i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 2 0 3 e2 1 6

Available online at www.sciencedirect.com

ScienceDirect

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

Role of novel additives (reservoir rock and activated

carbon) in bio-oil synthesis from LRC microwave
pyrolysis

Bambang Sardi a,*, Irianto Uno b, Fitrawati A. Marhum b,

Amar Ali Akbar c, Thahirah Arief d, Muhammad Arif e, Ali Altway f,
Mahfud Mahfud f
a
Department of Environmental Engineering, Tadulako University, Palu 94118, Indonesia
b
Department of Geological Engineering Tadulako University, Palu 94118, Indonesia
c
Department of Architecture Engineering Tadulako University, Palu 94118, Indonesia
d
Department of Chemical Engineering, National Cheng Kung University, Tainan 701, Taiwan
e
DG Mineral and Coal, Ministry of Energy and Mineral Resources - Republic of Indonesia, Jakarta 10110, Indonesia
f
Department of Chemical Engineering, Sepuluh Nopember Institute of Technology, Surabaya 60111, Indonesia

highlights graphical abstract

Microwave pyrolysis on LRC was

carried out with catalyst Fe/RC and
Fe/AC.

Effect of coal/catalyst ratio, time,
and power were investigated.

Highest bio-oil was obtained at
ratio of 1:100, 60 min, and 600 W.

Bio-oil was found to contain
carboxyl and aliphatic units.

article info abstract

Article history: The ferric sulfate was added to reservoir rock catalyst (RC) and activated carbon catalyst (AC)
Received 27 May 2023 to obtain Fe/RC and Fe/AC. Microwave pyrolysis (MP) was carried out to process low-rank coal
Received in revised form (LRC) using catalysts and receptors (Fe/RC and Fe/AC). A comparison was made between the
5 July 2023 product distribution and the process factors (temperature, time, and power). The results
Accepted 20 July 2023 show that the product is affected by MP with Fe/CR and Fe/AC through temperature accel-
Available online 07 August 2023 eration and final temperature. When compared to conventional pyrolysis (CP) with the same
conditions (620  C and 60 min), the bio-oil generated from MP þ 1.0% RC þ 24.6% Fe was 42.0%,

* Corresponding author.
E-mail address: bambang.teknikkimia@gmail.com (B. Sardi).
https://doi.org/10.1016/j.ijhydene.2023.07.217
0360-3199/© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
204 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 2 0 3 e2 1 6

Keywords: 4.4% greater than CP. Meanwhile, using MP þ 1.0% AC þ 24.6% Fe, 47.1% bio-oil was produced,

Activated carbon with an increase of 4.0%. Meanwhile, using 1.0% RC þ 24.6% Fe, the highest bio-oil production

Fe receptor was seen at 60 min, 620  C, and 600 W, generating 42.0% bio-oil. Study results can form the

LRC basis for obtaining fuel, chemicals, and environmental improvements.

Microwave pyrolysis © 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Reservoir rock

were what caused the shift in the product's distribution. At MP

1. Introduction
Fuel consumption at the end of 2021 will continue to be driven
by fossil fuels. The total proven coal reserves at the end of 2020
include 753,639 million tons of anthracite and bituminous
coals and 320,469 million tons of low-rank coal (LRC) [1]. LRC is
an ineffective and economically inefficient direct fuel that
pollutes the environment. Therefore, pyrolysis is a clean
alternative technology needed to convert LRC into fuel [2].
The fundamental difficulty with the pyrolysis is the use of
low-conventional heating, which results in a liquid yield that
is dominated by tar, gain impossible to use the ultimate
product, bio-oil, directly as fuel [3e5]. There is an immediate
need for another method that is more effective and efficient
(i.e., produces less tar). This technology is microwave pyroly-
sis (MP) with a catalyst and the receptor [5e9].
When using MP technology, the catalyst and receptor are
the primary alternatives. Reservoir rock catalyst (RC) and
activated carbon catalyst (AC), as well as metal-based re-
ceptors, are desirable because to their higher reactivity,
abundance of reserves, and potential for large financial
returns [10e12]. The mineral composition of the reservoir rock
is CaCO3, SiO2, and Mg3(SiO2) (OH)4. Alternative catalysts op-
tions include carbon-based catalysts [i.e., black carbon, acti-
vated carbon, carbon nanotubes, and coconut activated
carbon (CAC)] [11,13e17] which are based on reservoir rock
compositions such as Ca, K, Fe, CuO, CaCl2, K2CO3, Al2O3,
FeSO4, and Fe3O4 [13,18e20]. Fe3O4 and CuO may act as re-
ceptors in microwave pyrolysis (MP), significantly affecting
the performance of liquid products [21,22].
The quality and behavior of pyrolysis products can differ
when catalysts from reservoir rocks and metal receptors are
used simultaneously. Larger polycyclic aromatic compounds
may be converted into lighter tars by the action of metal cat-
alysts (K, Ca, and Fe) [8]. Metal catalysts such as K2CO3, CaCl2,
and FeSO4 can effectively increase synthesis gases (H2 and CO)
distribution and lower asphaltene content in tar [18,23].
Meanwhile, the open literature has reported on the use of
activated carbon and Fe2O3 catalysts in MP in lignite-type
LRCs. Wu et al. [24] have performed research on LRC with
blucoke (AC) and Fe2O3 catalysts for converting lignite into
bio-oil, syngas, and char. They explained that the addition of
the AC/Fe2O3 catalyst was aimed at maximizing bio-oil and
syngas products. They found that the use of AC/Fe2O3 for
producing liquid products and syngas is 3e4 times higher
because of the MP effect.
Meanwhile, Zhou et al. [6] compare the MP þ non-catalyst
to the MP þ FeS2 catalyst. They discovered an increase in the
final temperature and the pace of the temperature increase
þ 12.0% FeS2, liquid fuels and syngas products increased by
27.2% and 8.7%, respectively, over MP þ non-catalyst treat-
ment. This indicates that the FeS2 catalyst increases the pro-
portion of light liquid fuel while reducing tar. Mushtaq et al.
[25] enhanced syngas and liquid fuel efficiency with a recep-
tor/LRC ratio and microwave power using the MP þ Fe3O4 re-
ceptor. Meanwhile, using LRC, the highest tar efficiency was
achieved using MP with a 75.0% CAC catalyst load of 18.6% and
H2 gas producing 40.2e65.2%. Coal tar consists of aromatic
hydrocarbons (naphthalene, benzene, and xylene) and satu-
rated aliphatic hydrocarbons [26].
Most of the early research focused on how LRC could be
used as a raw material for MP with a catalyst for one of the
parts of reservoir rock, AC, and metal receptors [27e29]. The
presence of reservoir rocks catalyst, which include CaCO3, SiO2,
and Mg3(SiO2) (OH)4 is a combination of the compositions of AC
and zeolite. So, the presence of a reservoir rock catalyst can not
only increase in the yield of liquid fuel but also the quality of
the product. So far, the focus of related research has been on
minimizing the presence of tar in the pyrolysis liquid product
and maximizing the yield of liquid fuel and syngas products
[30,31]. In general, it can be concluded that research so far has
only focused on improving quality by adding catalysts and re-
ceptors. The presence of Fe receptors can increase the
decomposition of organic sulfur [31e33]. The focus of this
study is also on how the final temperatures of catalyst-
containing materials (CP þ Fe/catalyst and MP þ Fe/catalyst)
and catalyst-free materials (CP þ non-catalyst þ non-receptor)
effect product composition. The maximal bio-oil production
conditions including temperature, time, and power are also
investigated in this work. Utilizing GC-MS, FTIR, density, and
viscosity measurements of bio-oil products were reported.
Syngas or synthesis gas, is approximate to hydrogen, methane,
ethane, propane, and n-butane, and bio-oil is anticipated being
comparable with diesel oils and gasoline. Therefore, using LRC
as a raw material, the findings of this study can form as the
basis for clean coal and advanced fuel production technologies.
2. Material and method
2.1. The characterization of sample, catalysts, and
receptors
LRC, Fe receptors, RC, and AC catalyst preparations were
completed. The sub-bituminous LRC was from the Bobong
Formation in the Taliabu Utara, Indonesia. The LRC had high
levels of sulfur and ash, and the proximate and final analyses
were provided in Table 1. The LRC was dried to a moisture
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 2 0 3 e2 1 6 205

Table 1 e Catalyst and characteristics.

Sample Proximate analysis Ultimate analysis
FC V M A H N C Odiff. St
Sub-bituminous coal 38.04 43.56 6.54 11.86 6.87 0.76 74.75 12.21 5.41
AC catalyst 66.62 22.60 9.76 1.02 3.38 0.47 65.42 30.73 0.00
SiO2 CaCO3 Mg3(Si2O5) (OH)4
RC catalyst 65.5 28.0 6.5

Fig. 1 e Production process of Fe2(SO4)3 receptors from waste of Fe and H2(SO4)3.

content of 0.05% after being crushed and filtered to a particle
size of 4 meshes. Desulfurization and deashing were per-
formed using Fe, which is generated by a chemical reaction
between Fe and H2SO4, to lower the high sulfur and ash con-
tent of the LRC, according to the study of Yue et al. [34]. The
production process of Fe2(SO4)3 from waste of Fe and H2(SO4)3
is shown in Fig. 1.
Meanwhile, RC and AC were used to support the pyrolysis
performance, where the calcination process was used to
produce AC from CAC and reservoir rock from reservoir
minerals. When baked in an oven at 120  C for 720 min,
reservoir rocks from the Batui-Banggai District and CAC from
the commercial market were placed in a desiccator. Then,
catalyst was calcined for 180 min with a rate of 0.02 L/min at
500  C. Finally, the reduction was completed using H2 gas for
120 min, a temperature of 550  C and a speed of 0.02 L/min.
When everything has been completed, the catalyst is cooled in
an equipment using N2 gas flowing at a rate of 0.02 L/min until
it reaches 50  C. Also, included was a presentation of the
chemical analysis of RC and AC in Table 1.
Table 1, show an analysis of the chemical characteristics of
RC and the AC. The ASTM technique was utilized to charac-
terize the LRC and AC (ultimate and proximate analyses).
Proximate analysis includes ASTM D3175-17 (volatile mate-
rial), ASTM D3173-17 A (moisture), ASTM D3174-12 (ash),
ASTM D3172-12 (fixed carbon), and ASTM D5865-13 (calorific
value). While the final analysis includes total carbon,
hydrogen, and nitrogen (ASTM D5373-13), total sulfur (ASTM
D4239-17), and oxygen (ASTM D3176-17), reservoir rocks were
analyzed using XRD.
2.2. Equipment and processes of experimental
LRC (4 mesh size) 150 g mixed with 1.0% catalyst þ 24.6% re-
ceptor. Where RC and AC act as catalysts and Fe acts as a re-
ceptor. The process temperature was operated between 570  C
and 650  C with a 10  C increment. A 2.54 GHz microwaves
reactor that already had an LRC, catalyst, and receptor was
used for the pyrolysis. The vacuum pressure and time for the
microwave pyrolysis were set at 10 mmH2O and 60 min,
respectively. The input power was 600 W (RC) and 450 W (AC).
Syngas, char, and liquid (bio-oil and tar phases) on trays 1, 2, 3,
and tray-end are the final products. A schematic of the
apparatus of the catalyst and the receptor on the MP is
exhibited in Fig. 2.
The input power was set to 0e800 W, while the time vari-
ation was set at 15e135 min. The total weight loss (TWL),
which represented the syngas and yield of liquid, was deter-
mined by the data acquired from the LRC pyrolysis process,
catalyst, and receptor at a vacuum pressure of 10 mmH2O,
which was the highest production condition.
Temperature variations were conducted at 570e650  C,
with a 10  C increment. A mixture of 150 g of LRC with RC þ Fe
and AC þ Fe at a ratio of 1.0% catalyst to 24.6% receptor was
206 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 2 0 3 e2 1 6

Fig. 2 e The schematic illustration of the MP system employed in this investigation [16].

prepared. The mixture of LRC, catalyst, and receptor was then

subjected to pyrolysis. Pyrolysis conditions were set at a vac- mliquid mtray I þ mtray II þ mtray III þ mtray end
Yliquid ¼  100% ¼
uum pressure of 10 mmH2O, a frequency of 2.54 GHz, and an mfeed mcoal
input power of 525 W for 60 min. The liquid (phase of bio-oil  100%
and tar) and solid (syngas and char) products were produced (1)
in trays 1, 2, 3, and at the end of the tray. In Fig. 2 depicts a
device circuit of a catalyst and receptor-assisted MP system. msolid mchar
Ysolid ¼  100% ¼  100% (2)
At a catalytic pyrolysis (non-microwave) and MP-catalyst- mfeed mcoal
receptor (150e800 W), input power was varied, while time
was varied from 15 to 135 min. The coal, catalyst, and receptor Ysyngas ¼ 100%  Yliquid  Ysolid (3)
were then pyrolyzed at a vacuum pressure of 10 mmH2O for
each condition of maximal liquid and syngas such as TWL. Total weight loss ðTWLÞ ¼ Yliquid þ Ysyngas (4)

Using an energy dispersion spectrometer, the micromor-

2.3. Method of analysis and calculation
phology and elemental content of solid products were exam-
ined using the JSM-6360LV SEM-EDS analyzer. The
Eqs. (1)e(4) the pyrolysis products, including the density of the
investigation was performed using the Supra 55 sapphire type
liquid, were calculated, followed by determination of the total
SEM (30 kV, 1.6 nm). In line with Method of analysis and
weight loss (TWL).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 2 0 3 e2 1 6
Fig. 3 e Temperature rise at various Fe/RC and þ Fe/AC combination ratio.
calculation of the LRC characteristics, a direct ASTM analysis
of the solid products was done. Using a powder diffractometer
and X-ray diffraction (XRD), the crystal structures of LRC, Fe/
RC, and Fe/AC in the char were examined. Shimadzu
(Guangzhou) Analyzer and TS Co., Ltd. In China provided the
Type-700 diffractometer that was used. The copper K-rays,
monochromatic graphite at 30 mA (40 kV), and thallium-
activated sodium iodide detector were all included in the
diffractometer. The scanning range was 2q at a speed of
0.02  C/s between 5 and 80 .
FTIR was used to examine the functional groups of organic
tar. An additional 32 cm1 scans was carried out after a 4 cm1
resolution index between 4000 and 500 cm1 was recorded.
Infrared Spectroscopy, FTIR, IR Prestige-21, Shimadzu
(Guangzhou) Analysis, China. The potassium bromide (KBr)
method was used for FTIR analysis. Under the same KBr cut-
off assay circumstances, a non-background effect spectrum
of high quality is generated.
The tar component was examined using GC-MS
(6890e5973) type (GC-MS, Agilent Technology, Santa Clara,
CA, USA). High-purity helium (99.999%) was used as the carrier
syngas, flowing at a rate of 0.00014 L/min. The internal mea-
surements of the RXI-5 ms column of the GC are 30 m  0.25 m x
0.25 m.
3. Results and discussion
3.1. Effect of rise temperature on the characteristics of
the pyrolysis product
The rate of temperature increases and the ultimate tempera-
ture of pyrolysis carried out in the presence of a catalyst and a
receptor are decisive in determining the distribution of the
207
product [6,7]. The rise in temperature will be a significant
contributor to pyrolysis [14]. Fig. 3 displays the temperature
profiles of CP and MP at varying ratios of Fe/RC and Fe/AC. MP
is superior to CP in terms of temperature increase, MP þ Fe/RC
is superior to CP þ Fe/RC, and MP þ Fe/AC is superior to
CP þ Fe/AC. The MP temperature increases to 815  C in 20 min
when MP þ 1.0% RC þ 24.6% Fe is used, while it does so in
18 min when MP þ 1.0% AC þ 24.6% Fe is used. While it takes
33.5 min for the temperature of the CP to rise to 815  C when
the ratio is CP þ 1.0% RC þ 24.6% Fe and 32 min when the ratio
is CP þ 1.0% AC þ 24.6% Fe. CP temperature increased by up to
815  C throughout the course of around 38 min at the ratio of
CP þ non-catalyst þ non-receptor. According to Zhou et al.
[35], the length of time it took for MP and CP to reach their final
temperatures in this investigation. In which it was discovered
that the desired primary liquid yield at MP þ 8.3% MoS2 up to
800  C was achieved in less than 25 min [36,37].
Furthermore, the rate of temperature growth was gradu-
ally slowed down by the combination ratios of MP þ Fe/AC and
MP þ Fe/RC. The total loading of a catalyst and receptors in
MP þ Fe/AC and MP þ Fe/RC causes coal to heat up 18 min
more quickly at 1.0% AC þ 24.6% Fe and 1.0% RC þ 24.6% Fe,
respectively. It takes roughly 16 min for the catalyst and re-
ceptor to fully load in order to reach 700  C. However, to absorb
microwaves, the LRC capacity is less than Fe/RC and Fe/AC.
According to earlier research, it is extremely possible to use
microwave absorbers and activators on MP to use the AC, RC,
and Fe receptors in a fast manner [6,7].
Fig. 4 shows the results of the calculation of the TWL and
LRC yields using Eqs. (1)e(4). In a typical pyrolysis, the non-
catalyst and non-receptor treatment resulted in a 33.9%
liquid yield. The yields of liquid CP following the addition of
1.0% RC þ 24.6% Fe and 1.0% AC þ 24.6% Fe to the coal were
37.5% and 43.1%, respectively. The addition of Fe/RC and Fe/
208 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 2 0 3 e2 1 6

Fig. 4 e Carbon distribution of liquid, syngas, and char (CP: conventional pyrolysis; MP: microwave pyrolysis).

AC resulted in lower char yields. It was discovered that by
adding 1.0% RC þ 24.6% Fe and 1.0% AC þ 24.6% Fe to coal, the
liquid yield in MP rose to 42.0% and 47.1%, respectively. On
both CP and MP, the trend of changes in liquid yield is the
same. The largest difference is 4.0% at the top MP against CP
for liquid yield at 1.0% AC þ 24.6% Fe. At the same condition,
CP has a larger yield of char than MP [14]. MP promoted LRC
cyclization and aromatization [38e41]. The liquid carbon dis-
tribution rose to 42.0% while utilizing MP þ 1.0% RC þ 24.6% Fe
from 37.5% when using CP þ 1.0% RC þ 24.6% Fe. Meanwhile,
the dispersion of liquid carbon rose to 47.1% when using MP þ
1.0% AC þ 24.6% Fe from 43.1% when using CP þ 1.0% AC þ
24.6% Fe. Liquid yields in MP (Fe/RC and Fe/AC) have higher
values than CP (Fe/RC and Fe/AC). This is because the heating
mechanism effects the surface morphology and yield of char
[38,42]. MP can facilitate LRC aromatization and cyclization
[43e46]. The direct result of aromatization and collapse of coal
micropores is a decrease in specific surface area (SSA) [47]. In
addition, the radiant power performed by syngas products
provides a major boost to enlargement and expansion of pores
[39,40]. MP in LRC can cause decomposition of functional
groups of aromatic hydrocarbons and oxygen. Removal of
these hydrophilic groups in hydroxyl, carbonyl, carboxyl, or
aldehydes will weaken the moisture holding capacity of the
LRC [43e46].
3.2. Product process determined from syngas and liquid
production conditions
The following diagram shows how to figure out if the tem-
perature, time, and power effect the best conditions for
making TWL (liquid and syngas yields).
Product of pyrolysis due to temperature
Most of the time, adding a receptor, the type of catalyst, and
the amount of catalyst charge effect the rate of temperature
rise and the pyrolysis temperature. The presence of receptors
and catalysts cause a rise in free H2 and a complete break-
down of complex aromatic compounds [7,24]. Fig. 5(a) depicts
the temperature-dependent pyrolysis of LRC via MP þ Fe/AC.
Fig. 5(a) depicts LRC using MP þ Fe/RC to create liquid and
syngas. The maximum TWL of 63.0% from the research results
was obtained at a temperature of 610  C. TWL increased from
57.5 to 63.0% at a temperature of 570e620  C. Meanwhile, TWL

Fig. 5 e Temperature effects on products: (a) Fe/RC and (b) Fe/AC.

 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 2 0 3 e2 1 6
decreased at 63.0e61.6% at 620e650  C. Found 46.1% at 650  C
for maximum liquid yield and 27.4% at 570  C for syngas yield.
The temperature trends resulting from the Fe/RC impact is
lower than the temperature required for the addition of cat-
alysts like Fe, K2CO3, CaCl2, and Fe3O4 receptors [8,18,25]. The
highest reaction temperature of MP þ Fe/AC at 4 mesh, 600 W,
60 min, 10 mmH2O, loading 1.0% RC þ 24.6% Fe is 610  C.
Fig. 5(b) demonstrates the temperature-dependent pyrol-
ysis of LRC via MP þ Fe/AC. The results showed that the
maximum TWL of 62.2% was obtained at 620  C. The increase
in TWL is 59.1e62.2% at a temperature of 570e620  C, while a
decrease in TWL is at 62.2e59.5% at a temperature of
620e650  C. At 44.4% at 620  C for maximum liquid yield and at
23.0% at 640  C for maximum syngas yield. The temperature
trend was found between the temperatures for the addition of
Fe3O4 þ CAC under the influence of Fe/AC [25,48]. As a result,
the reaction temperature of the charge MP þ 1.0% AC þ 24.6%
Fe at 10 mmH2O, 450 W, 60 min, and 4 meshes is 620  C.
Microwave power affecting pyrolysis products
Adding more receptors and catalysts to the coal will increase
the amount of syngas and liquid that can be made [25]. Fig. 6
shows how power effects the LRC via the MP, RC, and AC
catalysts as well as the Fe receptor. Fig. 6(a) shows MP þ Fe/RC
at LRC, which is affected by temperature. The production of
syngas and liquid via MP þ Fe/RC from coal is shown in
Fig. 6(a). The results of the study explained that at 63.0%, the
maximum TWL was achieved at a power of 600 W. TWL
increased by 59.2e63.0% from a power of 0e600 W. Mean-
while, TWL decreased from 63.0 to 60.0% at an input power of
600e800 W. The maximum syngas yield is 26.0% at 600 W, and
the maximum liquid yield is 45.1% at 325 W. In comparison to
the study's findings, the input power resulting from the in-
fluence of Fe/RC is relatively low [8,18,25].
Fig. 6(b) depicts the temperature-dependent pyrolysis of
LRC through MP þ Fe/AC. Fig. 6(b) shows that TWL obtained
62.6% of an input power of 450 W. The results showed that
TWL increased from 57.0 to 62.6% at the input power of
0e450 W. Meanwhile, TWL decreased from 62.6 to 59.0% at
Fig. 6 e Microwave power effects on product: (a) Fe/RC and (b) Fe/AC.
209
450e800 W input power. The maximum syngas and liquid
yields are 29.0% (at 325 W) and 45.0% (at 700 W). When
compared with the results of previous studies, the Fe/AC ef-
fects on the input power obtained his quite low [25,26]. The
input power is determined by the loss tangent (tan d ¼ E00 /E0 ),
namely the ability of the material to form heat energy from
changes in microwave electrical energy [49].
Pyrolysis products are affected by reaction time
The pyrolysis temperature and reaction time effect how a
product is made and where it is found [23]. Reaction time is
influenced by one factor, namely MP-catalyst-receptor. Fig. 7
depicts the pyrolysis of LRC with the addition of RC and AC
catalysts, as well as the effect of reaction time on the Fe re-
ceptor via MP. Fig. 7(a) illustrates how reaction time effects the
pyrolysis of LRC via MP þ Fe/RC. From the study, it was found
that the maximum TWL was 63.0% at the 60 min of the reaction
time. TWL increased from 57.0 to 63.0% at a reaction time of
15e60 min. Meanwhile, TWL decreased from 63.0 to 62.5% at a
reaction time of 60e135 min. Syngas and liquid yields of
maximum product were 24.7% at 135 min and 46.1% at 105 min,
respectively. When compared to the findings of earlier
research like those by Liu et al. [7], Zhang et al. [18], and Wang
et al. [22]. According to the findings, adding Fe/RC can reduce
the temperature increase time of the LRC by heating the MP to
the melting point of the interacting material. Melting points of
RC ¼ (~1390  C) and Fe ¼ (~480  C). As a result, the reaction
times of adding Fe/AC to coal MP significantly increases the
distribution and composition of the final product.
Fig. 7(b) demonstrates the pyrolysis of LRC via MP þ Fe/AC
which is affected by reaction time. Fig. 7(b) shows the
maximum TWL of 54.2% obtained at the 120 min. TWL
increased to 42.29e54.2% at a reaction time of 15e120 min.
Meanwhile, TWL decreased from 54.2 to 53.1% in
120e135 min. The maximum syngas and liquid yields were
18.9% at 75 min and 42.1% at 135 min, respectively. When
compared with the results of studies such as Liu and Xia [14]
and Zhang et al. [18] it is clear that the use of Fe/AC takes a
long period of time. The research demonstrates that the
210 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 2 0 3 e2 1 6

Fig. 7 e The effects of reaction time on the product: a) Fe/RC and (b) Fe/AC.

addition of 1.0% AC þ 24.6% Fe, which interacts with the
heating impact of the material's melting temperature on the
MP, can delay the LRC's temperature rise time. Where Fe has a
melting temperature of (~480  C) and AC has a temperature
(~3680  C). As a result, the increase in coal pyrolysis time in MP
with the addition of 1.0% AC þ 24.6% Fe was responsible for
the effective increase in product composition and dispersion.
3.3. Pyrolysis product analysis
Solid products
LRC and solid products MP þ 1.0% RC þ 24.6% Fe, MP þ 1.0% AC
þ 24.6% Fe and were analyzed directly. Where, LRC is treat-
ments into particle size 4 mesh and dried at 105  C for 12 h.
Meanwhile, the char from MP þ Fe/RC is a solid product which
is operated at a maximum process condition of temperature
620  C, power 600 W, and time 60 min. Meanwhile, the char of
MP þ Fe/AC is temperature 620  C, power 450 W, and time
120 min. The MP þ Fe/RC application enhanced the fixed car-
bon and ash content by 38.0e64.0% and 11.9e20.2%, respec-
tively. When MP þ Fe/AC was used, the fixed carbon and ash
content rose to 38.0e67.0% and 11.9e19.4%, respectively.
When MP þ Fe/RC was used, the volatile matter and moisture
content dropped by 43.6e11.9% and 6.5e3.9%, respectively.
When MP þ Fe/AC was applied to 43.6e9.4% and 6.5e4.1%,
respectively, the volatile matter and moisture content
decreased.
The increase in fixed carbon in MP þ Fe/RC and MP þ Fe/AC
was caused by the heterogeneous gas phase reaction, such as
CH4 decomposition on the solid carbon surface: CH4 /C þ H2
[50,51]. Other reactions are secondary reactions, such as
reverse water-gas-shift (CO2 þ H2 / CO þ H2O) and reverse
Boudouard (C þ CO2 / 2CO). Ash content of MP þ Fe/RC and
MP þ Fe/AC “increased because ash is content (%) ¼ 100% -
[fixed carbon (%) þ moisture (%) þ volatile matter (%)].”
As shown in Fig. 8, showing the char reaction pattern
produced from MP þ Fe/RC and MP þ Fe/AC at a temperature
of 620  C, the crude coal reaction pattern and the carbon black
reaction pattern are plotted for reference. The XRD spectrum
was used to look at the crystal reaction's peak, and the results
showed that the XRD pattern matched the inorganic minerals
found in the LRC. SiO2 and Ca4(Al8Si8O32) are the dominant

Fig. 8 e XRD spectra of solid product: LRC, Black carbon, Char of MP þ Fe/RC, and Char of MP þ Fe/AC.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 2 0 3 e2 1 6
crystal peaks of LRC. Meanwhile, the char crystal peaks at
MP þ Fe/RC and MP þ Fe/AC were mostly SiO2. Observed at 2q,
between 20 and 30 and 40 and 50 of reflections (100) and
(002), corresponding to two broad carbon peaks [52e55].
The increased temperature causes the LRC to begin to
undergo devolatilization, and its molecules begin to link
together through dehydration and decarboxylation reactions.
The presence of the expected graphite like domains of carbon
in the LRC and char (solid) structures was informed by the look
of the peaks of reaction, equivalent to (002) and (100) reflecting
graphite [53]. The reaction peak observed for the char of
MP þ Fe/RC produced in 620  C was similar to the char of
MP þ Fe/AC produced in 620  C. However, the char of MP þ Fe/
RC and MP þ Fe/AC produced in 620  C compared to crude coal
has a slightly lower carbon peak at 2q between 20 and 30
according to the reaction in (002). This result is coherent for
also research informed in the papers [52,54], in which the
carbon structure stacking parameters did not change until the
temperature of final of 600  C and risen rapidly into a tem-
perature rise rate. However, crystal peak of LRC is Ca4(Al8Si8-
O32) in contrast to the char crystal peak of MP þ Fe/RC and
MP þ Fe/AC which is produced in 620  C. No crystal peaks of
inorganic Ca4(Al8Si8O32) were found in the char of MP þ Fe/RC
and MP þ Fe/AC. This can point out as heating of microwave
selective produces hot spots of localized and induces reduc-
tion of carbothermic of Ca4(Al8Si8O32) in coal of crude to SiO2,
CaO, and Al2O3 at a bulk temperature of lows of 550  C.
LRC and solid products MP þ Fe/RC and MP þ Fe/AC were
further analyzed by micromorphology. The SEM image is
shown in Fig. 9. Due to the heating of the MP, the char stress is
warmer and uniform in the finely shaped particle structure.
Particles in MP are larger than LRC for MP þ Fe/RC and
MP þ Fe/AC performance. The LRC surface is looser (Fig. 9(a)).
Meanwhile, the surface of char MP þ Fe/RC (Fig. 9(b)) and
MP þ Fe/AC (Fig. 9(c)) was denser. This indicates that the
Fig. 9 e SEM picture of a stable product: (a) LRC, (b) MP þ Fe/RC, (c) MP þ Fe/AC.
211
fluidization states of the melt MP þ Fe/RC and MP þ Fe/AC can
induce the MP catalytic reaction. Fe/RC and Fe/AC in MP
function as absorbent agents that convert the energy of mi-
crowave for energy of heat. The results showed that hydrogen
of fire was produced from attached of hydrogen to the exposed
metal activity points. This consequently increases the reac-
tion of hydro. The structure of char space (Fig. 9(c)) seemed to
disappear with much larger hole's later irradiation of the mi-
crowave. Sahoo et al. [56] concluded that irradiation of a mi-
crowave may preferentially heat, minerals in coal premised
on different properties of dielectric, baiting pyrite to rot. This
is possible, because part of the collapses of structure under
stress of heating releasing many adhering particles of char
[57,58].
Liquid product
Fig. 10 shows the FTIR spectra of liquid product. The number
“1e6“ denotase the absorption peaks are found at 3408, 2583,
2375, 1675, and 610 cm1, respectively. Strain vibrations of
hydrogen bonds (i.e., eNH and eOH) and phenol bonds are at
the absorption peak of 3408 cm1, including the IR absorption
peak of the functional group [59]. Fe acts as receptors and RC
and AC catalysts exhibited a hydroxyl strain vibration at
3408 cm1 including slightly weaker MP þ Fe/RC and MP þ Fe/
AC. In the microwave, under the action of Fe/RC and Fe/AC,
hydroxy was decomposed into free hydrogen. This shows that
MP þ Fe/RC and MP þ Fe/AC performed better, resulting in a
higher amount of light bio-oil, especially using MP þ Fe/RC
and MP þ Fe/AC. Due to the catalytic activity of Fe/RC and Fe/
AC, hydroxy stretching vibrations occur during the MP. The
absorption peaks of 3408, 2583, 2375, 1675, and 610 cm 1 were
considered to be vibrations of aliphatic CeH. Thus, the addi-
tion of Fe/RC and Fe/AC is appropriate as the generation of
hydrocarbons of fatty and cycloparaffins for the production of
liquid, providing the added pyrolysis advantage [35].
212 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 2 0 3 e2 1 6
Fig. 10 e FTIR spectra of liquid product: (a) MP þ Fe/RC; (b) MP þ Fe/AC.
Higher bio-oil content with several times increase was
observed with the addition of MP þ Fe/RC and MP þ Fe/AC.
Thus, the intermediate bio-oil and heavy bio-oil are decom-
posed of easily into bio-oil of light by energy of microwave.
The lower intermediate and weight bio-oil content may be
caused to the presence of Fe/RC and Fe/AC. A big quantity of
hydrogen of free is produced, thus facilitated the reaction of
hydrogenation. This conclusion is supportive by the spectra of
FTIR of liquid and solid yields. MP þ Fe/RC and MP þ Fe/AC can
both significantly improve the bio-oil content. When using
MP þ Fe/RC, the content of heavy bio-oil was at least 3.0% and
the content of light bio-oil was at most 97.0%. While using
MP þ Fe/AC, the concentration of heavy bio-oil was at least
99.0% and that of light bio-oil was at most 1.0% in tar. Heavy
bio-oil is broken down into bio-oil of light and little of inter-
mediate bio-oil due to the synergy of MP þ Fe/RC and MP þ Fe/
AC [60].
Table 2 shows the bio-oil content determined by GC-MS.
Phenols, ketones, benzene, alkenes, alkanes, and naphtha-
lene are among the chemicals discovered as a result of the
synergy between MP þ Fe/RC and MP þ Fe/AC [61]. The tem-
perature and duration that produced the most aromatic
chemicals, such as phenol and naphthalene, increased
dramatically, whereas the benzene concentration gradually
declined. These findings are consistent with previously pub-
lished research findings [62]. In the next step of pyrolysis to
the maximum temperature, some of the benzene is trans-
formed to phenol and naphthalene molecules. The pyrolysis
temperature affects the production of the phenol component
during the process [63].
The large amount of lignin in lignite coal is linked to the
highest concentration of phenolic compounds in the pyrolysis
oil. Because lignite has a higher lignin content than biomass
feedstock, which mostly comprise hemicellulose and cellu-
lose, pyrolysis of lignite produces more oil products. The
generation of phenol from the breakdown of lignin has been
documented [64]. The pyrolysis oil from the pyrolysis of MW
lignite is significantly phenolic, according to GC-MS analysis.
This indicates oil reforming's suitability for value-added
chemicals [65]. Alkoxyl groups, not C1eC4 alkyl groups, are
present in all phenol derivatives, such as phenol 2-methyl;
phenol 3-methyl; phenol 4-methyl; phenol-2,3-dimethyl;
phenol-2,4-dimethyl; phenol 2,5-dimethyl; phenol 2,6-
dimethyl; phenol 2-ethyl; and phenol 3-ethyl. At 550e620  C,
the mechanism of the Diels-Alder reaction followed by
dehydrogenation has been hypothesized as a factor respon-
sible for the increase in aromatic in the produced oil [66].
When long-chain aliphatic esters are pyrolyzed, hydrocarbon
radicals are formed, which can grab hydrogen and create
acorns. Aromatic compounds can be produced through sec-
ondary reactions of hydrocarbons at high temperatures [67].
The Diels-Alder reaction is favored by high temperatures,
which results in a rise in the concentration of aromatic com-
pounds in the oil [66].
Phenol made up a significant portion of the oil in MP þ Fe/
RC and MP þ Fe/AC, accounting for 0.6e21.5% and 5.2e29.9%,
respectively. According to the GC-MS peak area. The phenol in
MP þ Fe/RC is mostly made up of phenol; phenol, 2-methyl-
phenol, 3-methyl-; phenol, 4-methyl-; phenol, 2,3-dimethyl-;
phenol, 2,4-dimethyl-; phenol, 2,5-dimethyl-; phenol, 2,6-
dimethyl-; phenol, 2-ethyl-; and phenol, 3-ethyl which ac-
count for 7.0e21.5%; 3.6e5.5%, 5.6e7.2%; 2.8e7.2%; 0e0.6%;
0e1.1%; 0e0.6%; 0e0.6%; 0e0.7%; and 0e1.0% of the oil fraction
in the area, respectively. Phenol is only detected in the oil
produced at 1.8e4.1 min of processing; phenol, 2-methyl- is
only detected in the oil produced at 3.2e5.2 min of processing;
phenol, 3-methyl- is only detected in the oil produced at
3.6e5.2 min of processing; phenol, 4-methyl- is only detected
in the oil produced at 3.6e5.2 min of processing; and phenol,
2,3-dimethyl -; phenol, 2,4-dimethyl-, phenol, 2,5-dimethyl-,
phenol, 2,6-dimethyl-, media are only detected after
0e6.1 min of processing; and phenol, 2-ethyl-, phenol, 3-ethyl-
, media are only detected after 0e6.4 min when the pyrolysis
temperature reached 620  C. Meanwhile, phenol in MP þ Fe/
AC is mostly made up of phenol; phenol, 2-methyl-; phenol, 3-
methyl-; and phenol, 4-methyl-, which account for 0e29.9%,
5.2e8.7%, 0e17.4%, and 0e17.4% of the oil fraction in the area,
respectively. Phenol is only detected in the oil produced at
0e4.2 min of processing; phenol, 2-methyl- is only detected in
the oil produced at 4.9e21.1 min of processing; and phenol, 3-
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 2 0 3 e2 1 6 213

Table 2 e Relative proportions of the principal pyrolysis constituents in the oils.

Chemical components Molecular formula Retention time (min) Area (%)
MP þ Fe/RC / 1.0%RC þ 24.6%Fe2(SO4)3
Phenol C6H6O 1.748 7.041
Benzenesulfonic acid, 4-hydroxy- C6H6O4 1.748 3.259
2-Cyclopenten-1-one, 5-hydroxy-2,3 C7H10O2 1.795 0.902
2-Nonynoic acid C9H14O2 1.795 1.102
1H-Imidazole, 4-(2-propenyl)- C6H8N2 1.795 0.773
Oct-2-ynoic acid C8H12O2 1.795 1.002
6-(1,4-Benzodioxan-2-ylcarbonylhy C14H12N4O5 1.795 2.261
Trans-1,3-dideuterio-1,3-cyclohex C6H12D2N2 2.220 4.105
1-Hexyn-3-ol C6H10O 2.220 3.529
N-propylacetamide C5H11NO 2.220 3.637
Cyclopentane, methyl- C6H12 2.330 2.000
Cyclohexane C6H12 2.391 1.510
Phenol, 2-methyl- C7H8O 3.200 4.450
Phenol, 3-methyl- C7H8O 3.644 5.588
Phenol, 2-methyl- C7H8O 3.644 5.588
Phenol, 4-methyl- C7H8O 3.644 2.794
Phenol C6H6O 4.130 21.470
Phenol, 2-methyl- C7H8O 4.929 5.500
Phenol, 3-methyl- C7H8O 5.165 7.248
Phenol, 2-methyl- C7H8O 5.165 3.624
Phenol, 4-methyl- C7H8O 5.165 7.248
Phenol, 2,4-dimethyl- C8H10O 6.094 1.104
Phenol, 2,3-dimethyl- C8H10O 6.094 0.552
Phenol, 2,6-dimethyl- C8H10O 6.094 0.552
Phenol, 2,5-dimethyl- C8H10O 6.094 0.552
Phenol, 2-ethyl- C8H10O 6.359 0.684
Phenol, 3-ethyl- C8H10O 6.359 1.026
Aspidofiline C21H26N2O2 19.175 0.200
Cyclopentanecarboxylic-2,2,4,4-D4 C8H8D4O3 19.175 0.092
Phosphine, (1-methylethyl)phenyl- C9H13P 19.175 0.090
3-(4-Methoxyphenyl)-5,8-dichloro- C18H15CL2N5O2 19.175 0.238
Hexadecanoic acid, 2,3-bis[(trimeth C25H54O4S12 19.175 0.280
MP þ Fe/AC / 1.0%AC þ 24.6%Fe2(SO4)3
Bicyclo [2.2.1] heptane,-5-(ethyl-1-a C9H17N 2.115 2.1644
Methyl-pent-4-enyl-amine C6H13N 2.115 1.5416
4-Octen-3-one C8H14O 2.115 1.9620
2-Heptanamine, 5-methyl- C8H19N 2.115 1.9620
Phenol C6H6O 4.177 29.8817
Benzenesulfonic acid, 4-hydroxy- C6H6O4S 4.177 13.8283
Phenol, 2-methyl- C7H8O 4.982 5.2200
Phenol, 3-methyl- C7H8O 21.133 17.3760
Phenol, 4-methyl- C7H8O 21.133 17.3760
Phenol, 2-methyl- C7H8O 21.133 8.6880

methyl-; and phenol, 4-methyl- media are only detected after
0e21.1 min of pyrolysis when the pyrolysis temperature
reached 620  C. The majority of the components include one
or two methyl or ethyl groups rather than methoxyl, indi-
cating that pyrolysis under these conditions induces not only
demethylation but also breaking of CO bonds in free radicals.
The loss of oxygen atoms in the form of CO2 and CO is
accompanied by the reformation of free radical groups,
resulting in low oxygen levels in the oil phase [68].
Benzene from MP þ Fe/RC and MP þ Fe/AC was benzena-
sulfonic acid, 4-hydroxy-, which accounted for 3.3% and 13.8%
of the peak area of GC-MS, respectively. During pyrolysis, the
alkenes and alkanes of MP þ Fe/RC and MP þ Fe/AC accounted
for 20.7% and 7.7% oil, respectively, with peak area and
maximum concentrations reported at 2.1 and 2.3 min.
MP þ Fe/RC liquid fuel is between C5eC10, C14eC20, and
C21eC50 based on chemical composition (carbon atomic
number). MP þ Fe/AC liquid fuel is between C5eC10, C14eC20,
and C21eC50 based on chemical composition (carbon atomic
number). C5eC10 is the carbon atomic number comparable to
gasoline, C14eC20 is the carbon atomic number equivalent to
diesel oil, and C21eC50 is the carbon atomic number equivalent
to residual oil. The density and viscosity of liquid fuel from
MP þ Fe/RC were 0.74e0.77 g/mL and 0.97e0.99 cSt, respec-
tively, confirming this. Meanwhile, the density and viscosity
of liquid fuel from MP þ Fe/AC are 0.72e0.89 g/mL and
0.77e0.99 cSt, respectively. Where liquid fuel density and
standard viscosity are 0.72e0.89 g/mL and 0.77e0.99 cSt,
respectively [69].
214 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 2 0 3 e2 1 6
Conclusions
In this research, processing of 4-mesh LRC with Fe/AC and Fe/
RC as catalysts and receptors was done using microwave py-
rolysis (MP). Time, temperature, and input power, including
process conditions, as well as product distribution effects, are
evaluated. Product distribution changes brought on by the
addition of Fe/RC and Fe/AC to MP, which raises temperature
and the ultimate temperature. In comparison to conventional
or non-microwave (CP) catalytic pyrolysis, treatment of
MP þ 1.0% RC þ 24.6% Fe at the same conditions (60 min and
620  C) resulted in 37.5% bio-oil, with an increase in bio-oil
yield of 0.4%. The production of bio-oil increased by 4.0%
when MP þ 1.0% AC þ 24.6% Fe was used and it also produced
47.1% bio-oil. Maximum bio-oil production was seen when
1.0% RC þ 24.6% Fewere used, yielding 42.0% bio-oil, 21.0%
syngas, and 37.0% char at 60 min, 610  C, and 600 W. While
this was going on, the use of 1.0% AC þ 24.6% Fe produced
49.2% bio-oil, 18.9% syngas, and 31.9% char at a reaction
duration of 120 min, a process temperature of 620  C, and an
input power of 450 W. Thus, the increases of Fe/RC and Fe/AC
both treatments contributed positively to the producion of
bio-oil from LRC through microwave application. Thus, this
study becomes the basis for reducing global carbon emissions
by converting LRC into clean fuels.
Credit authorship contribution statement
Bambang Sardi: Data curation, Methodology, Visualization,
Roles/Writing - original draft, Writing - review & editing.
Irianto Uno: Data curation, Methodology, Software, Supervi-
sion, Validation. Fitrawati A. Marhum: Methodology, Super-
vision, Formal analysis, Investigation, Project administration.
Amar Ali Akbar: Methodology, Supervision, Validation, Fund-
ing acquisition, Investigation, Project administration. Tha-
hirah Arief: Methodology, Validation, Funding acquisition,
Writing - review & editing, Software. Muhammad Arif: Meth-
odology, Visualization, Writing - review & editing. Conceptu-
alization. Ali Altway: Software, Supervision, Validation.
Mahfud Mahfud: Conceptualization, Formal analysis, Funding
acquisition, Investigation, Project administration, Resources.
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
This activity is funded through BPPDN (Beasiswa Pendidikan
Pascasarjana Dalam Negeri) No. B/67/D.D3/KD.02.00/2019
under the Education Fund Management Institute e Research,
Technology and Higher Education Ministry and Finance Min-
istry of the Republic of Indonesia.
references
[1] Yolcan OO. World energy outlook and state of renewable
energy: 10-Year evaluation. Innov Green Dev 2023;2:100070.
https://doi.org/10.1016/j.igd.2023.100070.
[2] Miura K. Mild conversion of coal for producing valuable
chemicals. Fuel Process Technol 2000;62:119e35. https://
doi.org/10.1016/S0378-3820(99)00123-X.
[3] Reddy BR, Shravani B, Das B, Dash PS, Vinu R. Microwave-
assisted and analytical pyrolysis of coking and non-coking
coals: comparison of tar and char compositions. J Anal Appl
Pyrolysis 2019;142:104614. https://doi.org/10.1016/
j.jaap.2019.05.003.
[4] Wu L, Zhou J, Zhou J, Liang K, Song Y, Zhang Q, et al.
Temperature-rising characteristics and product analysis of
low-rank coal microwave pyrolysis under CH4 atmosphere. J
Anal Appl Pyrolysis 2019;259:461e4. https://doi.org/10.1016/
j.jaap.2019.104632.
[5] Jamilatun S, Yuliestyan A, Aziz M. Catalytic pyrolysis of
spirulina platensis residue (SPR): thermochemical behavior
and kinetics. Int J Technol 2020;11:522e31. https://doi.org/
10.14716/ijtech.v11i3.2967.
[6] Zhou J, Wu L, Zhou J, Liang K, Song Y, Tian Y, et al. Products
optimization by FeS2 catalyst for low-rank coal microwave
pyrolysis. Fuel 2019;255:115759. https://doi.org/10.1016/
j.fuel.2019.115759.
[7] Liu C, Yue C. Metal sulfide assisted coal catalytic
hydrogenated microwave pyrolysis. Mater Sci Forum
2020;999:178e90. https://doi.org/10.4028/www.scientific.net/
MSF.999.178.
[8] Liu S, Tuo K, Wang L, Chen G, Ma W, Fang M. Microwave-
assisted metal-catalyzed pyrolysis of low-rank coal:
promising option towards obtaining high-quality products. J
Energy Inst 2020;93:1602e14. https://doi.org/10.1016/
j.joei.2020.01.022.
[9] Hossain MA, Jewaratnam J, Ganesan P. Prospect of hydrogen
production from oil palm biomass by thermochemical
process e a review. Int J Hydrogen Energy 2016;41:16637e55.
https://doi.org/10.1016/j.ijhydene.2016.07.104.
[10] Dong Y, Mao S, Guo F, Shu R, Bai J, Qian L, et al. Coal
gasification fine slags: investigation of the potential as both
microwave adsorbers and catalysts in microwave-induced
biomass pyrolysis applications. Energy 2022;238:121867.
https://doi.org/10.1016/j.energy.2021.121867.
[11] Sardi B, Ningrum RF, Ardiansyah VA, Qadariyah L,
Mahfud M. Production of liquid biofuels from microalgae
chlorella sp . via catalytic slow pyrolysis. Int J Technol
2022;13:147e56. https://doi.org/10.14716/ijtech.v13i1.4358.
[12] Thomson R, Kwong P, Ahmad E, Nigam KDP. Clean syngas
from small commercial biomass gasifiers; a review of gasifier
development, recent advances and performance evaluation.
Int J Hydrogen Energy 2020;45:21087e111. https://doi.org/
10.1016/j.ijhydene.2020.05.160.
[13] Lin H, Zhu H, Guo H, Yu L. Microwave-absorbing properties
of Co-filled carbon nanotubes. Mater Res Bull 2008;43:
2697e702. https://doi.org/10.1016/j.materresbull.2007.10.016.
[14] Liu Q, Xia H. The effect of additive on temperature rising
characteristics during coal pyrolysis in microwave field. Adv
Mater Res 2012;512e515:1790e4. https://doi.org/10.4028/
www.scientific.net/AMR.512-515.1790.
[15] Salema AA, Ani FN. Microwave-assisted pyrolysis of oil palm
shell biomass using an overhead stirrer. J Anal Appl Pyrolysis
2012;96:162e72. https://doi.org/10.1016/j.jaap.2012.03.018.
[16] Sardi B, Rachmawati H, Fakhry T, Setiawati E, Indrawan N,
Mahfud M. Advanced bio-oil production from a mixture of
microalgae and low rank coal using microwave assisted
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 2 0 3 e2 1 6
pyrolysis. Bioresour Technol Reports 2023;21:101367. https://
doi.org/10.1016/j.biteb.2023.101367.
[17] Aysu T, Durak H. Pyrolysis of giant mullein (Verbascum
thapsus L.) in a fixed-bed reactor: effects of pyrolysis
parameters on product yields and character. Energy Sources,
Part A Recover Util Environ Eff 2016;38:661e9. https://doi.org/
10.1080/15567036.2013.819049.
[18] Zhang Y, Chen G, Wang L, Tuo K, Liu S. Microwave-assisted
pyrolysis of low-rank coal with K2CO3, CaCl2, and FeSO4
catalysts. ACS Omega 2020;28. https://doi.org/10.1021/
acsomega.0c01400. A-J.
[19] Ruhswurmova N, Kim S, Yoo J, Chun D, Rhim Y, Lim J, et al.
Nickel supported on low-rank coal for steam reforming of
ethyl acetate. Int J Hydrogen Energy 2018;43:15880e90.
https://doi.org/10.1016/j.ijhydene.2018.06.104.
[20] Wang S, Zhang F, Cai Q, Li X, Zhu L, Wang Q, et al. Catalytic
steam reforming of bio-oil model compounds for hydrogen
production over coal ash supported Ni catalyst. Int J
Hydrogen Energy 2014;39:2018e25. https://doi.org/10.1016/
j.ijhydene.2013.11.129.
[21] Yagmur E, Simsek EH, Aktas Z, Togrul T. Effect of CuO
receptor on the liquid yield and composition of oils derived
from liquefaction of coals by microwave energy. Energy
Convers Manag 2008;49:3043e50. https://doi.org/10.1016/
j.enconman.2008.06.021.
[22] Wang N, Yu J, Tahmasebi A, Han Y, Lucas J, Wall T, et al.
Experimental study on microwave pyrolysis of an
Indonesian low-rank coal. Energy Fuel 2014;28:254e63.
https://doi.org/10.1021/ef401424p.
[23] Xu B, Kuang D, Liu F, Lu W, Goroncy AK, He T, et al.
Characterization of Powder River Basin coal pyrolysis with
cost-effective and environmentally-friendly composite
NaeFe catalysts in a thermogravimetric analyzer and a fixed-
bed reactor. Int J Hydrogen Energy 2018;43:6918e35. https://
doi.org/10.1016/j.ijhydene.2018.02.102.
[24] Wu L, Zhou J, Yang R, Tian W, Song Y, Zhang Q, et al.
Enhanced catalytic microwave pyrolysis of low-rank coal
using Fe2O3@bluecoke absorber prepared by a simple
mechanical ball milling. J Energy Inst 2021;95:193e205.
https://doi.org/10.1016/j.joei.2021.01.007.
[25] Mushtaq F, Mat R, Ani FN. Fuel production from microwave
assisted pyrolysis of coal with carbon surfaces. Energy
Convers Manag 2016;110:142e53. https://doi.org/10.1016/
j.enconman.2015.12.008.
[26] Mushtaq F, Mat R, Ani FN. A review on microwave assisted
pyrolysis of coal and biomass for fuel production. Renew
Sustain Energy Rev 2014;39:555e74. https://doi.org/10.1016/
j.rser.2014.07.073.
[27] Sardi B, Altway A, Mahfud M. Bio-oil production from low-
rank coal via novel catalytic microwave pyrolysis using
activated carbon þ Fe2(SO4)3 and HZSM-5 þ Fe2(SO4)3. Fuel
2022;324:124509. https://doi.org/10.1016/j.fuel.2022.124509.
[28] Sardi B, Uno I, Pasila F, Altway A, Mahfud M. Low rank coal
for fuel production via microwave-assisted pyrolysis: a
review. FirePhysChem 2023;3:106e20. https://doi.org/
10.1016/j.fpc.2023.02.002.
[29] Wu L, Guan Y, Li C, Zhou J, Liu T, Ye G, et al. Insight into
product characteristics from microwave co-pyrolysis of low-
rank coal and corncob: unraveling the effects of metal
catalysts. Fuel 2023;342:127860. https://doi.org/10.1016/
j.fuel.2023.127860.
[30] Wang W, Lemaire R, Bensakhria A, Luart D. 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 Pyrolysis
2022;163:105479. https://doi.org/10.1016/j.jaap.2022.105479.
215
[31] Zhang F, Zhang X, Song Z, Chen H, Zhao X, Sun J, et al. Fe/
HZSM-5 synergizes with biomass pyrolysis carbon to reform
CH4eCO2 to syngas in microwave field. Int J Hydrogen
Energy 2022;47:11153e63. https://doi.org/10.1016/
j.ijhydene.2022.01.158.
[32] Li L, Cao K, Cai D, Zhang Z, Zhao Z, Yu M, et al. Influences of
iron additives on microwave-assisted pyrolysis of woody
biomass and microwave-induced discharge with spherical
bio-char. Energy 2023;276:127549. https://doi.org/10.1016/
j.energy.2023.127549.
[33] Liu J, Jiang J, Jiang C, Wang Z, Chen P. Desulfurization
mechanism of high-sulfur coal by heating reduced iron
powder and magnetic separation. J Clean Prod
2022;370:133254. https://doi.org/10.1016/
j.jclepro.2022.133254.
[34] Yue G, Zhao L, Olvera OG, Asselin E. Speciation of the H2SO4-
Fe2(SO 4)3-FeSO4-H2O system and development of an
expression to predict the redox potential of the Fe3 þ/Fe 2 þ
couple up to 150  c. Hydrometallurgy 2014;147e148:196e209.
https://doi.org/10.1016/j.hydromet.2014.05.008.
[35] Zhou J, Wu L, Liang K, Zhang Q, Song Y, Tian Y, et al. The
synergistic mechanism on microwave and MoS2 in coal
pyrolysis. J Anal Appl Pyrolysis 2018;134:580e9. https://
doi.org/10.1016/j.jaap.2018.08.007.
[36] Kabe T, Ishihara A, Qian EW, Sutrisna IP, Kabe Y. Coal and
coal-related compounds: structures, reactivity and catalytic
reactions. 150. 1st ed. Netherlands: Elsevier Science; 2004.
[37] Vasireddy S, Morreale B, Cugini A, Song C, Spivey JJ. Clean
liquid fuels from direct coal liquefaction: chemistry,
catalysis, technological status and challenges. Energy
Environ Sci 2011;4:311e45. https://doi.org/10.1039/
c0ee00097c.
[38] Ania CO, Parra JB, Mene ndez JA, Pis JJ. Effect of microwave
and conventional regeneration on the microporous and
mesoporous network and on the adsorptive capacity of
activated carbons. Microporous Mesoporous Mater
2005;85:7e15. https://doi.org/10.1016/
j.micromeso.2005.06.013.
[39] Li H, Lin B, Yang W, Zheng C, Hong Y, Gao Y, et al.
Experimental study on the petrophysical variation of
different rank coals with microwave treatment. Int J Coal
Geol 2016;154e155:82e91. https://doi.org/10.1016/
j.coal.2015.12.010.
[40] Hong Y du, Lin B quan, Nie W, Zhu C jie, Wang Z, Li H.
Microwave irradiation on pore morphology of coal powder.
Fuel 2018;227:434e47. https://doi.org/10.1016/
j.fuel.2018.04.066.
[41] Tao S, Chen S, Tang D, Zhao X, Xu H, Li S. Material
composition, pore structure and adsorption capacity of low-
rank coals around the first coalification jump: a case of
eastern Junggar Basin, China. Fuel 2018;211:804e15. https://
doi.org/10.1016/j.fuel.2017.09.087.
[42] Bikane K, Yu J, Shah SM, Long X, Paterson N, Pini R, et al.
High pressure CO2 gasification of Morupule coal: kinetics
and morphological development of chars. Chem Eng J
2023;462:142136. https://doi.org/10.1016/j.cej.2023.142136.
[43] Ge L, Zhang Y, Wang Z, Zhou J, Cen K. Effects of microwave
irradiation treatment on physicochemical characteristics of
Chinese low-rank coals. Energy Convers Manag
2013;71:84e91. https://doi.org/10.1016/
j.enconman.2013.03.021.
[44] Xia W, Yang J, Liang C. Effect of microwave pretreatment on
oxidized coal flotation. Powder Technol 2013;233:186e9.
https://doi.org/10.1016/j.powtec.2012.09.010.
[45] Niu Z, Liu G, Yin H, Zhou C, Wu D, Yousaf B, et al. In-situ FTIR
study of reaction mechanism and chemical kinetics of a
Xundian lignite during non-isothermal low temperature
216 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 9 ( 2 0 2 4 ) 2 0 3 e2 1 6
pyrolysis. Energy Convers Manag 2016;124:180e8. https://
doi.org/10.1016/j.enconman.2016.07.019.
[46] Yuan S, Liu JZ, Zhu JF, Zhou QQ, Wang ZH, Zhou JH, et al.
Effect of microwave irradiation on the propensity for
spontaneous combustion of Inner Mongolia lignite. J Loss
Prev Process Ind 2016;44:390e6. https://doi.org/10.1016/
j.jlp.2016.10.011.
[47] Li H, Shi S, Lin B, Lu J, Ye Q, Lu Y, et al. Effects of microwave-
assisted pyrolysis on the microstructure of bituminous coals.
Energy 2019;187:1e14. https://doi.org/10.1016/
j.energy.2019.115986.
[48] Wang K. Pyrolysis and catalytic pyrolysis of protein-and
lipid-rich feedstock. Iowa State University; 2014. https://
doi.org/10.31274/etd-180810-1175.
[49] Binner E, Lester E, Kingman S, Dodds C, Robinson J, Wu T,
et al. A review of microwave coal processing. J Microw Power
Electromagn Energy 2014;48:35e60. https://doi.org/10.1080/
08327823.2014.11689870.
[50] Fidalgo B, Fernandez Y, Dominguez A, Pis J, Menendez JA.
Microwave-assisted pyrolysis of CH4/N2 mixtures over
activated carbon. J Anal Appl Pyrolysis 2008;82:158e62.
https://doi.org/10.1016/j.jaap.2008.03.004.
[51] Domı́nguez A, Fidalgo B, Ferna  ndez Y, Pis JJ, Menendez JA.
Microwave-assisted catalytic decomposition of methane
over activated carbon for CO2-free hydrogen production. Int J
Hydrogen Energy 2007;32:4792e9. https://doi.org/10.1016/
j.ijhydene.2007.07.041.
[52] Takagi H, Maruyama K, Yoshizawa N, Yamada Y, Sato Y. XRD
analysis of carbon stacking structure in coal during heat
treatment. Fuel 2004;83:2427e33. https://doi.org/10.1016/
j.fuel.2004.06.019.
[53] Hassan HMA, Abdelsayed V, Khder AERS, Abouzeid KM,
Terner J, El-Shall MS, et al. Microwave synthesis of graphene
sheets supporting metal nanocrystals in aqueous and
organic media. J Mater Chem 2009;19:3832e7. https://doi.org/
10.1039/b906253j.
[54] Abdelsayed V, Shekhawat D, Smith MW, Link D,
Stiegman AE. Microwave-assisted pyrolysis of Mississippi
coal : a comparative study with conventional pyrolysis. Fuel
2018;217:656e67. https://doi.org/10.1016/j.fuel.2017.12.099.
[55] Hong W, Zhang Y, Jiang H, Li S, Chen J, Zhang L. Co-pyrolysis
of corn stalk and coal fly ash: a case study on catalytic
pyrolysis behavior, bio-oil yield and its characteristics. Case
Stud Therm Eng 2022;38:102346. https://doi.org/10.1016/
j.csite.2022.102346.
[56] Sahoo BK, De S, Meikap BC. Improvement of grinding
characteristics of Indian coal by microwave pre-treatment.
Fuel Process Technol 2011;92:1920e8. https://doi.org/10.1016/
j.fuproc.2011.05.012.
[57] Miura M, Kaga H, Tanaka S, Takahashi K, Ando K. Rapid
microwave pyrolysis of wood. J Chem Eng Jpn
2000;33:299e302. https://doi.org/10.1252/jcej.33.299.
[58] Gong X, Guo Z, Wang Z. Effects of Fe2O3 on pyrolysis
reactivity of demineralized higher rank coal and its char
structure. Huagong Xuebao/CIESC J 2009;60:2321e6.
[59] Sabar MA, Ali MI, Fatima N, Malik AY, Jamal A, Farman M,
et al. Degradation of low rank coal by Rhizopus oryzae
isolated from a Pakistani coal mine and its enhanced
releases of organic substances. Fuel 2019;253:257e65. https://
doi.org/10.1016/j.fuel.2019.04.101.
[60] Sharifzadeh M, Sadeqzadeh M, Guo M, Borhani TN, Murthy
Konda NVSN, Garcia MC, et al. The multi-scale challenges of
biomass fast pyrolysis and bio-oil upgrading: review of the
state of art and future research directions. Prog Energy
Combust Sci 2019;71:1e80. https://doi.org/10.1016/
j.pecs.2018.10.006.
[61] Deng W, Feng Y, Fu J, Guo H, Guo Y, Han B, et al. Catalytic
conversion of lignocellulosic biomass into chemicals and
fuels. Green Energy Environ 2023;8:10e114. https://doi.org/
10.1016/j.gee.2022.07.003.
[62] Ravenni G, Elhami OH, Ahrenfeldt J, Henriksen UB,
Neubauer Y. Adsorption and decomposition of tar model
compounds over the surface of gasification char and active
carbon within the temperature range 250e800  C. Appl
Energy 2019;241:139e51. https://doi.org/10.1016/
j.apenergy.2019.03.032.
[63] Nyoni B, Hlangothi SP. 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 Pyrolysis 2023;171:105950.
https://doi.org/10.1016/j.jaap.2023.105950.
[64] Zhai R, Hu J, Jin M. Towards efficient enzymatic
saccharification of pretreated lignocellulose: enzyme
inhibition by lignin-derived phenolics and recent trends in
mitigation strategies. Biotechnol Adv 2022;61:108044. https://
doi.org/10.1016/j.biotechadv.2022.108044.
[65] Gao K, Sahraei OA, Iliuta MC. Ni-based catalysts supported
on acid/alkali-activated coal fly ash residue for improved
glycerol steam reforming. Appl Catal B Environ
2022;301:120791. https://doi.org/10.1016/
j.apcatb.2021.120791.
[66] Li Z, Jiang Y, Li Y, Zhang H, Li H, Yang S. Advances in
DielseAlder/aromatization of biomass furan derivatives
towards renewable aromatic hydrocarbons. Catal Sci
Technol 2022;12:1902e21. https://doi.org/10.1039/
C4CY00072B.
[67] Dong Y, Tian B, Guo F, Du S, Zhan Y, Zhou H, et al.
Application of low-cost Fe-based catalysts in the microwave-
assisted pyrolysis of macroalgae and lignocellulosic biomass
for the upgradation of. Fuel 2021;300:120944. https://doi.org/
10.1016/j.fuel.2021.120944.
[68] Lu X, Deng J, Xiao Y, Zhai X, Wang C, Yi X. Recent progress
and perspective on thermal-kinetic, heat and mass
transportation of coal spontaneous combustion hazard. Fuel
2022;308:121234. https://doi.org/10.1016/j.fuel.2021.121234.
[69] Alawa B, Chakma S. Investigation in compression ignition
engine performance using alternative fuels produced from
waste packaging materials. Resour Conserv Recycl Adv
2022;14:200075. https://doi.org/10.1016/j.rcradv.2022.200075.