis, Fuel 79 (15) (2000) 1883–1889, https://doi.org/
10.1016/S0016-2361(00)00078-8.
[175] M.P. Aznar, M.A. Caballero, J.A. Sancho, E. Francés, Plastic waste elimination by
co-gasification with coal and biomass in fluidized bed with air in pilot plant, Fuel
Process. Technol. 87 (5) (2006) 409–420.
[176] W. He, S. Xu, M. Liu, Y. Zhao, L. Zhang, T. Huang, Z. Liu, Interactions between
coal and solvent during the solvent extraction of coal in view of free radicals, ACS
Omega 6 (46) (2021) 31058–31065.
[177] Y. Wu, J. Zhu, J. Yang, L. Jin, H. Hu, Insight into co-pyrolysis interaction of
Pingshuo coal and low-density polyethylene under varied mixing configurations
via in-situ PY-TOF-MS, J. Anal. Appl. Pyrol. 168 (2022), 105698, https://doi.org/
10.1016/j.jaap.2022.105698.
[178] X. Jin, L. Yan, B. Cui, J. Kong, M. Wang, L. Chang, F. Ronsse, W. Bao, Nickel
loaded on carbon materials prepared from co-pyrolysis of biochar and caking coal
for catalytic conversion of volatiles, J. Anal. Appl. Pyrol. 169 (2023), 105825,
https://doi.org/10.1016/j.jaap.2022.105825.
[179] Y.-L. Zhang, W.-G. Wu, S.-H. Zhao, Y.-F. Long, Y.-H. Luo, Experimental study on
pyrolysis tar removal over rice straw char and inner pore structure evolution of
char, Fuel Process. Technol. 134 (2015) 333–344.
[180] Y. Hou, Z. Feng, Y. He, Q.i. Gao, L. Ni, M. Su, H. Ren, Z. Liu, W. Hu, Co-pyrolysis
characteristics and synergistic interaction of bamboo residues and disposable face
mask, Renew. Energy 194 (2022) 415–425.
[181] L. Wu, J. Liu, J. Zhou, Q. Zhang, Y. Song, S. Du, W. Tian, Evaluation of tar from
the microwave co-pyrolysis of low-rank coal and corncob using orthogonal-test-
based grey relational analysis (GRA), J. Clean. Prod. 337 (2022), 130362, https://
doi.org/10.1016/j.jclepro.2022.130362.
23
Chemical Engineering Journal 474 (2023) 145900
[182] R. Zhou, R. Cao, Y. Liu, D. Ma, Q. Yao, J. Wang, M. Sun, X. Ma, Study on the
characteristics and mechanism of fast co-pyrolysis of coal tar asphaltene and
biomass, J. Anal. Appl. Pyrol. 161 (2022), 105409, https://doi.org/10.1016/j.
jaap.2021.105409.
[183] T. Su, Y. Song, X. Lan, Product characteristics and interaction mechanism in low-
rank coal and coking coal co-pyrolysis process, J. Chem. Eng. Jpn. 53 (4) (2020)
167–176, https://doi.org/10.1252/jcej.18we172.
[184] S. Qiu, S. Zhang, Y. Fang, G. Qiu, C. Yin, R.G. Reddy, Q. Zhang, L. Wen, Effects of
poplar addition on tar formation during the co-pyrolysis of fat coal and poplar at
high temperature, RSC Adv. 9 (48) (2019) 28053–28060.
[185] S. Li, J. Li, J. Xu, Investigating the release behavior of biomass and coal during the
co-pyrolysis process, Int. J. Hydrogen Energy 46 (70) (2021) 34652–34662,
https://doi.org/10.1016/j.ijhydene.2021.08.053.
[186] W. He, Z. Liu, Q. Liu, L. Shi, X. Shi, J. Wu, X. Guo, Behavior of radicals during
solvent extraction of three low rank bituminous coals, Fuel Process. Technol. 156
(2017) 221–227.
[187] Y. Wu, J. Zhu, S. Zhao, D. Wang, L. Jin, H. Hu, Co-pyrolysis behaviors of low-rank
coal and polystyrene with in-situ pyrolysis time-of-flight mass spectrometry, Fuel
286 (2021), 119461, https://doi.org/10.1016/j.fuel.2020.119461.
[188] S. Mariyam, M. Shahbaz, T. Al-Ansari, H.R. Mackey, G. McKay, A critical review
on co-gasification and co-pyrolysis for gas production, Renew. Sustain. Energy
Rev. 161 (2022), 112349, https://doi.org/10.1016/j.rser.2022.112349.
[189] B. Lin, J. Zhou, Q. Qin, X. Song, Z. Luo, Thermal behavior and gas evolution
characteristics during co-pyrolysis of lignocellulosic biomass and coal: a TG-FTIR
investigation, J. Anal. Appl. Pyrol. 144 (2019), 104718, https://doi.org/10.1016/
j.jaap.2019.104718.
[190] T.M. Ismail, S.W. Banks, Y. Yang, H. Yang, Y. Chen, A.V. Bridgwater, K. Ramzy,
M. Abd El-Salam, Coal and biomass co-pyrolysis in a fluidized-bed reactor:
numerical assessment of fuel type and blending conditions, Fuel 275 (2020),
118004, https://doi.org/10.1016/j.fuel.2020.118004.
[191] B. Tian, W. Zhao, Q. Guo, Y. Tian, A comprehensive understanding of synergetic
effect and volatile interaction mechanisms during co-pyrolysis of rice husk and
different rank coals, Energy 254 (2022), 124388, https://doi.org/10.1016/j.
energy.2022.124388.
[192] Y. Li, S. Huang, Q. Wang, H. Li, Q. Zhang, H. Wang, Y. Wu, S. Wu, J. Gao,
Hydrogen transfer route and interaction mechanism during co-pyrolysis of
Xilinhot lignite and rice husk, Fuel Process. Technol. 192 (2019) 13–20.
[193] K. Xu, S. Hu, L. Zhang, H. Li, Y. Chen, Z. Xiong, J. Xu, L. Jiang, Y.i. Wang, S. Su,
J. Xiang, Effect of temperature on Shenfu coal pyrolysis process related to its
chemical structure transformation, Fuel Process. Technol. 213 (2021), 106662,
https://doi.org/10.1016/j.fuproc.2020.106662.
[194] D. Li, S. Lei, F. Lin, L. Zhong, W. Ma, G. Chen, Study of scrap tires pyrolysis -
products distribution and mechanism, Energy 213 (2020), 119038, https://doi.
org/10.1016/j.energy.2020.119038.
[195] L. Florentino-Madiedo, M.F. Vega, E. Díaz-Faes, C. Barriocanal, Evaluation of
synergy during co-pyrolysis of torrefied sawdust, coal and paraffin. a kinetic and
thermodynamic study, Fuel 292 (2021), 120305, https://doi.org/10.1016/j.
fuel.2021.120305.
[196] Y. Yang, J. Xu, Z. Liu, Q. Guo, M. Ye, G. Wang, J. Gao, J. Wang, Z. Shu, W. Ge,
Z. Liu, F. Wang, Y.-W. Li, Progress in coal chemical technologies of China, Rev.
Chem. Eng. 36 (1) (2019) 21–66.
[197] H. Tian, H. Jiao, J. Cai, J. Wang, Y. Yang, A.V. Bridgwater, Co-pyrolysis of
Miscanthus Sacchariflorus and coals: A systematic study on the synergies in
thermal decomposition, kinetics and vapour phase products, Fuel 262 (2020),
116603, https://doi.org/10.1016/j.fuel.2019.116603.
[198] Z. Yang, J. Zhang, J. Huang, G. Qian, X. Duan, X. Zhou, In-situ catalytic upgrading
of tar and coke during biomass/coal co-pyrolysis, Ind. Eng. Chem. Res. 59 (39)
(2020) 17182–17191.
[199] J. Song, C. Tang, S. Yu, X. Yang, L. Yang, Prediction of product yields using fusion
model from co-pyrolysis of biomass and coal, Bioresour. Technol. 353 (2022),
127132, https://doi.org/10.1016/j.biortech.2022.127132.