Fuel 303 (2021) 121268

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Investigation on hydrogen migration and redistribution characteristics

during co-pyrolysis of lignite with hydrogen-rich carbonaceous matters
Sheng Huang a, Linhui Pan a, Yanling Li c, Shiyong Wu a, b, *, Youqing Wu a, *, Jinsheng Gao a
a
Department of Chemical Engineering for Energy Resources, East China University of Science and Technology, Shanghai 200237, China
b
State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, Ningxia University, Yinchuan 750021, China
c
National-Local Joint Engineering Research Center of Biomass Refining and High-Quality Utilization, Institute of Urban and Rural Mining, Changzhou University, 21
Gehu Middle Rd, Changzhou, Jiangsu 213164, China

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

Keywords: The hydrogen migration and distribution characteristics in products during co-pyrolysis of Xilinhot lignite (XL)
Lignite with hydrogen-rich carbonaceous matters, rice husk (RH, abundant in hydroxy hydrogen) and vacuum residue
Co-pyrolysis (VR, abundant in aliphatic hydrogen), were investigated, and the interaction mechanisms were also elucidated.
Hydrogen migration
The results show that the co-pyrolysis behaviors of XL/RH and XL/VR mixtures are completely different. Co-
Hydrogen redistribution
Interaction mechanism
pyrolysis of XL/RH produces more gas and water and less tar than expected, while XL/VR co-pyrolysis yields
more char and less gas. The hydrogen migrated into water and gas are higher than expected during co-pyrolysis
of XL/RH, and the hydrogen migrated into tar (12.28–15.30%) and char (35.27–47.70%) are lower than theo­
retical values (13.33–18.75% and 37.50–49.05%). This indicates that the addition of RH is favorable for the
migration of hydrogen from tar and char to gas and water during XL pyrolysis. Differently, the hydrogen
migrated into tar (19.73–31.59%) is higher than expected (17.04–30.03%), and hydrogen migrated into water
(16.57–21.29%) is less than theoretical values (18.16–23.55%) during XL/VR co-pyrolysis. This implies that the
addition of VR is conducive to the migration of hydrogen from water to tar during XL pyrolysis. Consequently,
the contents of n-hexane solubles (nHS) in tars from XL/VR co-pyrolysis are higher than expected, indicating the
improvement of tar quality. In conclusion, co-pyrolysis of lignite with hydrogen-rich carbonaceous matters
cannot always enhance tar yield and/or improve tar quality, which largely depend on the content and occurrence
of hydrogen in hydrogen-rich carbonaceous matters.

1. Introduction technology are basically in the pilot or industrial demonstration stage

Low-rank coals (including lignite and sub-bituminous coal) are
abundant fossil resources, which account for 50% of the global total coal
deposits [1–2]. However, high water and oxygen contents and low
calorific value severely limit low-rank coals application in traditional
utilization technologies, such as combustion and gasification. In light of
this, more attention has been paid to develop a reasonable method for
the efficient utilization of low-rank coals [3–4]. Low temperature py­
rolysis is regard as an effective way to upgrade low-rank coals. Mean­
while, high value-added tar and gas can also be obtained [5–8]. Low
temperature pyrolysis of low-rank coals has made great progress in the
past decades [9]. Due to many severe technical problems still existed,
such as low tar yield, high content of heavy components in tar, and the
difficulties of gas–solid effective separation, the developed pyrolysis
[9–10]. So far, there is still no large-scale commercial operation plant of
low temperature pyrolysis of low-rank coals.
It is well known that coal is abundant in carbon and deficient in
hydrogen, and the content and occurrence of hydrogen in coal deter­
mine the distributions and characteristics of products during the low
temperature pyrolysis process [11–12]. It is desired that more hydrogen
migration into desired products and less hydrogen migration into un­
desired products. In order to enhance tar yield and to improve tar
quality, many attempts were made, such as coal pretreatment [13–14],
design new reactor to control coal pyrolysis and secondary cracking of
volatiles [15–16], hydropyrolysis [17–18], catalytic pyrolysis [19–20]
and co-pyrolysis of low-rank coals with hydrogen-rich carbonaceous
matters [21–27], etc. Till now, co-pyrolysis of low-rank coals with
hydrogen-rich carbonaceous matters, such as biomass [21–23],

* Corresponding authors.
E-mail addresses: wsy@ecust.edu.cn (S. Wu), wyq@ecust.edu.cn (Y. Wu).

https://doi.org/10.1016/j.fuel.2021.121268
Received 24 March 2021; Received in revised form 17 May 2021; Accepted 13 June 2021
Available online 1 July 2021
0016-2361/© 2021 Elsevier Ltd. All rights reserved.
S. Huang et al.
petroleum residue [6,24], coal liquefaction residue [7] and plastic
[25–27], are investigated to clarify whether the hydrogen in hydrogen-
rich carbonaceous matters is beneficial to enhance tar yield and/or
improve tar quality.
Although co-pyrolysis of low-rank coals with hydrogen-rich carbo­
naceous matters were extensively investigated, the majority of them
focus on the synergic effects on product yields and the optimization of
experimental conditions for obtaining higher tars yield [24–30]. As
mentioned above, the content and occurrence of hydrogen in raw ma­
terials is crucial to the distributions and properties of products during
pyrolysis process. However, the investigations on the interaction
mechanisms during co-pyrolysis of low-rank colas with hydrogen-rich
carbonaceous matters from the perspective of hydrogen migration and
redistribution is scarce. Therefore, it is very imperative to investigate
hydrogen migration and redistribution behaviors to elucidate the
interaction mechanisms during co-pyrolysis of low-rank coals with
hydrogen-rich carbonaceous matters.
In this paper, the co-pyrolysis behaviors of lignite with hydrogen-
rich carbonaceous matters, rice husk (RH, abundant in hydroxy
hydrogen) and vacuum residue (VR, abundant in aliphatic hydrogen),
were investigated. Product and hydrogen distributions were analyzed
and compared with the theoretical values to elucidate hydrogen
migration and redistribution behaviors during co-pyrolysis process. This
paper is aiming at providing fundamental information to better under­
stand the potential interaction mechanisms between low-rank coals and
hydrogen-rich carbonaceous matters with different types of hydrogen.
2. Experimental
2.1. Materials
In the present study, Xilinhot lignite (XL) was obtained from Xilinhot
coal mine, located in Xilinhot City, Inner Mongolia. Rich husk (RH) was
collected from the countryside of Gaoyou City, Jiangsu Province. Vac­
uum residue (VR) was collected from Sinopec Shanghai Gaoqiao
Petrochemical Co., LTD. XL and RH was ground to below 74 μm before
pyrolysis experiments. VR is a very viscous solid at the room tempera­
ture and can be cut into small pieces using scissors. The proximate and
ultimate analyses of samples are shown in Table 1.
As shown in Table 1, the hydrogen content of XL is extremely low
(4.16%), and the hydrogen contents of RH (abundant in hydroxy
hydrogen) and VR (abundant in aliphatic hydrogen) are higher than that
of XL. So, RH and VR were used as hydrogen-rich carbonaceous matters
in this study.
2.2. Experimental procedures
The individual and co-pyrolysis experiments were performed ac­
cording to the Chinese National Standard GB/T 480–2010. The XL/RH
and XL/VR mixtures were direct mixing of solid–solid, and the mixing of
XL/RH and XL/VR mixtures usually last for about 30 min. In short, about
15 g of sample was put into aluminum retort, and the heating program
was as follows: rapidly heated from room temperature to 260 within
20 min, then heated to 550 in a rate of 5 /min and held for 20 min
[31]. A conical bottle was put in ice/water mixture to collect liquid
product (tar and water), and a vacuum air bag was connected to collect
Table 1
Proximate analysis and ultimate analysis of XL, RH and VR.
Samples Proximate analysis (%)
Mad Ad Vdaf
XL 1.65 11.19 43.92
RH 1.57 13.16 68.32
VR 0.04 0.23 99.69
ad: air-dried basis; d: dry basis; daf: dry and ash free basis; a: by difference.
Fuel 303 (2021) 121268
gaseous product. After the completion of pyrolysis process, aluminum
retort was took out and cooled down. The char was took out from
aluminum retort and weighted to calculate the char yield (wt%, on a dry
and ash free basis of raw materials). The mass of liquid product was
calculated by weight the increment of the conical flask. The mass of
pyrolysis water was obtained according to the Chinese National Stan­
dard GB/T 480–2010, and the mass of tar was obtained by subtracting
the mass of water from the mass of the liquid. Gas yield was calculated
by difference.
In order to investigate the compositions and hydrogen types of tars,
another two more times of each pyrolysis experiment were performed.
Gas chromatography-mass spectrometer (GC/MS) analysis were per­
formed by dissolving liquid products into n-hexane. Besides, the indi­
vidual and co-pyrolysis tars were collected by C2Cl4. Then the solutions
were detected by 1H NMR to determine the types of hydrogen in tar.
For convenience, XL(100-x)RHx (x = 5, 10, 15, 20 or 30) was used to
donate the XL/RH mixtures with 5, 10, 15, 20 and 30 wt% RH,
respectively. XL-nHS, RH-nHS and XL(100-x)RHx-nHS were used to
donate the n-hexane solubles of tars from the individual and co-
pyrolysis, respectively.
Each co-pyrolysis experiment was carried out at least three times in
order to determine the variability of the results and to assess the
experimental relative errors<5.0%.
2.3. Analysis
2.3.1. Proximate and ultimate analyses
The proximate analyses of raw materials were made according to
Chinese standard GB/T 212–2008. The ultimate analyses (C, H, N and S
contents) of raw materials, chars and tars were performed using
elemental analyzer (Vario Micro Cube, Elementar Trading Shanghai Co.,
Ltd.). The data was corrected by deducting the blank measurement and
comparing with standard sample. The contents of C, H, N and S in the
samples were obtained simultaneously.
2.3.2. Gas chromatography analysis
Concentrations of individual component in gaseous products during
co-pyrolysis process were tested using a 9800 type gas chromatography
(GC) (Shanghai Kechuang Analytical Instrument Co., Ltd.) equipped
with a TDX-01 column (thermal conductivity detector, TCD, for
detecting H2, CH4, CO, and CO2) and a Plot-Al2O3 column (flame ioni­
zation detector, FID, for detecting C2 to C4 hydrocarbons). The hydrogen
content in gas (wt%, on product basis) was obtained by calculating the
total mass of hydrogen in hydrogen-containing compounds, such as CH4,
H2, C2H6.
2.3.3. 1Hydrogen-nuclear magnetic resonance
Tars were analyzed by 1H NMR with a Bruker Avance Neo 600 MHz
to investigate the hydrogen types in tars. The test temperature was set to
be 25 , spectral widths was 11.9 KHz, delay times was 6 s. 0.5 mL
CDCl3 was placed in a 5 mm NMR tube. Tetramethylsilane (TMS) was
used as internal chemical shift reference. Hydrogen types were classified
into HA, HO, Hα, Hβ and Hγ (as shown in Fig. 1) based on the attribution
of chemical shift [32–34], and the corresponding chemical shifts are
presented in Table 2. The relative contents of each hydrogen type to the
total hydrogen were calculated by the integral calculations. And the
Ultimate analysis (%)
Cdaf Hdaf Ndaf St,d Oadaf
71.13 4.16 1.16 0.46 > 23.10
48.27 6.14 0.77 0.04 > 38.88
86.82 9.71 0.29 2.67 >0.50
2
S. Huang et al.
Fig. 1. Assignments of various types of hydrogen protons.
Table 2
Assignments of chemical shifts of different hydrogen types in 1H NMR spectra.
Chemical shift Signal Type of hydrogen
(ppm)
6.5–9.5 HA Aromatic hydrogen
4.5–5.5 HO Phenolic hydrogen
2.1–4.5 Hα Aliphatic hydrogen on Cα to aromatic rings
1.1–2.1 Hβ Aliphatic hydrogen on Cβ and the CH2, CH beyond the
Cβ to aromatic rings
0.5–1.1 Hγ Aliphatic hydrogen on Cγ and the CH3 beyond the Cγ to
aromatic rings
total integral value of each spectrum was normalized to the corre­
sponding value of the TMS area (chemical shift from − 0.08 to 0.08
ppm).
2.3.4. Gas chromatography-Mass spectrometer analysis
The n-hexane solubles (nHS) of tars were analyzed with a GC/MS
analyzer (Agilent 6890/5973 N, Agilent Technologies, USA), which was
equipped with a capillary column coated with HP-5MS (crosslink 5% PH
ME siloxane, 30 m × 0.25 mm inner diameter, 0.25 μm film thicknsess,
helium as a carrier gas at a flow rate of 1.0 mL/min, mass scanning range
of 30 ~ 500 amu). The column was heated to 60 ◦ C and held for 2 min,
and then heated to 300 ◦ C at a rate of 5 ◦ C/min and held for 10 min. The
organic compounds were identified by comparing the mass spectra to
NIST05 and Wiley7n library data, and their relative contents (the con­
tent of each peak area) were obtained by the methods of normalization
of peak areas.
2.4. Calculation
2.4.1. Theoretical values
In order to evaluate the interactions between raw materials during
co-pyrolysis, theoretical values were calculated using weighted average
sum as shown in Eq. (1).
Ymix,i = xYA,i + (1 − x)YB,i
where i is a kind of pyrolysis product (tar, water, gas or char) or a kind of
gaseous product (H2, CO, CH4, CO2 or C2-C4 hydrocarbon) or a kind of
hydrogen (HA, HO, Hα, Hβ or Hγ); Ymix,i is the theoretical yield of i from
the co-pyrolysis; YA,i and YB,i are the yields of i from XL, RH or VR in­
dividual pyrolysis, respectively; and × is the mass fraction (on the dry
and ash free basis) of RH or VR in the mixture. For convenience, theo­
retical values are denoted as T and experimental values are denoted as E.
2.4.2. Hydrogen distribution and balance during pyrolysis process
The total hydrogen content in feed is calculated using weighted
average of the hydrogen content of individual XL, RH or VR (measured
by ultimate analysis). The hydrogen contents of individual and co-
pyrolysis products on a dry and ash free feed basis are calculated by
multiplying hydrogen content in product (wt%, on a daf product basis)
and each product yield (wt%, on a daf feed basis), respectively.
The relative contents of hydrogen in each pyrolysis product are
calculated by dividing hydrogen contents of pyrolysis products on a dry
Fuel 303 (2021) 121268
and ash free feed basis to the calculated total hydrogen content
∑
( hydrogen).
3. Results and discussion
3.1. Product distribution during co-pyrolysis of XL/RH and XL/VR
mixtures
The product distributions (on the basis of dry and ash free feed) from
individual (XL, RH and VR) and co-pyrolysis of XL/RH and XL/VR
mixtures are shown in Fig. 2. Meanwhile, the theoretical product yields
(equal to the weighted average of product yields from individual py­
rolysis) were also provided. As shown in Fig. 2(a), XL lignite pyrolysis
produces mainly char (67.68%) with moderate yield of gas (17.11%)
and low yields of water (9.40%) and tar (5.81%). It can be noted that tar
yield of XL lignite is extremely low. According to the classification of
Mineral Resources Industry Requirements Manual (Revised in 2014), tar
yield on dry basis < 7%, 7–12% and > 12% belong to oil-bearing coal,
oil abundant coal and high oil coal, respectively [35]. Therefore, XL
lignite investigated in this study belongs to oil-bearing coal. During RH
pyrolysis, char, gas, tar and water are uniformly distributed, and their
yields are 27.86%, 22.28%, 21.59% and 28.27%, respectively. It is
worth noting that tar and water yields from RH are about four and three
times of those from XL, while char yield of RH is much lower than that of
XL. This is likely due to the fact that the contents of volatiles and hy­
droxyl groups of RH are obviously higher than those of XL.
For co-pyrolysis of XL/RH mixtures, with RH ratio increase from 5%
to 30%, tar, water and gas yields increase from 5.84%, 11.07% and
17.25% to 8.55%, 16.75% and 19.23%, while char yield decrease from
65.85% to 55.47%. Furthermore, it can be noted that the experimental
tar yields (5.84–8.55%) are obviously lower than that of expected
(6.59–10.55%), and the experimental gas (17.25–19.23%) and water
(11.07–16.75%) yields are higher than those of theoretical values
(17.37–18.66% and 10.34–15.06%). Therefore, it can be concluded that
the addition of RH (abundant in hydroxy hydrogen) is not favorable for
tar production during XL pyrolysis.
As shown in Fig. 2(b), different from XL and RH, VR pyrolysis pro­
duces mainly tar (68.74%) with moderate yields of char (17.18%) and
gas (11.70%) and extremely low yield of water (2.38%). For co-pyrolysis
of XL/VR blends, with the increase of VR ratio from 4% to 18%, tar yield
greatly increase from 8.59% to 16.38%, while char, gas and water yields
slightly decrease from 65.80%, 16.88% and 8.59% to 60.60%, 15.26%
and 7.76%. Different from the co-pyrolysis behaviors of XL/RH mix­
tures, the experimental char yields (60.60%–65.80%) from co-pyrolysis
of XL/VR mixtures are slightly higher than theoretical values
(58.78–65.54%), while the experimental gas yields (15.26–16.88%) are
slightly lower than expected (16.16–17.02%). However, the experi­
(1) mental tar (8.59–16.38%) and water (7.76–8.59%) yields are almost
equal to the theoretical values (8.47–16.90% and 8.16–9.10%). This
implies that there is no synergetic effects on tar and water production
during co-pyrolysis of XL/VR blends.
3.2. Hydrogen distributions in products from individual and co-pyrolysis
processes
3.2.1. Hydrogen distributions in tar
The percentage of hydrogen in tars (hydrogen content of tar multi­
plied by tar yield), on the basis of dry and ash free feed, are provided in
Fig. 3. It can be seen that the percentage of hydrogen migrated into tar
during XL pyrolysis is 0.50%, while the hydrogen migrated into tars
from RH and VR are up to 1.73% and 7.11%, respectively. This indicates
that more hydrogen transferred into tars during individual pyrolysis of
RH and VR than that of XL, and this is likely related to hydrogen content
and occurrence in feed [11–12]. With increasing RH or VR ratio, the
percentage of hydrogen transferred into tars increased gradually from
0.53% and 0.88% to 0.72% at RH ratio of 30% and 1.64% at VR ratio of
3
S. Huang et al.
Fig. 2. Products distribution during co-pyrolysis of XL/RH (a) and XL/VR (b) mixtures (E-experimental value; T-theoretical value).
Fig. 3. Experimental and theoretical values of hydrogen in tars from XL/RH (a) and XL/VR (b) co-pyrolysis.
18% during XL/RH and XL/VR co-pyrolysis.
As shown in Fig. 3(a), the experimental values of hydrogen migrated
into tars (0.53–0.72%) are all lower than expected values (0.56–0.87%)
during co-pyrolysis of XL/RH mixtures. This is likely due to the catalytic
effect of alkali and alkaline earth metals (AAEMs) in RH [23,28,36].
Compared with XL, RH is abundant in AAEMs, and AAEMs can not only
intensify the cracking of tar from RH but also tar from XL (part of AAEMs
in RH are volatilized into gas phase at the pyrolysis temperature of 550
, especially the element K), resulting in the migration of hydrogen
from tar to gas. This is in accord with the hydrogen distributions in
gaseous products during XL/RH co-pyrolysis (as shown in Fig. 8).
Conversely, the experimental values of hydrogen migrated into tars
(0.88–1.64%) are all higher than theoretical values (0.73–1.50%) during
XL/VR co-pyrolysis. Compared with RH, VR is abundant in aliphatics
[6,24,37–38]. Therefore, VR can provide more hydrogen-rich light
radicals (such as hydrogen, methyl and ethyl radicals etc.), which would
combine with free radical fragments generated from XL to form medium-
molecular weight compounds (i.e. tar) otherwise these free radical
fragments from XL would polymerize to form char if XL was pyrolyzed
alone.
4
Fuel 303 (2021) 121268
In order to clarify hydrogen types in tars from individual and co-
pyrolysis processes, tars were detected by 1H NMR and the relative
contents of each type of hydrogen in tars (on the basis of total hydrogen
in tar) are plotted in Fig. 4. In tar from XL, Hβ (40.06%) are dominated,
the contents of Hα (25.89%), HA (17.33%) and Hγ (14.17%) are mod­
erate, and the content of HO (2.55%) is extremely low. However, in tar
from RH, Hα (38.31%) and Hβ (35.85%) are equally dominated, and the
contents of HA, Hγ and HO are 13.41%, 9.65% and 2.78%, respectively.
In tar from VR, Hβ (56.82%) are dominated, the contents of Hγ (24.67%)
and Hα (11.52%) are moderate, and the content of HA (5.10%) and HO
(1.89%) are relatively low. It can be noted that the contents of Hβ and Hγ
of tar from VR are much higher than those in tars from XL and RH, while
the contents of Hα and HA of tar from VR are much lower than those in
tars from XL and RH, indicating that aromatics content in tar from VR is
relatively low while the content of aliphatics is relatively high, which is
in accord with the results shown in Fig. 6 (b).
In tars from XL/RH co-pyrolysis, the relative contents of Hβ, HA and
HO decrease and content of Hα obviously increase with increasing RH
ratio. Moreover, the experimental contents of Hα and HA are higher and
that of Hβ and HO are lower than expected values in tars from co-
S. Huang et al.
Fig. 4. Hydrogen types in tars from XL/RH (a) and XL/VR (b) co-pyrolysis.
pyrolysis of XL/ RH. This implies that the addition of RH shortens alkyl
side chain of tar molecules, and this is probably due to the migration of
methoxyl free radicals from RH into tar during co-pyrolysis of XL/RH.
With the increase of VR ratio from 4% to 18%, the relative contents
of Hα and HA gradually decrease from 19.53% and 11.80% to 15.57%
and 8.61%. On the contrary, the relative contents of Hβ and Hγ increase
from 47.41% and 19.17% to 52.01% and 21.88% with increasing VR
ratio. Ho contents varied slightly in the range of 1.82–2.10% at different
VR ratios. Besides, it can be noted that the experimental values of HA and
Hα are lower than expected, while the experimental values of Hβ and Hγ
are higher than theoretical values. This indicates that the tars from XL/
VR co-pyrolysis contain more long chain aliphatics and/or aromatics
with long alkyl side chain than expected, which is in line with the results
that the experimental aliphatics content (67.88%) is much higher than
theoretical value (42.20%, as shown in Fig. 6).
The tars from individual (XL, RH and VR) and co-pyrolysis of XL/RH
and XL/VR mixtures were dissolved in n-hexane to determine the con­
tent of n-hexane solubles (nHS) in tar. As plotted in Fig. 5, the contents
of nHS in tars from XL and RH are 86.31% and 55.43%, while that from
VR is up to 99.53%. It can be observed that the experimental values of
nHS content in tars from XL90RH10 and XL70RH30 are almost equal to the
Fig. 5. Content of nHS in tars from individual and co-pyrolysis of XL/RH (a) and XL/VR (b) co-pyrolysis.
5
Fuel 303 (2021) 121268
theoretical values. However, the experimental values of nHS content of
tars from XL93VR7 and XL82VR18 are higher than calculated values,
suggesting the improvement of tars quality during XL/VR co-pyrolysis
process. Zhu et al [1] found that tar quality exhibited a better perfor­
mance according to the significant positive synergetic effect from light
tar (boiling point < 360 ◦ C) content during co-pyrolysis of Naomaohu
lignite and cedar. Therefore, the tar quality during co-pyrolysis not only
depend on the properties of raw materials, but also on the reactor
structure, experimental conditions, etc.
The n-hexane solubles were detected by GC/MS to determine their
composition. As plotted in Fig. 6, the components in n-hexane solubles
can be classified into aliphatics, monoaromatics, polyaromatics, phe­
nols, other oxygen-containing compounds (OOCs, including alcohols,
ketones, aldehydes, esters, ethers and furans) and others (nitrogen- and
sulfur-containing compounds, et al.). The compounds in each group are
listed in Tables S1–S5.
As shown in Fig. 6(a), the compositions of n-hexane solubles in tars
from XL and RH individual pyrolysis varied significantly. The main
components in XL-nHS are aliphatics (33.05%), polyaromatics (29.53%)
and phenols (25.17%). Differently, phenols (62.30%) are the dominated
components in RH-nHS, followed by OOCs (22.59%), and the contents of
S. Huang et al.
Fig. 6. Compositions of nHS in tars from individual and co-pyrolysis of XL/RH (a) and XL/VR (b) mixtures.
monoaromatics and polyaromatics are negligible. The significant dif­
ference is related to the chemical compositions of XL and RH. In
XL70RH30-nHS-E, the main components are phenols (52.95%) and ali­
phatics (22.51%). Besides, it can be noted that the experimental poly­
aromatics content (XL70RH30-nHS-E) is lower than theoretical value
(XL70RH30-nHS-T), while the experimental phenols and aliphatics con­
tents are higher than expected. This suggests that the abundant pheno­
lic hydroxyl groups in RH would combine with the free radicals released
from XL to produce more phenols otherwise these free radical fragments
from XL would polymerize to form polyaromatics or char if XL was
pyrolyzed alone.
As shown in Fig. 6(b), in VR-nHS, aliphatics are the most predomi­
nant component, accounting for 86.91% of VR-nHS. The contents of
other components are all extremely low. This indicates that the main
components in VR-nHS are aliphatics [6,24]. This is in line with the
results shown in Fig. 4(b). In XL82VR18-nHS-E, aliphatics are also
dominated (67.88%) components. Besides, phenols and monoaromatics
Fig. 7. Gaseous product yields during individual and co-pyrolysis of XL/RH (a) and XL/VR (b) mixtures.
6
Fuel 303 (2021) 121268
account for 12.91% and 8.43%, respectively. Moreover, it can be
observed that the experimental aliphatics content (67.88%) is much
higher than theoretical value (42.20%), this is in line with the 1H NMR
results that the contents of Hβ and Hγ (especially Hβ) in tar from
XL82VR18 are much higher than expected value. Moreover, the experi­
mental contents of polyaromatics and phenols are lower than expected,
especially polyaromatics.
3.2.2. Hydrogen distributions in gaseous product
The yields of each gaseous components (on the basis of dry and ash
free feed) during individual (XL, RH and VR) and co-pyrolysis (XL/RH
and XL/VR blends) are plotted in Fig. 7. It can be observed that CO2 and
CO are the dominated components in gases from XL and RH individual
pyrolysis, and the yields of hydrogen-containing gas (H2, CH4 and C2-C4
hydrocarbons) are relatively low. CO2 yields from XL and RH are
13.03% and 15.40%, respectively. CO yield from RH is much higher
than that from XL, this is largely ascribe to the abundant C-O and C-O-C
S. Huang et al.
bonds in RH [39–40]. However, the dominated components in gas from
VR are CH4 and C2-C4 hydrocarbons, and their yields are 3.58% and
7.30%, which are much higher than those in gases from XL and RH. CO
and CO2 yields in gas from VR are extremely low, and they only account
for 0.29% and 0.46% of feed. This is likely due to the fact that oxygen-
containing components in VR is scarce, which is in accord with the ul­
timate analysis results of VR (as shown in Table 1).
As shown in Fig. 7(a), the experimental yields of CO, H2 and CH4 are
comparable with the theoretical values during co-pyrolysis of XL/RH
mixture. When RH ratio is lower than 20%, the experimental CO2 yield
is comparable with calculated value, while the experimental CO2 yield is
higher than expected when RH ratio is higher than 20%. Although the
yield of C2-C4 hydrocarbons is tiny, the experimental yields are obvi­
ously higher than expected values. As Li et al reported [41], the AAEMs
in raw materials (such as coal and biomass) can promote the thermal
cracking of tar to produce C2–C4 hydrocarbons. Therefore, the AAEMs in
RH intensify not only the cracking of tar from RH but also that from XL
to produce C2-C4 hydrocarbons.
As plotted in Fig. 7(b), with increasing VR ratio, CO2 yield decrease
monotonously from 12.04% to 9.97%, while CH4 and C2-C4 yields in­
crease from 1.24% and 1.11% to 1.48% and 1.61%, respectively. Be­
sides, the experimental CO2 and CH4 yields are slightly lower than
theoretical values, while the yields of C2-C4 hydrocarbons (1.11–1.61%)
are obviously higher than expected (0.44–1.40%).
Fig. 8 displays the percentage of hydrogen in gases from individual
and co-pyrolysis processes (on a dry and ash free basis of feed). It can be
noted that the percentage of hydrogen in gases from XL and RH are
0.44% and 0.17%. However, the percentage of hydrogen in gas from VR
is 2.13%, which are much higher than that from XL and RH. This is in
line with the relatively high yields of CH4 and C2-C4 hydrocarbons from
VR. With the increase of RH or VR ratio, the percentage of hydrogen in
gases from XL/RH co-pyrolysis varied slightly (0.46–0.50%), while the
percentage of hydrogen in gases from co-pyrolysis of XL/VR increased
gradually from 0.56% to 0.71%.
Moreover, the experimental values (0.46–0.50%) of hydrogen per­
centage in gases are higher than theoretical values (0.36–0.43%) during
co-pyrolysis of XL/RH mixtures. For co-pyrolysis of XL/RH blends, the
abundant AAEMs in RH can not only intensify the cracking of tar from
RH but also tar from XL, leading to the transfer of hydrogen from tar to
gas, and this is in agreement with the product distributions of XL/RH co-
pyrolysis (as shown in Fig. 2). Although the experimental gas yields are
lower than theoretical values, the experimental values (0.56–0.71%) of
hydrogen percentage in gases are almost equal to the theoretical values
(0.51–0.74%) during co-pyrolysis of XL/VR mixtures.
Fig. 8. Experimental and theoretical values of hydrogen in gas from co-pyrolysis of XL/RH (a) and XL/VR (b) mixtures.
7
Fuel 303 (2021) 121268
3.2.3. Hydrogen distributions in char
The percentage of hydrogen in chars (hydrogen content of char
multiplied by char yield) from individual (XL, RH and VR) and co-
pyrolysis (XL/RH and XL/VR mixtures) processes, on a dry and ash
free basis of feed, are provided in Fig. 9. As shown in Fig. 9, the per­
centage of hydrogen in char from XL is 2.12%, which are 0.85% and
0.58% from chars of RH and VR individual pyrolysis. This is largely due
to the fact that the char yield from XL is much higher than that from RH
and VR (char yields from XL, RH and VR are 67.68%, 27.86% and
17.18%, respectively). With increasing RH or VR ratio, the percentage of
hydrogen transferred into chars decreased gradually from 2.05% and
2.07% to 1.67% at RH ratio of 30% and 1.98% at VR ratio of 18% during
co-pyrolysis of XL/RH and XL/VR mixtures.
Besides, it can be noted that the experimental values of hydrogen
migrated into chars are slightly lower than expected during co-pyrolysis
of XL/RH blends. Compared with XL pyrolysis alone, some large free
radicals from XL would combine with medium or large oxygen-
containing free radicals from RH during co-pyrolysis, and oxygen
would induce the condensation of char and hydrogen is removed in the
form of water [11]. On the contrary, the experimental values of
hydrogen migrated into chars are slightly higher than theoretical values
during XL/VR co-pyrolysis processes. This is probably due to that some
large free radicals from XL would combine with medium or large
hydrogen-rich alkyl free radicals from VR to produce char, and more
hydrogen would introduce into char during XL/VR co-pyrolysis.
3.2.4. Hydrogen distributions in water
The percentage of hydrogen in water from individual (XL, RH and
VR) and co-pyrolysis (XL/RH and XL/VR mixtures) processes, on a dry
and ash free basis of feed, are plotted in Fig. 10. It can be found that the
percentage of hydrogen in water from XL is 1.04%, while that from RH is
3.14%. This is largely due to the fact that RH is abundant in hydroxyl
groups, especially phenolic hydroxyl groups [39–40]. Differently, the
percentage of hydrogen in water from VR is tiny, 0.26%. With the in­
crease of RH ratio from 5% to 30%, the percentage of hydrogen migrated
into water during co-pyrolysis of XL/RH blends increase from 1.23% to
1.86%. However, the percentage of hydrogen in water during XL/VR co-
pyrolysis decrease from 0.95% to 0.86% with increasing VR ratio.
As shown in Fig. 10(a), the experimental values (1.23–1.86%) of
hydrogen migrated into water are higher than expected (1.15–1.67%)
during co-pyrolysis of XL/RH blends. RH is abundant in hydroxyl groups
(phenolic hydroxyl groups and alcoholic hydroxyl groups), and hy­
droxyl groups would combine with hydrogen easily not only from RH
but also from XL to produce water during co-pyrolysis of XL/RH
S. Huang et al. Fuel 303 (2021) 121268

Fig. 9. Experimental and theoretical values of hydrogen in char from co-pyrolysis of XL/RH (a) and XL/VR (b) mixtures.

Fig. 10. Experimental and theoretical values of hydrogen in water from co-pyrolysis of XL/RH (a) and XL/VR (b) mixtures.

mixtures. However, the experimental values (0.86–0.95%) of hydrogen in all products are almost equal to hydrogen in feed, and the relative
migrated into water are almost equal to the theoretical values error is below 5.50% for XL/RH and 3.80% for XL/VR mixtures co-
(0.91–1.01%) during XL/VR co-pyrolysis. pyrolysis. The above results indicates a good accuracy of the co-
pyrolysis experiments.
3.3. Hydrogen migration and redistribution characteristics during co- Hydrogen distributions in pyrolysis products from XL, RH and VR
pyrolysis processes individual pyrolysis and XL/RH and XL/VR co-pyrolysis (on the basis of
total hydrogen in feed) are plotted in Fig. 11. For XL, 51.47% and
Tables 3 and 4 shows hydrogen distributions in pyrolysis products 25.50% of hydrogen transfers into char and water, and only 12.25% and
during co-pyrolysis of XL/RH and XL/VR mixtures. As Tables 3 and 4 10.78% of hydrogen transfers into tar and gas. This indicates that about
shows, the summation of hydrogen (on the basis of dry and ash free feed) 77% of hydrogen transfers into char and water, and the hydrogen
transfers into tar is limited. This is largely ascribe to the chemical
Table 3
structures and properties of XL lignite. Differently, for RH, 53.31% of
Hydrogen redistribution during co-pyrolysis of XL/RH mixtures. hydrogen transfers into water and the hydrogen transfers into char and
gas are 14.43% and 2.89%, respectively. Meanwhile, hydrogen transfers
Samples Hydrogen in Hydrogen in product (wt%, on a daf feed Relative
feed (wt%, basis) error b
into tar is 29.37%, which is much higher than that of XL lignite.
on a daf feed (%) For XL/RH co-pyrolysis, the hydrogen transfers into tar and water
Char Tar Water Gas Σa
basis) increase from 12.28% and 28.62% to 15.30% and 39.29% with
XL 4.16 2.12 0.50 1.04 0.44 4.10 1.51 increasing RH ratio. Meanwhile, the hydrogen transfers into char
XL95RH5 4.26 2.05 0.53 1.23 0.49 4.30 0.88 decrease from 47.70% to 35.27% with the increase of RH ratio, and the
XL90RH10 4.38 1.90 0.55 1.40 0.46 4.31 1.54 hydrogen transfers into gas varied slightly in the range of 10.14%–
XL85RH15 4.51 1.86 0.57 1.49 0.48 4.40 2.49 11.40%. Besides, the experimental hydrogen migrated into water
XL80RH20 4.65 1.79 0.57 1.55 0.50 4.41 5.18
XL70RH30 5.01 1.67 0.72 1.86 0.48 4.73 5.50
(28.62–39.29%) and gas (10.14–11.40%) are higher than expected
RH 6.14 0.85 1.73 3.14 0.17 5.89 4.12 (27.38–35.99% and 7.76–10.24%), and the hydrogen migrated into tar

8
S. Huang et al. Fuel 303 (2021) 121268

Table 4
Hydrogen redistribution during co-pyrolysis of XL/VR mixtures.
b
Samples Hydrogen in feed (wt%, on a daf feed basis) Hydrogen in product (wt%, on a daf feed basis) Relative error (%)
a
Char Tar Water Gas ΣH

XL 4.16 2.10 0.50 1.04 0.44 4.08 1.97

XL96VR4 4.39 2.07 0.88 0.95 0.56 4.46 1.50
XL93VR7 4.54 2.10 0.99 0.97 0.59 4.65 2.32
XL90VR10 4.71 2.09 1.12 0.93 0.59 4.73 0.38
XL87VR13 4.90 1.97 1.37 0.88 0.66 4.88 0.35
XL82VR18 5.14 1.98 1.64 0.86 0.71 5.19 1.03
VR 9.71 0.58 7.11 0.26 2.13 10.08 3.80
a
The summation of hydrogen in products.
b ∑
Refers to the relative error of hydrogen to Hydrogen in feed.

Fig. 11. Hydrogen redistribution in products during co-pyrolysis of XL/RH (a) and XL/VR (b) mixtures.

Fig. 12. Simplified reaction mechanism and hydrogen migration pathway during XL/RH co-pyrolysis (blue ball represents carbon atom, white ball represents
hydrogen atom, red ball represents oxygen atom). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of
this article.)

9
S. Huang et al.
(12.28–15.30%) and char (35.27–47.70%) are lower than theoretical
values (13.33–18.75% and 37.50–49.05%). This indicates that the
addition of RH is conducive to the migration of hydrogen from char and
tar into gas and water during XL pyrolysis. The simplified reaction
mechanism and hydrogen migration pathway during XL/RH co-
pyrolysis is shown in Fig. 12.
For VR, 70.54% of hydrogen transfers into tar, and the hydrogen
transfers into gas, char and water are 21.14%, 5.74% and 2.58%,
respectively. The hydrogen migrated into tar increase markedly from
19.73% to 31.59% with the increase of VR ratio from 4% to 18%, while
the hydrogen migrated into char and water gradually decrease from
46.42% and 21.29% to 38.16% and 16.57%. The hydrogen migrated
into gas varied slightly in the range of 12.55–13.68%. Moreover, the
experimental hydrogen migrated into char and gas are almost equal to
the theoretical values. However, the hydrogen migrated into tar
(19.73–31.59%) is slightly higher than expected (17.04–30.03%), and
the hydrogen migrated into water (16.57–21.29%) is less than theoret­
ical values (18.16–23.55%). This illustrates that the addition of VR is
conducive to the migration of hydrogen from water into tar during XL
pyrolysis. The experimental tar yields are almost equal to the theoretical
values (as shown in Fig. 2), this suggests the improvement of tar quality
during XL/VR co-pyrolysis. The simplified reaction mechanism and
hydrogen migration pathway during XL/VR co-pyrolysis is shown in
Fig. 13.
In conclusion, co-pyrolysis of low-rank coals with hydrogen-rich
carbonaceous matters cannot always enhance tar yield and/or
improve tar quality, which largely depend on hydrogen content and
occurrence of hydrogen-rich carbonaceous matters.
4. Conclusions
(1) The co-pyrolysis of XL/RH produces more gas and water and less
tar than expected. Compared with XL, much more hydrogen
transfers into tar and water (29.37% and 53.31% for RH, and
12.25% and 25.50% for XL) and less hydrogen transfers into char
and gas during RH pyrolysis. The experimental hydrogen
Fig. 13. Simplified reaction mechanism and hydrogen migration pathway during XL/VR co-pyrolysis (blue ball represents carbon atom, white ball represents
hydrogen atom, red ball represents oxygen atom). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of
this article.)
10
Fuel 303 (2021) 121268
migrated into water (28.62–39.29%) and gas (10.14–11.40%) are
higher than expected (27.38–35.99% and 7.76–10.24%) during
XL/RH co-pyrolysis, and the hydrogen migrated into tar
(12.28–15.30%) and char (35.27–47.70%) are lower than theo­
retical values (13.33–18.75% and 37.50–49.05%). This indicates
that the addition of RH is favorable for the migration of hydrogen
from tar and char to gas and water during XL pyrolysis, probably
ascribe to AAEMs in RH intensify not only the cracking of tar from
RH but also that from XL. Consequently, more C1-C4 hydrocar­
bons was produced.
(2) The co-pyrolysis of XL/VR yields more char and less gas than
expected. During VR pyrolysis, 70.54% of hydrogen transfers into
tar, which are much higher than that of XL (12.25%) and RH
(29.37%) individual pyrolysis. The hydrogen migrated into tar
increase markedly from 19.73% to 31.59% with the increase of
VR ratio from 4% to 18%, while hydrogen migrated into char and
water gradually decrease from 46.42% and 21.29% to 38.16%
and 16.57%. The experimental hydrogen migrated into char and
gas are almost equal to the theoretical values, while the hydrogen
migrated into tar (19.73–31.59%) is higher than expected
(17.04–30.03%), and hydrogen migrated into water
(16.57–21.29%) is less than theoretical values (18.16–23.55%).
This indicates that the addition of VR is conducive to the
migration of hydrogen from water to tar during XL pyrolysis.
Consequently, the contents of nHS in tar from XL/VR co-pyrolysis
are higher than expected, indicates the improvement of tar
quality.
(3) The co-pyrolysis behaviors of XL/RH and XL/VR are completely
different, and the addition of hydrogen-rich carbonaceous mat­
ters during lignite pyrolysis cannot always enhance tar yield and/
or improve tar quality, which largely depend on hydrogen con­
tent and occurrence of hydrogen-rich carbonaceous matters.
CRediT authorship contribution statement
Sheng Huang: Writing - original draft, Conceptualization,
S. Huang et al.
Methodology, Funding acquisition. Linhui Pan: Investigation, Writing -
review & editing. Yanling Li: Investigation, Methodology, Formal
analysis, Visualization. Shiyong Wu: Supervision, Resources. Youqing
Wu: Supervision, Resources. Jinsheng Gao: Conceptualization, Project
administration.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
We gratefully acknowledge financial support of this work by the
National Natural Science Foundation of China (Grant No. 21506060),
the National Key Basic Research and Development Program of China
(Grant No. 2018YFB0604602), and the Fundamental Research Funds for
the Central Universities (Grant No. 222201718003).
Appendix A. Supplementary data
The compositions of n-HEX solubles in tars from individual and co-
pyrolysis are minutely listed in supplementary data (Tables S1–S5).
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.fuel.2021.121268.
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