Fuel 324 (2022) 124509

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Fuel
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Bio-oil production from low-rank coal via novel catalytic microwave

pyrolysis using activated carbon + Fe2(SO4)3 and HZSM-5 + Fe2(SO4)3
Bambang Sardi, Ali Altway, Mahfud Mahfud *
Departement of Chemical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111, Indonesia

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

Keywords: The need for clean-coal technology is still demanding to counter environmental issues. Global coal is dominated
LRC by low-rank coal (LRC). Microwave pyrolysis (MP) is an advanced technologies to convert LRC into clean energy
Microwave pyrolysis such as bio-oil. However, the main pyrolysis challenges are low heating efficiency and the products dominated by
Activated carbon
heavy-tars. This study focused on MP to treat LRC using AC + Fe2(SO4)3 and HZSM-5 + Fe2(SO4)3 as catalysts
HZSM-5 catalyst
Fe2(SO4)3 receptor
and receptor. Effects on product distribution and process conditions (time, temperature, and power) were
evaluated. Results showed that AC + Fe2(SO4)3 and HZSM-5 + Fe2(SO4)3 increased the rate of temperature rise
and final temperature of MP, causing changes in product distribution. As compared to non-microwave or con­
ventional catalytic pyrolysis (CP) at the same condition (620℃ and 60 min), bio-oil produced from MP + 1.0%
AC + 24.6%Fe2(SO4)3 was 47.1%, 13.2% higher than the CP. Meanwhile, using MP + 1.0%HZSM-5 + 24.6%
Fe2(SO4)3, 42.5% bio-oil was produced by an increase of 8.6%. Using 1.0%AC + 24.6%Fe2(SO4)3, the maximum
bio-oil production was observed at 120 min, 620℃, and 450 W, generating 49.2% bio-oil. Meanwhile, using
1.0%HZSM-5 + 24.6%Fe2(SO4)3, the maximum bio-oil production was observed at 105 min, 620℃, and 525 W,
generating 42.2% bio-oil. The outcomes of the studies could be a basis for future clean fuel production utilizing
LRC that could reduce global carbon emission.

1. Introduction producing lower levels of tar) is highly required, namely microwave

pyrolysis (MP) with the presence of catalysts and receptors [7–9]. The
Global use of coal in power generation still shows dominance as advantages of this technology include highly product distribution and
compared to other fuels. Most of the coal quality in the world is still quality, and high energy efficiency [10–12]. The temperature rise rates
classified as low-rank coal (LRC). Currently, total LRC reserves, which and the final temperature of MP + catalyst + receptor are critical in
include the coal of sub-bituminous and lignite worldwide are 319,879 determining product distribution (i.e., high bio-oil production) [8,9].
million tons [1]. Utilization of LRC as a direct fuel is not efficient and Thus, the selection of catalyst + receptor is paramount in the application
economical, and causes environmental pollution. Thus, an alternative of MP technology. Catalysts based activated carbon and zeolite and
clean technology is required to process LRC into fuel, namely pyrolysis metal receptors are of interest because of their high reactivity and
[2]. abundant reserves, offering high economical return. Various zeolite
Some of the major products resulted from LRC pyrolysis are typically catalysts such as ultra-stable Y (USY), Linde type L (LTL), and ZSM-5
syngas, bio-oil, tar and char [3]. Of the main products, heavy tar must be [13–15], including carbon-based catalysts such as coconut activated
purified by fractional distillation to obtain a commercial product [4]. carbon (CAC), carbon nanotubes, and activated carbon (AC) [16,17], are
However, up to present, the main challenge of pyrolysis is low con­ also good alternatives. Meanwhile, metal-based receptors, namely Fe
ventional heating, resulting in liquid-yield dominated by tar, making the and Mg can be used to increase catalytic activity and char resistance
final product (i.e., bio-oil) cannot be used directly as fuel [5,6]. An [10].
alternative technology having better efficiency and performance (i.e., The concurrent use of zeolite catalysts and metal receptors can

Abbreviations: AC, Activated Carbon; ASTM, American Society for Testing and Materials; CAC, Coconut activated carbon; CP, Conventional catalytic pyrolysis;
FTIR, Fourier transform infrared; GC, Gas chromatography; GC-MS, Gas chromatography–mass spectrometry; LRC, Low rank coal; LTL, Linde type L; MP, Microwave
pyrolysis; SSA, Specific surface area; TWL, Total weight loss; USY, Ultra-stable Y; XRD, X-Ray Diffraction; ZSM, Zeolite Socony Mobil.
* Corresponding author.
E-mail address: [email protected] (M. Mahfud).

https://doi.org/10.1016/j.fuel.2022.124509
Received 17 December 2021; Received in revised form 23 April 2022; Accepted 3 May 2022
0016-2361/© 2022 Elsevier Ltd. All rights reserved.
B. Sardi et al. Fuel 324 (2022) 124509

Table 1
Characterization of coal and catalyst.
Sample Analysis of proximate Analysis of ultimate

M A V FC C H N St Odiff.

Sub-bituminous coal 6.54 11.86 43.56 38.04 74.75 6.87 0.76 5.41 12.21
AC catalyst 9.76 1.02 22.60 66.62 65.42 3.38 0.47 0.00 30.73

SiO2/Al2O3 Na2.2Al2Si91O18 H-Al2O3-SiO2 SiO2

HZSM-5 catalyst ≥ 97 <1 <1 <1

change the surface properties of the zeolite. Metal receptors such as Fe radicals, which are stabilized by hydrogen species formed by dehydro­
and Mg cause low temperature acid sites, improving zeolite catalytic genation of hydrocarbons [22,23]. The use of MP + ZSM-5 + Fe2SO4 on
activity. Zeolite USY + Mg performs outstanding in terms of increased LRC increased tar. Through the CP, the bio-oil was produced at 2.2%.
stability with decreased catalytic activity [13]. Other zeolites that are The tar yield increased from 7.0 to 9.5%, when the charge of the Fe2O3
generally used in catalytic pyrolysis are ZSM-5 and LTL, synthesized receptor increased from 0 to 10%. With loading of Fe2O3 at 10%, the
from direct hydrothermal. In addition, H-silica zeolite shows good per­ catalyst showed the best impact with an increase rate of 62.6% [14].
formance for the formation of hydrogen, phenol, and methane. The Previous studies mainly reported the use of LRC as the raw material
pyrolysis temperature and heating rate are generally within 400-600℃ of MP with catalysts of AC and ZSM-5 and metal receptors, focusing on
and 5℃/min [15]. product characteristics. However, they are still limited: (1) to overcome
The use of AC catalysts and metal receptors on MP has been reported the problem of increasing heavy-tar, and (2) to further investigate direct
in open literature. Reddy et al. [17] conducted a study of high rank coal conversion of LRC into bio-oil and syngas with high efficiencies. Also,
(HRC) + Fe + MP and LRC + Fe + MP to convert char into good quality the currently available literature only focuses on improving the quality
carbon nanostructure. They found that the addition of Fe receptor pro­ and yield of bio-oil by adding only a catalyst or a receptor. In this study,
duced nanoparticles and carbon-nanotubes in a relatively short time due AC and HZSM-5 were used as catalysts as these catalysts considered
to MP heating. Tar, char, and syngas yields are generally influenced by having capability of producing bio-oil with high efficiency. Also, the
the type of coal. The produced tars mainly contained aromatic com­ presence of Fe2(SO4)3 as a receptor was found to be reducing sulfur and
pound and the syngas majorly contained methane, carbon monoxide, ash content of the bio-oil through oxidation reactions [24]. Fe2(SO4)3 is
and hydrogen. Significant increase in tar and syngas was found when also considered low-cost metals that can reduce the production costs,
using high ash coals. Iqbal et al. [18] conducted a comparative study improving economic viability. Also, the effect of temperature rise rate
between MP + AC + CoMnOx and MP + CoMnOx under the same re­ and final temperature of CP + catalyst + receptor and MP + catalyst +
action conditions. They found that MP + AC + CoMnOx decreased CO2 receptor on product composition was evaluated. This study also explores
concentration of the syngas and increased catalyst activity and selec­ the process conditions (i.e., time, temperature, and input power) that
tivity of C2+ hydrocarbons. can offer maximum production of bio-oil. FTIR, GC–MS, density, and
MP has a number of heating advantages as compared to CP, including viscosity analyses were used to describe the produced bio-oil. Bio-oil is
non-contact, bulk, rapid, inside out, and selective heating [19]. Using expected to be equivalent to gasoline and diesel oil, whilst syngas will be
LRC, Wang et al. [14] compared MP with CP using metal receptors equivalent to hydrogen, methane, ethane, propane, and n-butane. The
(including MoS2, FeS2, and Fe3O4) and ZSM-5 catalyst. The addition of outcomes of this study could be a basis for clean-coal and advanced fuel
ZSM-5 + Fe2O3 was found to be increasing bio-oil production, including production technology using LRC as the raw-material.
heavy tar. At temperature of 694.9℃, input power of 700 W, and re­
action time of 15 min, the bio-oil and syngas were produced at 9.5% and 2. Material and method
49.7%, respectively. Liu and Yue [8] used MP + metal sulfide catalyst
(including FeS2 and MoS2) to convert LRC into bio-oil. They found that 2.1. Sample preparation, catalysts, receptors, and their characterization
high temperature rise rate increase bio-oil production. Also, the pro­
duced heavy oil and light oil were 4.5% and 67.6% using MoS2 catalyst, The preparation of LRC, Fe2(SO4)3 receptor, catalyst of HZSM-5 and
wherein the light oil content increased 10.3 times than that without the AC were carried out. Sub-bituminous LRC was mined from the Bobong
catalyst. As comparison, the yield of bio-oil with FeS2 and MoS2 catalysts Formation in the Taliabu Utara, Indonesia (-1.673139◦ , 124.561139◦ ).
was 27.1% and 28.4%, respectively. Zhou et al. [9] compared MP + non- The LRC contained high sulfur, high ash, with ultimate and proximate
catalyst with MP + FeS2 catalyst. They found that the change in product analyses presented in Table 1. The LRC was crushed and filtered to a
distribution was caused by an increase in the final temperature and the particle size of 4 mesh, and dried to a moisture content of <0.05%. To
temperature rise rate. The bio-oil and syngas products at MP + 12.0% reduce the high sulfur and ash of the LRC, desulfurization and deashing
FeS2 were 27.2% and 8.7%, with the bio-oil increasing 6.4% as were carried out with Fe2(SO4)3, made from a chemical reaction be­
compared to MP + non-catalyst treatment. Hence, FeS2 catalyst tween Fe and H2SO4, according to the study of Ehsani [24].
decreased tar while increasing fraction of light bio-oil. Wang et al. [10] Meanwhile, in order to support the pyrolysis performance, HZSM-5
used the MP + Fe3O4 receptor which showed the yield of syngas and bio- and AC were used. Wherein, the manufacture of HZSM-5 from ZSM-5
oil increased with an increasing receptor to LRC ratio and microwave and AC from CAC was conducted through calcination method. ZSM-5
power. and CAC purchased from the commercial market were heated in an
HZSM-5 + Fe and HZSM-5 + Ga in the reactor reduced oxygenated oven at 120℃ (for 720 min) and then stored in a desiccator. Then, the
and aliphatic compounds while increasing light aromatics. As compared catalyst was calcined at 500℃ at a speed of 0.02 L/min for 180 min.
to the CP, the content of aromatic chemical increased from 55.4% to Finally, the reduction with H2 gas at 550℃ and a speed of 0.02 L/min
81.8–89.6% [20]. Also, the product of light aromatic increased 2.9–3.1 was conducted for 120 min. After completion, the catalyst was cooled in
times. This was caused by dehydrogenation, carbon deposition, deoxy­ an apparatus by flowing N2 gas at a speed of 0.02 L/min until it reached
genation, and cracking. Among these two catalysts, HZSM-5 + Ga 50℃. The analysis of chemical composition of the HZSM-5 and AC are
showed higher selectivity for the removal of oxygen and light aromatic presented in Table 1. Characterization of LRC and AC was carried out
hydrocarbons [21]. The incorporation of a metal catalyst in the reaction using ASTM method (i.e., ultimate and proximate analysis). HZSM-5 was
system promotes hydrogen. The initial stage of coal pyrolysis produces analyzed using XRD.

2
B. Sardi et al. Fuel 324 (2022) 124509

Fig. 1. Schematics diagram of the MP system used in this study.

2.2. Experimental apparatus and process micromorphology was analyzed using energy dispersion spectrometer
(SEM-EDS, JSM-6360LV, JEOL Ltd. Japan). The analysis was carried out
Temperature variation was performed at 570-650℃, with an incre­ at a voltage of 30 kV (1.6 nm) via Supra 55 sapphire type SEM.
ment of 10℃. A mixture of 150 g of LRC (with 4 mesh sizes) with AC + X-ray diffraction analysis of the crystal structure of LRC, AC +
Fe2(SO4)3 and HZSM-5 + Fe2(SO4)3 at a ratio of 1.0%catalyst + 24.6% Fe2(SO4)3, HZSM-5 + Fe2(SO4)3, and LRC in char-yields were done using
receptor were prepared. Then, the pyrolysis was conducted at the a powder diffractometer. Diffractometer was equipped with a thallium-
mixture of LRC, catalyst, and receptor. Pyrolysis conditions were set up activated sodium iodide detector; copper K-α radiation, and a graphite
at a vacuum pressure of − 10 mmH2O, a frequency of 2.54 GHz, and an monochromatic at 30 mA (40 kV) was set up. The diffractometer was a
input power of 525 W for 60 min. The products generated were liquid (i. type-700 (XRD, Shimadzu (Guangzhou) Analysis and Technology Ser­
e., a phase of bio-oil and tar) at tray 1, tray 2, tray 3, and tray-end, vices Co., Ltd., in China). Range of scan was 2θ at a rate of 0.02℃/s
including syngas and char. A device circuits of catalyst and receptor- between 5◦ and 80◦ .
assisted MP is shown in Fig. 1. Variation of input power was set up at Infrared spectroscopy used FTIR spectrometer (FTIR, IR Prestige-21,
a catalytic pyrolysis (non-microwave) and MP + catalyst + receptor Shimadzu (Guangshou) Analysis and Technology Service Co., Ltd.,
(150–800 W), while variation of time was conducted at 15–135 min. The China) was used. The FTIR was used to analyze the organic functional
coal together with catalyst and receptor were then pyrolyzed at a vac­ groups of tar. Indices between 4000 and 500 cm− 1 were recorded at a
uum pressure of − 10 mmH2O for each maximum production condition resolution of 4 cm− 1 and an additional 32 scans were performed. The
of liquid and syngas (i.e., total weight loss). FTIR analysis was performed using potassium bromide (KBr) technique.
A high-quality non-background-effect spectrum under the same condi­
tions was prepared with the KBr slice blank assay.
2.3. Calculation and analysis method
GC-mass spectrometry type GC(6890)-MS(5973) (GC–MS, Agilent
technologies, Santa Clara, CA, USA) was used to analyze the tar
Eqs. (1) to (4) were used to calculate pyrolysis products, including
component. The GC had internal dimensions of 30 μm × 0.25 μm × 0.25
the density of the liquid, followed by determining the total weight loss
μm on column RXI-5 ms. The carrier syngas was high purity helium
(TWL).
(99.999%) at a flow rate of 0.00014 L/min.
mliquid mtray I + mtray II + mtray III + mtray end
Yliquid = x 100% = x 100% (1)
mfeed mcoal 3. Results and discussion

msolid mchar
Ysolid = x 100% = x 100% (2) This sections mainly discusses the results obtained from the experi­
mfeed mcoal
ment works, classified into several sections including, the effect of
temperature, determination of the maximum liquid and syngas (TWL)
Ysyngas = 100% − Yliquid − Ysolid (3)
production condition, and the analysis of the final products.
Total weight loss (TWL) = Yliquid + Ysyngas (4)

Solid products were analyzed proximate through ASTM according to

LRC characteristics in section 2.1. Then, the elemental composition and

3
B. Sardi et al. Fuel 324 (2022) 124509

Fig. 2. Temperature-rising at different blend ratio of HZSM-5 + Fe2(SO4)3 and

AC + Fe2(SO4)3 (CP: convention pyrolysis; MP: microwave pyrolysis).

3.1. Effect of temperature rise characteristics of pyrolysis products

Fig. 3. Carbon distribution of char, liquid and syngas products. (CP: conven­
tion pyrolysis; MP: microwave pyrolysis).
As temperature considered a major parameter that considerably af­
fects the characteristics of the MP products, the main results are pre­
5 + Fe2(SO4)3 to absorb microwaves was better than that of the LRC. The
sented as follows:
study showed that the use of AC, HZSM-5 and Fe2(SO)4 receptor in MP
was quite feasible to be used as absorbent and microwave activator in
3.1.1. Pyrolysis product
fast pyrolysis. The addition of a catalyst in the pyrolysis reaction showed
The catalysts played critical roles in the MP process. Various pyrol­
the distribution of carbon, solid, and syngas being converted to liquid
ysis products were found to be in the form of liquid (i.e., bio-oil and tar)
yields [9]. The effect of the MP with the addition of catalysts and re­
and solid. The characteristics of the products among those produced by
ceptors caused cracking of complex aromatic compounds and conse­
the catalysts [i.e., AC + Fe2(SO4)3 and HZSM-5 + Fe2(SO4)3] and those
quently increased the amount of free hydrogen [8].
produced by a non catalyst process (CP and MP) were compared.
TWL and yield of LRC were calculated using Eqs. (1) to (4). The
conventional pyrolysis, the yield of liquid was 33.9% under treatment of
3.1.2. Temperature effect on yield of product and distribution of carbon
a non-catalyst and a non-receptor. With the addition of 1.0%AC + 24.6%
The temperature rise rates and the final temperature of pyrolysis
Fe2(SO4)3 and 1.0%HZSM-5 + 24.6%Fe2(SO4)3 into the coal, the liquid
carried out with the addition of a catalyst and a receptor is the key to the
yield of CP was 43.1% and 41.7%. So, the addition of 1.0%AC + 24.6%
reaction in determining product distribution [8,9]. One of the factors
Fe2(SO4)3 and 1.0%HZSM-5 + 24.6%Fe2(SO4)3 caused a decrease in
that affect the rate of heating is temperature [25]. Thus, the temperature
char yield. In the MP, by adding 1.0%AC + 24.6%Fe2(SO4)3 and 1.0%
rise rates due to the addition of AC + Fe2(SO4)3 and HZSM-5 + Fe2(SO4)3
HZSM-5 + 24.6%Fe2(SO4)3 to the coal, the liquid yield was found to be
to the MP or the CP of the LRC processing is a factor that affects the yield
increased to 47.1% and 42.5%. Liquid yield in the MP has the same
and the product distribution. The temperature profiles of CP and MP at
changing trends as the CP. This was because the heating mechanism
different ratios of AC + Fe2(SO4)3 and HZSM-5 + Fe2(SO4)3 is presented
affecting the surface morphology and char yield [28]. An MP could
in Fig. 2. In terms of increasing temperature, MP was better than CP, MP
facilitate aromatization and cyclization of the LRC. The direct result of
+ HZSM-5 + Fe2(SO4)3 was better than CP + HZSM-5 + Fe2(SO4)3, and
the aromatization and collapse of coal micropores was a decline in the
MP + AC + Fe2(SO4)3 was better than CP + AC + Fe2(SO4)3. The length
area of specific surface area (SSA) [29]. In addition, the jet strength
of time for the MP temperature rise to reach 815℃ at the ratio of MP +
exercised by the product syngas provided a swell impetus for greatness
1.0%AC + 24.6%Fe2(SO4)3 was 18 min and MP + 1.0%AC + 24.6%
and the expansion of pores [30,31].
Fe2(SO4)3 to reach 815℃ required 19 min. Meanwhile, the length of
The addition of 1.0%AC + 24.6%Fe2(SO4)3 and 1.0%HZSM-5 +
time for the CP temperature increase to reach 815℃ at the ratio of CP +
24.6%Fe2(SO4)3 were chosen as the optimum rate, shown in Fig. 3.
1.0%AC + 24.6%Fe2(SO4)3 was 32 min and CP + 1.0%HZSM5 + 24.6%
Distribution of carbon added by AC + Fe2(SO4)3 and HZSM-5 +
Fe2(SO4)3 was 33 min. Meanwhile, the time required for the CP tem­
Fe2(SO4)3 produced higher liquid products, compared to without the
perature rises to reach 815℃ at the ratio of CP + non-catalyst + non-
addition of catalysts and receptors. This was because MP in LRC could
receptors were about 38 min. The effect of the length of time to reach the
cause decomposition of aromatic hydrocarbon functional and oxygen
final temperature of MP and CP in this study is in accordance with Zhou
groups. Groups elimination of hydrophilic this in hydroxyl, carbonyl,
et al. [26]. Wherein, the desired main liquid yield at MP + 8.3%MoS2 for
carboxyl, or aldehyde would weaken the moisture holding capacity of
up to 800℃ was detected before 25 min. Catalysts and receptors played
LRC [32–35].
an important role in suppressing the retrogressive reaction at this stage
by limiting radical passage and preventing recombination reactions
[3,27]. 3.2. Determination of maximum liquid and syngas production conditions
Meanwhile, the MP process temperature at different ratios of MP + on pyrolysis
AC + Fe2(SO4)3 and MP + HZSM-5 + Fe2(SO4)3 introduced trends of
various changing. However, the capacity of AC + Fe2(SO4)3 and HZSM- To determine the maximum liquid and syngas (TWL) production

4
B. Sardi et al. Fuel 324 (2022) 124509

Fig. 4. Effect of temperature on product yields: (a) AC + Fe2(SO4)3; and (b) HZSM-5 + Fe2(SO4)3.

conditions for the pyrolysis process, effects of temperature, power and significantly with time. On this basis, the reaction temperature of MP +
time are discussed below in details. AC + Fe2(SO4)3 at 4 mesh, 450 W, 60 min, − 10 mmH2O, loading 1.0%
AC + 24.6%Fe2(SO4)3 is 620℃.
3.2.1. Temperature effect on products of pyrolysis Fig. 4b shows liquid and syngas production from the LRC via MP +
The temperature of pyrolysis and the rate of temperature increase are HZSM-5 + Fe2(SO4)3. The results showed that the temperature was
generally influenced by the amount of charge and the type of catalyst obtained at 620℃ with a maximum TWL of 61.5%. The temperature
and receptor addition. The addition of a catalyst and a receptor on MP obtained from the effect of HZSM-5 + Fe2(SO4)3 was below the tem­
causes the complete breakdown of complex aromatic compounds and perature for the addition of ZSM-5 + Fe2O3 and Fe3O4 [10,14]. Study of
increases the amount of free H2 [8,27]. The effect of temperature on the the effect of ZSM-5 + Fe in liquid production from coal through MP had
pyrolysis of the LRC through MP + AC + Fe2(SO4)3 is shown in Fig. 4. been reported by Wang et al. [14]. At 694.9℃, the TWL and liquid were
The results showed that the temperature was obtained at 620℃ with a observed at 59.2% and 9.5%, respectively. The addition of ZSM-5 +
maximum TWL of 62.23 % (Fig. 4a). Fe2O3 and Fe3O4 was found to be supporting each other to maximize the
The temperature trend obtained from the effect of AC + Fe2(SO4)3 liquid production. The presence of ZSM-5 + Fe2O3 in MP causes the
was between the temperature for the addition of the CAC and the Fe3O4 microwave to effectively increase the liquid product (bio-oil), including
[10,16]. The study of the effect of CAC in the production of fuel from the heavy tar. The presence of Fe3O4 receptors caused the cracking of
coal through MP had been carried out by Mushtaq et al. [16]. At 326℃, aromatic complex compounds to occur completely and increase the
the TWL and liquid were 38.0% and 18.6%. Meanwhile, the study of the active free hydrogen [10]. Free hydrogen resulted in an increase in
effect of Fe3O4 in the production of fuel from coal through MP had been breaking down the heavy tar into bio-oil. Under conditions of MP +
carried out by Wang et al. [10]. At 770℃, the TWL and liquid were HZSM-5 + Fe2(SO4)3 at 4 mesh, power of 525 W, length of reaction of 60
44.6% and 4.7%, respectively. The presence of CAC in LRC causes an min, operating pressure of − 10 mmH2O, catalyst loading 1.0%HZSM-5,
even distribution of carbon to achieve pyrolysis conditions under the and receptor loading 24.6%Fe2(SO4)3, the temperature was found to be
microwave cavity environment. Thus, the liquid product composed of 620℃. The yield of pyrolysis products increased significantly when the
aromatic compounds, including phenol and naphthalene, increased maximum temperature of MP + AC + Fe2(SO4)3 and MP + HZSM-5 +

Fig. 5. Effect of microwave power on product yields: (a) AC + Fe2(SO4)3; and (b) HZSM-5 + Fe2(SO4)3.

5
B. Sardi et al. Fuel 324 (2022) 124509

Fig. 6. Effect of reaction time on product yield: (a) AC + Fe2(SO4)3; and (b) HZSM-5 + Fe2(SO4)3.

Fe2(SO4)3 was increased. The amount of liquid product (bio-oil) pro­ They found that at an input power of 0–700 W, the TWL, concentration
duced is proportional to the heating rate and the maximum temperature of liquid and syngas were observed at 55.7–59.2%, 6.4–9.5%, and
reached. Under these conditions, the maximum pyrolysis temperature 49.3–49.7%, respectively. These results indicate that an increase in
causes a larger rate of volatile matter release from hot coal particles, as power on the ZSM-5 + Fe2O3 and Fe3O4 caused an increase in liquid and
well as a greater likelihood of the pyrolysis process. syngas. The increase in the TWL of coal in MP with the addition of the
Fe3O4 receptor (23.8–68.5%) was greater than that of the ZSM-5 +
3.2.2. The effect of microwave power pyrolysis products Fe2O3 (55.7–59.2%) [10]. Thus, if the addition of HZSM-5 + Fe2(SO4)3
The yield of liquid and syngas products will increase with increasing combined in MP with a ratio of 1.0%HZSM-5 + 24.6%Fe2(SO4)3 it
ratio of catalyst and receptor to coal and input power [10]. The effect of causes an increase in TWL (57.3–60.2%) with the input power is 525 W.
power on LRC pyrolysis through MP, AC and HZSM-5 catalysts and The maximum TWL using both catalysts was 62.6% at 450 W with
Fe2(SO4)3 receptors is display in Fig. 5. The results showed that the input AC + Fe2(SO4)3. Then, the second highest was achieved at 60.2% using
power was obtained at 450 W, with a TWL of 62.6% (Fig. 5a). The input HZSM-5 + Fe2(SO4)3 at 525 W. This is due to the ability of LRC + 1.0%
power obtained from the effect of AC + Fe2(SO4)3 is quite low as AC + 24.6%Fe2(SO4)3 at tan δ = (~2.4) to convert microwave electrical
compared to the results of the previous study [10,16]. Mushtaq et al. energy into heat energy faster than the ability of LRC + 1.0%HZSM-5 +
[16] investigated the effect of CAC in the production of fuel from coal 24.6%Fe2(SO4)3 at tan δ = (~1.1). So that the ability to form total
through MP. They found that with an input power of 450–600 W, these products from liquid and syngas at the same optimum temperature re­
conditions resulted in TWL and liquid of 22.5–38.0% and 12.7–18.6%, quires power LRC + 1.0%AC + 24.6%Fe2(SO4)3 450 W lower than
respectively. As comparison, Wang et al. [10] analyzed the effect of power LRC + 1.0%HZSM-5 + 24.6% Fe2(SO4)3 525 W. The yield of
power on fuel products from coal through MP with the addition of re­ pyrolysis products increased significantly when the maximum input
ceptors. They found that at an input power of 380–700 W, a temperature power of MP + AC + Fe2(SO4)3 and MP + HZSM-5 + Fe2 (SO4)3 was
of 550-890℃ and time of 30 min, an increase in TWL, including con­ increased. The heating rate and temperature obtained at the maximum
centration of liquid and syngas had been observed at 23.8–68.5%, input power level are related to the increase in the liquid product (bio-
1.0–15.0%, and 22.8–53.5%, respectively. oil). Under these conditions, the maximum input rate of paralysis pro­
Several values have been reported in terms of the tangent of motes a faster release of volatile stuff from hot coal particles and a larger
dielectric loss at microwave frequency of 2.54 GHz. For instance, when chance of pyrolysis.
the LRC was used, this value (tan δ) can be 0.1 and when the HZSM-5
was used, this value (tan δ) can be 0.4 [36]; when the AC was used, 3.2.3. Reaction time effect on products of pyrolysis
this value (tan δ) was about 1.7 [37]; when the Fe2(SO4)3 was used, this The reaction time and pyrolysis temperature affect the distribution
value (tan δ) was found to be about 2.3 [38]; finally, when the Fe3O4 was and composition of the product [3]. MP + catalyst + receptor are one of
used, tan δ was observed at 7.5 and and when the Fe2O3 was used, this the factors that affect time. The study on the effect of the time of LRC
value (tan δ) can be 3.3 [39]. With these values, under MP condition, the through MP, AC and HZSM-5 catalysts and Fe2(SO4)3 receptors is display
TWL of LRC with the addition of Fe3O4 receptors (23.8–68.5%) was in Fig. 6. The results showed that the reaction time was obtained in the
greater than that with the AC (22.5–38.0%). Thus, if the addition of AC 120th min with a maximum TWL of 68.1% (Fig. 6a). The time obtained
+ Fe2(SO4)3 was combined with 1.0%AC + 24.6%Fe2(SO4)3, that con­ from the use of AC + Fe2(SO4)3 is quite long compared to the results of
dition would lead to an increase in TWL of 57.0–62.6% with an input previous studies such as Zhang et al. [40] and Liu and Xia [25]. Zhang
power of 450 W. et al. [40] investigated the production of fuel through MP + FeSO4. The
Fig. 5b shows liquid and syngas production from LRC via MP + yields of the TWL and liquid were 40.0% and 13.5%, respectively, for 30
HZSM-5 + Fe2(SO4)3. The results showed that the input power was min at 800 W. Meanwhile, Liu and Xia [25] examined the production of
achieved at 525 W with a maximum TWL of 60.2%. The input power fuel through MP + AC. The yields of the TWL and liquid were 35.6% and
obtained from the effect of HZSM-5 + Fe2(SO4)3 was quite low as 24.1%, respectively, for 45 min at 700 W and 750℃. The results showed
compared to the previous results conducted by Wang et al. [14] and that the MP heating effect of the melting temperature of the interacting
Wang et al. [10]. Reported by Wang et al. [14] the authors studied the material with the addition of 1.0%AC + 24.6%Fe2(SO4)3 can slow the
effect of ZSM-5 + Fe2O3 in liquid production from LRC through MP. temperature rise time of the LRC. With melting temperature of AC=

6
B. Sardi et al. Fuel 324 (2022) 124509

Fig. 7. XRD spectra of solid product.

(~3,680℃) and Fe2(SO4)3=(~480℃). Thus, the time of adding 1.0% which is operated at a maximum process condition of 620℃ tempera­
AC + 24.6%Fe2(SO)4 coal MP effectively improves the distribution and ture, 450 W power, and 120 min time. Meanwhile, the char of MP +
composition of the product. HZSM-5 + Fe2(SO4)3 is temperature 620℃, power 525 W, and time 105
Fig. 6b shows liquid and syngas production from LRC via MP + min. When MP + 1.0%AC + 24.6%Fe2(SO4)3 was applied, the ash
HZSM-5 + Fe2(SO4)3. The results showed that the time was obtained in content increased from 11.9 to 19.4% and the fixed carbon increased
the 105 min with a maximum TWL of 66.5%. The time obtained from the from 38 to 67%. While in the application of MP + 1.0%HZSM-5 + 24.6%
use of HZSM-5 + Fe2(SO4)3 is quite long compared to the results of Fe2(SO4)3, the ash content increased from 11.9 to 31.8% and fixed
previous studies such as Wang et al. [10] and Wang et al. [14]. The re­ carbon increased from 38.0 to 52.5%. In terms of water content and
sults showed that the heating effect of MP from the melting temperature volatile, using MP + 1.0%AC + 24.6%Fe2(SO4), the water content in
of the interacting material with the addition of 1.0%HZSM-5 + 24.6% char decreased from 6.5 to 4.1%, while volatile decreased from 43.6 to
Fe2(SO4)3 can accelerate the temperature rise time of the LRC. With 9.4%. In comparison, with MP + 1.0%HZSM-5 + 24.6%Fe2(SO4)3, the
melting temperature of HZSM-5 at SiO2/Al2O3=(~60), moisture content decreased from 6.5 to 4.1% and volatile matter
SiO2=(~1,710℃), Al2O3=(~2,072℃), and Fe2(SO4)3=(~480℃). Thus, decreased from 43.6 to 11.6%.
the time of adding 1.0%HZSM-5 + 24.6%Fe2(SO)4 coal MP effectively The increase in fixed carbon in MP + 1.0%AC + 24.6%Fe2(SO4)3 and
improves the distribution and composition of the product. The compo­ MP + 1.0%HZSM-5 + 24.6%Fe2(SO4)3 was caused by the heterogeneous
sition of the resulting bio-oil product is a complex mixture of organic gas phase reaction, such as CH4 decomposition on the solid carbon
compounds with various chemical groups. surface: CH4 →C +H2 [41,42]. Other reactions are secondary reactions,
The maximum TWL from the two catalyst treatments at the time such as reverse water–gas-shift (CO2 + H2 → CO + H2O) and reverse
variation was 68.1% at 120 min using AC + Fe2(SO4)3. The second Boudouard (C + CO2 → 2CO). Ash content of MP + 1.0%AC + 24.6%
largest was when using HZSM-5 + Fe2(SO4)3 at 66.5% and 105 min. Of Fe2(SO4)3 and MP + HZSM-5 + 24.6%Fe2(SO4)3′′ increased because ash
the two types of catalysts, AC has a time of 120 min, while the HZSM-5 content (%) = 100% – [fixed carbon (%) + moisture (%) + volatile
has a time of 105 min. This is due to the distribution and composition of matter (%)].”.
MP coal products with a melting temperature of AC = (~3,680℃) and As shown in Fig. 7, showing the char reaction pattern produced from
Fe2(SO4)3 = (~480℃) of 1.0%AC + 24.6%Fe2(SO4)3 higher than the MP + 1.0%AC + 24.6%Fe2(SO4)3 and MP + 1.0%HZSM-5 + 24.6%
melting temperature of HZSM-5 = SiO2/Al2O3, SiO2 = (~1,710℃), Fe2(SO4)3 at a temperature of 620℃, the crude coal reaction pattern and
Al2O3 = (~2,072℃), and Fe2(SO4)3 = (~480℃). That, the time for the the carbon black reaction pattern are plotted for reference. XRD spectra
formation of the total product from liquid and syngas at the same tem­ were used to observe sharp, crystal reaction peaks, and the results
perature requires a time of LRC + 1.0%AC + 24.6%Fe2(SO4)3 120 min showed that this XRD pattern correspond to the minerals inorganic
longer than the time of LRC + 1.0%HZSM-5 + 24.6%Fe2(SO4)3 105 min. present in the LRC. Most char crystal peaks of MP + 1.0%AC + 24.6%
The highest residence period increased TWL, liquid product (bio-oil), Fe2(SO4)3 and MP + 1.0%HZSM-5 + 24.6%Fe2(SO4)3 are SiO2, while the
and syngas from MP + AC + Fe2(SO4)3 and MP + HZSM-5 + Fe2(SO4)3. LRC crystal peaks are dominated by SiO2 and Ca4(Al8Si8O32). The XRD
Due to cracking, polymerization, and condensation processes of volatile spectrum shows that two broad carbon peaks corresponding to re­
organic compounds formed from lignite pyrolysis, the yield of the liquid flections (002) and (100) are observed at 2θ between 40 and 50◦ and 20
product rose dramatically as compared to the syngas fraction. and 30◦ .
The increased temperature causes the LRC to begin to undergo
3.3. Analysis of pyrolysis product devolatilization, and its molecules begin to link together through
dehydration and decarboxylation reactions. The presence of the ex­
The product characterization was analyzed in terms of solid and pected graphite like domains of carbon in the LRC and char (solid)
liquid as discussed below. structures was informed by the look of the peaks of reaction, equivalent
to (002) and (100) reflecting graphite [43]. The reaction peak observed
3.3.1. Solid products for the char of MP + 1.0%AC + 24.6%Fe2(SO4)3 produced in 620℃ was
LRC and solid products MP + 1.0%AC + 24.6%Fe2(SO4)3, MP + similar to the char of MP + 1.0%HZSM-5 + 24.6%Fe2(SO4)3 produced in
1.0%HZSM-5 + 24.6%Fe2(SO4)3 and were analyzed directly. Where, 620℃. However, if the char of MP + 1.0%AC + 24.6%Fe2(SO4)3 and MP
LRC is pretreatments into particle size 4 mesh and dried at 105℃ for 12 + 1.0%HZSM-5 + 24.6%Fe2(SO4)3 produced in 620℃ compared to
h. Meanwhile, the char from MP + AC + Fe2(SO4)3 is a solid product crude coal has a slightly lower carbon peak at 2θ between 20 and 30℃

7
B. Sardi et al. Fuel 324 (2022) 124509

Fig. 8. SEM images of solid product: (a) LRC; (b) Char of AC + Fe2(SO4)3; (c) Char of HZSM-5 + Fe2(SO4)3.

Fig. 9. FTIR spectra of bio-oil product.

according to the reaction in (002). This result is coherent for also 3.3.2. Liquid products
research informed in the papers [44,45], in which the carbon structure The FTIR of the liquid product is shown in Fig. 9. A number of ab­
stacking parameters did not change until the temperature of final of sorption peaks at 3300, 2583, 2375, 2083, 1675, and 625 cm− 1.
600℃ and risen rapidly into a temperature rise rate. However, crystal Described to the peak of IR absorption of the group of functions, the peak
peak of LRC is Ca4(Al8Si8O32) in contrast to the char crystal peak of MP of absorption at 3300 cm− 1 is included in the stretch vibrations of
+ 1.0%AC + 24.6%Fe2(SO4)3 and MP + 1.0%HZSM-5 + 24.6% phenol bonds and hydrogen bonds (i.e., –NH and –OH) [49,50]. The
Fe2(SO4)3 which is produced in 620℃. No crystal peaks of inorganic hydroxy stretch vibrations at MP, AC and HZSM-5 catalysts, and
Ca4(Al8Si8O32) were found in the char of MP + 1.0%AC + 24.6% Fe2(SO4)3 receptors at 3300 cm− 1 are clearly rather weak at MP + AC +
Fe2(SO4)3 and MP + 1.0%HZSM-5 + 24.6%Fe2(SO4)3. This can point out Fe2(SO4)3 and MP + HZSM-5 + Fe2(SO4)3. Thus, the hydroxy was
as heating of microwave selective produces hot spots of localized and decomposed into free hydrogen by microwave under the catalytic con­
induces reduction of carbothermic of Ca4(Al8Si8O32) in coal of crude to ditions of AC and HZSM-5 catalysts and Fe2(SO4)3 receptors. This shows
SiO2, CaO, and Al2O3 at a bulk temperature of lows of 550℃. that MP + AC + Fe2(SO4)3 and MP + HZSM-5 + Fe2(SO4)3 performed
LRC and solid products HZSM-5 + Fe2(SO4)3 and AC + Fe2(SO4)3 better, resulting in a higher amount of light bio-oil, especially using MP
were further analyzed by micromorphology. The SEM image is shown in + AC + Fe2(SO4)3 and MP + HZSM-5 + Fe2(SO4)3. Due to the catalytic
Fig. 8. Due to the heating of the MP, the char stress is warmer and activity of AC and HZSM-5 catalysts and Fe2(SO4)3 receptors, hydroxy
uniform in the finely shaped particle structure. Particles in MP are larger stretching vibrations occur during the MP. The absorption peaks of
than LRC for AC + Fe2(SO4)3 and HZSM-5 + Fe2(SO4)3 performance. The 2583, 2375, 2083, 1675, and 625 cm− 1 were considered to be vibrations
LRC surface is looser (Fig. 8a). Meanwhile, the surface of char AC + of aliphatic C–H. Thus, the addition of AC + Fe2(SO4)3 and HZSM-5 +
Fe2(SO4)3 (Fig. 8b) and HZSM-5 + Fe2(SO4)3 (Fig. 8c) was denser. This Fe2(SO4)3 is appropriate as the generation of hydrocarbons of fatty and
indicates that the fluidization states of the melt AC + Fe2(SO4)3 and cycloparaffins for the production of liquid, providing the added pyrol­
HZSM-5 + Fe2(SO4)3 can induce the MP catalytic reaction. AC and ysis advantage.
HZSM-5 catalysts and Fe2(SO4)3 receptors in MP function as absorbent Highlight bio-oil content with several times increase was observed
agents that convert the energy of microwave for energy of heat. The with the addition of MP + AC + Fe2(SO4)3 and MP + HZSM-5 +
results showed that hydrogen of fire was produced from attached of Fe2(SO4)3. Thus, the intermediate bio-oil and heavy bio-oil are decom­
hydrogen to the exposed metal activity points. This consequently in­ posed of easily into bio-oil of light by energy of microwave. The lower
creases the reaction of hydro. The structure of char space (Fig. 8c) intermediate and weight bio-oil content may be caused to the presence
seemed to disappear with much larger holes later irradiation of the of AC and HZSM-5 catalysts and Fe2(SO4)3 receptors. A big quantity of
microwave. Sahoo et al. [46] concluded that irradiation of a microwave hydrogen of free is produced, thus facilitated the reaction of hydroge­
may preferentially heat, minerals in coal premised on different proper­ nation. This conclusion is supportive by the spectra of FTIR of liquid and
ties of dielectric, baiting pyrite to rot. This is possible, because part of the solid yields. In using MP + AC + Fe2(SO4)3, the content of light bio-oil in
collapses of structure under stress of heating releasing many adhering tar reaches a maximum of 96.4% and content of heavy bio-oil at least
particles of char [47,48]. 3.6%. Meanwhile, when using MP + HZSM-5 + Fe2(SO4)3, the content of

8
B. Sardi et al. Fuel 324 (2022) 124509

Table 2 hydrocarbon radicals are formed, which can grab hydrogen and create
Relative proportions of the principal pyrolysis constituents in the oils. acorns. Aromatic compounds can be produced through secondary re­
actions of hydrocarbons at high temperatures [59,60]. The Diels-Alder
reaction is favored by high temperatures, which results in a rise in the
concentration of aromatic compounds in the oil [61].
Phenol made up a significant portion of the oil in MP + AC +
Fe2(SO4)3 and MP + HZSM-5 + Fe2(SO4)3, accounting for 5.2–29.9%
and 0.5–27.2%, respectively. According to the GC–MS peak area. The
phenol in MP + AC + Fe2(SO4)3 is mostly made up of phenol; phenol, 2-
methyl-; phenol, 3-methyl-; and phenol, 4-methyl-, which account for
0–29.9%, 5.2–8.7%, 0–17.4%, and 0–17.4% of the oil fraction in the
area, respectively. Phenol was only detected in the oil produced at
2.2–4.2 min of processing; phenol, 2-methyl- was only detected in the oil
produced at 5.0 min of processing; and phenol, 3-methyl-; and phenol, 4-
methyl- media were only detected after 5.0–21.1 min of pyrolysis when
the pyrolysis temperature reached 620 ◦ C. Meanwhile, phenol from MP
+ HZSM-5 + Fe2(SO4)3 mainly consists of phenol; phenol, 2-methyl-;
phenol, 3-methyl-; phenol, 4-methyl-; phenol, 2,4-dimethyl-; phenol,
2,5-dimethyl-; phenol, 2,6-dimethyl-; phenol, 2-ethyl-; and phenol, 3-
ethyl which represents 0–27.2%; 4.1–6.3%; 0–8.3%; 0–8.3%; 0–0.9%;
0–0.9%; 0–0.5%; 0–1.85%; and 0–1.24% of the oil fraction in the area.
Phenol was only detected in the oil produced at 2.3–4.2 min of pro­
cessing, while phenol, 2-methyl- was detected in the oil produced at
4.9–5.2%; phenol, 3-methyl- and phenol, 4-methyl- were only detected
in the oil produced at 5.2%; and phenol, 2,4-dimethyl-; phenol, 2,5-
dimethyl-; and phenol, 2,6-dimethyl- was detected at 6.14 min; and
phenol, 2-ethyl-; phenol, 3-ethyl was detected at 6.4 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, indicating 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
re-formation of free radical groups, resulting in low oxygen levels in the
oil phase [62].
Benzene from MP + AC + Fe2(SO4)3 and MP + HZSM-5 + Fe2(SO4)3
was benzenasulfonic acid, 4-hydroxy-, which accounted for 13.8% and
light bio-oil in tar reaches a maximum of 92.5% and content of heavy 12.6% of the peak area of GC–MS, respectively. During pyrolysis, the
bio-oil of at least 7.5%. Heavy bio-oil is broken down into bio-oil of light alkenes and alkanes of MP + AC + Fe2(SO4)3 and MP + HZSM-5 +
and little of intermediate bio-oil due to the synergy of MP + AC + Fe2(SO4)3 accounted for 5.5% and 18.9% oil, respectively, with peak
Fe2(SO4)3 and MP + HZSM-5 + Fe2(SO4)3. area and maximum concentrations reported at 2.1 and 2.3 min.
Table 2 shows the bio-oil content determined by GC–MS. Phenols, MP + AC + Fe2(SO4)3 liquid fuel is between C5–C10, C14–C20, and
ketones, benzene, alkenes, alkanes, and naphthalene are among the C21–C50 based on chemical composition (carbon atomic number). MP +
chemicals discovered as a result of the synergy between MP + AC + HZSM-5 + Fe2(SO4)3 liquid fuel is between C5–C10, C14–C20, and C21–C50
Fe2(SO4)3 and MP + HZSM-5 + Fe2(SO4)3 [51,52]. The temperature and based on chemical composition (carbon atomic number). C5–C10 is the
duration that produced the most aromatic chemicals, such as phenol and carbon atomic number comparable to gasoline, C14–C20 is the carbon
naphthalene, increased dramatically, whereas the benzene concentra­ atomic number equivalent to diesel oil, and C21–C50 is the carbon atomic
tion gradually declined. These findings are consistent with previously number equivalent to residual oil. The density and viscosity of liquid
published research findings [10]. In the next step of pyrolysis to the fuel from MP + AC + Fe2(SO4)3 are 0.74–0.77 g/mL and 0.85–0.88 cSt,
maximum temperature, some of the benzene is transformed to phenol respectively, confirming this. Meanwhile, the density and viscosity of
and naphthalene molecules. The pyrolysis temperature affects the pro­ MP + HZSM-5 + Fe2(SO4)3 liquid fuel were 0.74–0.78 g/mL and
duction of the phenol component during the process [53]. 0.77–0.80 cSt, respectively. Where liquid fuel density and standard
The large amount of lignin in lignite coal is linked to the highest viscosity are 0.72–0.89 g/mL and 0.77–0.99 cSt, respectively.
concentration of phenolic compounds in the pyrolysis oil. Because
lignite has a higher lignin content than biomass feedstock, which mostly 3.3.3. Syngas products
comprise hemicellulose and cellulose, pyrolysis of lignite produces more In MP + AC + Fe2(SO4)3 and MP + HZSM-5 + Fe2(SO4)3, overall
oil products. The generation of phenol from the breakdown of lignin has syngas yield declined with increasing 0–4% catalyst concentration, most
been documented [54]. The pyrolysis oil from the pyrolysis of MW likely due to decreased tar formation while other light hydrocarbon
lignite is significantly phenolic, according to GC–MS analysis. This in­ gases (C1-C4) increased. This could mean that the degradation of coal to
dicates oil reforming’s suitability for value-added chemicals [55]. carbon isn’t the only reaction that occurs with char, as various light
Alkoxyl groups, not C1-C4 alkyl groups, are present in all phenol de­ hydrocarbons (C1-C4) are detected. This is in line with the drop in char
rivatives, such as phenol 2-methyl; phenol 3-methyl; phenol 4-methyl; yield seen with the 0–4% catalyst, and could imply that the extra cata­
phenol-2,4-dimethyl; phenol 2,5-dimethyl; phenol 2,6-dimethyl; lyst is still contributing to the acceleration of light hydrocarbon syn­
phenol 2-ethyl; and phenol 3-ethyl. At 550–620 ◦ C, the mechanism of thesis during the coal pyrolysis reaction. For the pyrolysis reaction, the
the Diels-Alder reaction followed by dehydrogenation has been hy­ average composition of the gas leaving the reactor was examined. As a
pothesized as a factor responsible for the increase in aromatic in the function of the catalyst, the composition of gas (H2) and light hydro­
produced oil [56–58]. When long-chain aliphatic esters are pyrolyzed, carbons (CH4, C2H6, C3H8, and C4H10) changes. With the inclusion of a

9
B. Sardi et al. Fuel 324 (2022) 124509

Table 3 not a catalyst is present, the CO/CO2 ratio is always greater than 1.
Shows the relative proportions of the syngas’ main pyrolysis elements.
4. Conclusions

In this study, microwave pyrolysis (MP) was used to treat LRC (with a
size of 4 mesh) using AC + Fe2(SO4)3 and HZSM-5 + Fe2(SO4)3 as
catalyst + receptor. Effects on product distribution and process condi­
tions (time, temperature, and power) were evaluated.
AC + Fe2(SO4)3 and HZSM-5 + Fe2(SO4)3 increased the temperature
rate and final temperature of MP, causing changes in product distribu­
tion. Compared to non-microwave or conventional catalytic pyrolysis
(CP) at the same conditions (620℃ and 60 min), the treatment of MP +
1.0%AC + 24.6%Fe2(SO4)3 resulted in 47.1% bio-oil, 21.0% syngas,
31.9% char, with bio-oil production increasing 13.2%. Meanwhile, the
use of MP + 1.0%HZSM-5 + 24.6%Fe2(SO4)3, produced 42.5% bio-oil,
24.0% syngas, 33.5% char, with an increase in bio-oil yield of 8.6%.
Using 1.0%AC + 24.6%Fe2(SO4)3, the maximum bio-oil production
was observed at reaction time of 120 min, process temperature of 620℃,
and an input power of 450 W, resulting in 49.2% bio-oil, 18.9% syngas,
and 31.9% char. Meanwhile, using 1.0%HZSM-5 + 24.6%Fe2(SO4)3, the
maximum bio-oil production was observed at 105 min, 620℃, and 525
W, yielding 42.2% bio-oil, 24.3% syngas, and 33.5% char.
Thus, both treatments with 1.0%AC + 24.6%Fe2(SO4)3 and 1.0%
HZSM-5 + 24.6%Fe2(SO4)3 under microwave application positively
contributed to the conversion of LRC to bio-oil. The outcomes of the
study can be a basis for future clean fuel production by utilizing LRC,
reducing global carbon emissions.

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.

catalyst, the creation of these important hydrocarbons, particularly CH4, Acknowledgements

C2H6, C3H8, and C4H10, has enhanced. H2, CH4, and C2H6 contribute
0.003, 8.9, and 75.4% of the gas composition in the presence of a This activity is funded through BPPDN (Beasiswa Pendidikan Pas­
catalyst at MP + AC + Fe2(SO4)3. In MP + HZSM-5 + Fe2(SO4)3, the gas casarjana Dalam Negeri) No. B/67/D.D3/KD.02.00/2019 under the
composition (CH4, C2H6, C3H8, and C4H10) contributed 0.6, 22.9, 58.5, Education Fund Management Institute – Research, Technology and
3.7, and 14.2%, respectively, as indicated in Table 3. Higher Education Ministry and Finance Ministry of the Republic of
This drop in H2 generation is correlated with an increase in light Indonesia.
hydrocarbons, implying that the catalyst-assisted breakdown of LRC into
carbon is decreasing and the creation of these light hydrocarbons is References
increasing. As the catalyst concentration was increased, the amount of
hydrocarbons formed in the gas composition rose, showing that some [1] British Petroleum. BP Statistical Review of World Energy 2019. In: BP, editor. BP
catalysts can be activated and integrated in the gas phase as methoxy Stat Rev World Energy. 68th ed., London: BP Statistical Review of World Energy.
2019. 42.
groups or on the char surface. Some inorganic minerals on the charcoal [2] Miura K. Mild conversion of coal for producing valuable chemicals. Fuel Process
surface may be able to act as catalytically active microwave sites, Technol 2000;62:119–35. https://doi.org/10.1016/S0378-3820(99)00123-X.
allowing the catalyst to activate and break the first CH bond without [3] Kabe T, Ishihara A, Qian EW, Sutrisna IP, Kabe Y. Coal and Coal-Related
Compounds: Structures, Reactivity and Catalytic Reactions. vol. 150. 1st ed.
causing complete dehydrogenation and the creation of the observed C1
Netherlands: Elsevier Science. 2004.
to C4 molecules. [4] Gorin E. Chemistry of coal utilization. Second supplementary volume. New York:
It is also worth noting that these organic molecules continue to form Wiley. 1981.
[5] Reddy BR, Shravani B, Das B, Dash PS, Vinu R. Microwave-assisted and analytical
even after the coal has been completely devolatilized, under microwave-
pyrolysis of coking and non-coking coals: Comparison of tar and char compositions.
raised temperature conditions, and in the presence of a catalyst. The J Anal Appl Pyrolysis 2019;142:104614. https://doi.org/10.1016/j.
distribution of the gaseous products obtained in pure air shows a rela­ jaap.2019.05.003.
tively small amount of hydrocarbons and only for a reaction time of 60 [6] Song Y, Shi J, Fu J, Lan X, Zhang Q, Zhou J. Analysis of products by conventional
and microwave induced pyrolysis for low rank coal. Adv Mater Res 2012;524–527:
min to 90 min before completely disappearing. On the other hand, py­ 871–5. https://doi.org/10.4028/www.scientific.net/AMR.524-527.871.
rolysis of coal in the presence of a catalyst results in the formation of [7] Liu S, Tuo K, Wang L, Chen G, Ma W, Fang M. Microwave-assisted metal-catalyzed
light hydrocarbons. pyrolysis of low-rank coal: Promising option towards obtaining high-quality
products. J Energy Inst 2020;93:1602–14. https://doi.org/10.1016/j.
In all catalyst concentrations, CO concentration was always higher joei.2020.01.022.
than CO2, comparable to what was found in a recent work comparing [8] Liu C, Yue C. Metal Sulfide Assisted Coal Catalytic Hydrogenated Microwave
microwave and conventional coal pyrolysis under N2. Many secondary Pyrolysis. Mater Sci Forum 2020;999:178–90. https://doi.org/10.4028/www.
scientific.net/MSF.999.178.
reactions, such as reverse water–gas transfer (CO2 + H2 = CO + H2O), [9] Zhou J, Wu L, Zhou J, Liang K, Song Y, Tian Y, et al. Products optimization by FeS2
reverse Boudouard (C + CO2 = 2CO), or reconstitute the LRC (CH4 + catalyst for low-rank coal microwave pyrolysis. Fuel 2019;255:115759.
CO2 = 2H2 + 2CO), can occur during microwave pyrolysis of coal due to
the complicated chemical composition of coal. Regardless of whether or

10
B. Sardi et al. Fuel 324 (2022) 124509

[10] Wang N, Yu J, Tahmasebi A, Han Y, Lucas J, Wall T, et al. Experimental study on [36] Marland S, Merchant A, Rowson N. Dielectric properties of coal. Fuel 2001;80:
microwave pyrolysis of an Indonesian low-rank coal. Energy Fuels 2014;28(1): 1839–49. https://doi.org/10.1016/S0016-2361(01)00050-3.
254–63. [37] Omar R, Idris A, Yunus R, Khalid K, Isma MIA. Characterization of empty fruit
[11] Abdelsayed V, Shekhawat D, Smith M, Hammache S. Microwave-Assisted bunch for microwave-assisted pyrolysis. Fuel 2011;90:1536–44. https://doi.org/
Conversion of Low Rank Coal under Methane Environment. Energy Fuels 2019;33: 10.1016/j.fuel.2011.01.023.
905–15. https://doi.org/10.1021/acs.energyfuels.8b03805. [38] Al-harahsheh M, Kingman S, Bradshaw S. Scale up possibilities for microwave
[12] Singh S, Neculaes VB, Lissianski V, Rizeq G, Bulumulla SB, Subia R, et al. leaching of chalcopyrite in ferric sulphate. Int J Miner Process 2006;80:198–204.
Microwave assisted coal conversion. Microwave assisted coal conversion FUEL https://doi.org/10.1016/j.minpro.2006.04.003.
2015;140:495–501. [39] Zhou B, Zhou J, Zhang Z, Hu T, Yang L, Lin G. Dielectric characterizations and
[13] Rizkiana J, Guan G, Widayatno WB, Yang J, Hao X, Matsuoka K, et al. Mg-modified heating behavior of siderite in microwave field. Mater Res Express 2018;5:1–23.
ultra-stable Y type zeolite for the rapid catalytic co-pyrolysis of low-rank coal and https://doi.org/10.1088/2053-1591/aad9b2.
biomass. RSC Adv 2016;6(3):2096–105. [40] Zhang Y, Chen G, Wang L, Tuo K, Liu S. Microwave-Assisted Pyrolysis of Low-Rank
[14] Wang G, Li X, Wang Q, Li W. Effect of Fe-modified ZSM-5 catalyst during Coal with K2CO3, CaCl2, and FeSO4 Catalysts. ACS. Omega 2020;5(28):17232–41.
microwave assisted pyrolysis of Mengdong lignite for the oil production. IOP Conf [41] Fidalgo B, Fernandez Y, Dominguez A, Pis J, Menendez JA. Microwave-assisted
Ser: Mater Sci Eng 2020;729(1):012077. pyrolysis of CH4/N2 mixtures over activated carbon. J Anal Appl Pyrolysis 2008;
[15] Motazedi K, Karami D, Mahinpey N. Catalytic Pyrolysis of Low Rank Canadian 82:158–62. https://doi.org/10.1016/j.jaap.2008.03.004.
Boundary Dam Coal over ZSM-5 and LTL Zeolites. Can J Chem Eng 2015;93: [42] Domínguez A, Fidalgo B, Fernández Y, Pis JJ, Menéndez JA. Microwave-assisted
1651–6. https://doi.org/10.1002/cjce.22247. catalytic decomposition of methane over activated carbon for CO2-free hydrogen
[16] Mushtaq F, Mat R, Ani FN. Fuel production from microwave assisted pyrolysis of production. Int J Hydrogen Energy 2007;32:4792–9. https://doi.org/10.1016/j.
coal with carbon surfaces. Energy Convers Manag 2016;110:142–53. https://doi. ijhydene.2007.07.041.
org/10.1016/j.enconman.2015.12.008. [43] Hassan HMA, Abdelsayed V, Khder AERS, AbouZeid KM, Terner J, El-Shall MS,
[17] Reddy BR, Ashok I, Vinu R. Preparation of carbon nanostructures from medium et al. Microwave synthesis of graphene sheets supporting metal nanocrystals in
and high ash Indian coals via microwave-assisted pyrolysis. Adv Powder Technol aqueous and organic media. J Mater Chem 2009;19(23):3832.
2020;31:1229–40. https://doi.org/10.1016/j.apt.2019.12.017. [44] Abdelsayed V, Shekhawat D, Smith MW, Link D, Stiegman AE. Microwave-assisted
[18] Iqbal S, Davies TE, Hayward JS, Morgan DJ, Karim K, Bartley JK, et al. Fischer pyrolysis of Mississippi coal : A comparative study with conventional pyrolysis.
Tropsch Synthesis using promoted cobalt-based catalysts. Catal Today 2016;272: Fuel 2018;217:656–67. https://doi.org/10.1016/j.fuel.2017.12.099.
74–9. [45] Takagi H, Maruyama K, Yoshizawa N, Yamada Y, Sato Y. XRD analysis of carbon
[19] Mushtaq F, Mat R, Ani FN. A review on microwave assisted pyrolysis of coal and stacking structure in coal during heat treatment. Fuel 2004;83:2427–33. https://
biomass for fuel production. Renew Sustain Energy Rev 2014;39:555–74. https:// doi.org/10.1016/j.fuel.2004.06.019.
doi.org/10.1016/j.rser.2014.07.073. [46] Sahoo BK, De S, Meikap BC. Improvement of grinding characteristics of Indian coal
[20] Zhang Z, Chang H, Gao T, Lan T, Zhang J, Sun M, et al. Catalytic upgrading of coal by microwave pre-treatment. Fuel Process Technol 2011;92:1920–8. https://doi.
pyrolysis volatiles over metal-loaded HZSM-5 catalysts in a fluidized bed reactor. org/10.1016/j.fuproc.2011.05.012.
J Anal Appl Pyrolysis 2019;139:31–9. [47] Miura M, Kaga H, Tanaka S, Takahashi K, Ando K. Rapid microwave pyrolysis of
[21] Veses A, Puértolas B, Callén MS, García T. Catalytic upgrading of biomass derived wood. J Chem Eng Japan 2000;33:299–302. https://doi.org/10.1252/jcej.33.299.
pyrolysis vapors over metal-loaded ZSM-5 zeolites: Effect of different metal cations [48] Gong X, Guo Z, Wang Z. Effects of Fe2O3 on pyrolysis reactivity of demineralized
on the bio-oil final properties. Microporous Mesoporous Mater 2015;209:189–96. higher rank coal and its char structure. Huagong Xuebao/CIESC J 2009;60:2321–6.
https://doi.org/10.1016/j.micromeso.2015.01.012. [49] Petersen HI, Rosenberg P, Nytoft HP. Oxygen groups in coals and alginite-rich
[22] Taylor ND, Belit AT. Effects of Lewis acid catalysts on the cleavage of aliphatic and kerogen revisited. Int J Coal Geol 2008;74:93–113. https://doi.org/10.1016/j.
aryl-aryl linkages in coal-related structures. Fuel 1980;59:499–506. https://doi. coal.2007.11.007.
org/10.1016/0016-2361(80)90177-5. [50] Li Q, Lin B, Zhao C, Wu W. Chemical structure analysis of coal char surface based
[23] Olah GA, Bruce MR, Edelson EH, Husain A. Superacid coal chemistry: 1. HF:BF3 on Fourier-transform infrared spectrometer. Zhongguo Dianji Gongcheng Xuebao/
catalysed depolymerization—ionic hydroliquefaction of coals under mild Proceedings Chinese Soc Electr Eng 2011;31:46–52.
conditions. Fuel 1984;63:1130–7. https://doi.org/10.1016/0016-2361(84)90200- [51] Sonoyama N, Nobuta K, Kimura T, Hosokai S, Hayashi J-I, Tago T, et al. Production
X. of chemicals by cracking pyrolytic tar from Loy Yang coal over iron oxide catalysts
[24] Ehsani MR. Desulfurization of Tabas Coals Using Chemical Reagents. Iran J Chem in a steam atmosphere. Fuel Process Technol 2011;92(4):771–5.
Chem Eng Eng 2006;25:59–66. https://doi.org/10.30492/ijcce.2006.8091. [52] Zhang X, Lin B, Li Y. Experimental study on the effects of electrode materials on
[25] Liu Q, Xia H. The effect of additive on temperature rising characteristics during coal breaking by plasma. Fuel 2020;270:117085. https://doi.org/10.1016/j.
coal pyrolysis in microwave field. Adv Mater Res 2012;512–515:1790–4. https:// fuel.2020.117085.
doi.org/10.4028/www.scientific.net/AMR.512-515.1790. [53] Zeng F, He D, Guan J, Zhang Q. Effect of minerals in coal on the product yield of
[26] Zhou J, Wu L, Liang K, Zhang Q, Song Y, Tian Y, et al. The synergistic mechanism coal pyrolysis and phenols in the low-temperature tar. Adv Mater Res 2012;
on microwave and MoS2 in coal pyrolysis. J Anal Appl Pyrolysis 2018;134:580–9. 512–515:1129–36. https://doi.org/10.4028/www.scientific.net/AMR.512-
[27] Vasireddy S, Morreale B, Cugini A, Song C, Spivey JJ. Clean liquid fuels from direct 515.1129.
coal liquefaction: Chemistry, catalysis, technological status and challenges. Energy [54] Granada E, Eguía P, Comesaña JA, Patiño D, Porteiro J, Miguez JL. Devolatilization
Environ Sci 2011;4:311–45. https://doi.org/10.1039/c0ee00097c. behaviour and pyrolysis kinetic modelling of Spanish biomass fuels. J Therm Anal
[28] Ania CO, Parra JB, Menéndez JA, Pis JJ. Effect of microwave and conventional Calorim 2013;113:569–78. https://doi.org/10.1007/s10973-012-2747-y.
regeneration on the microporous and mesoporous network and on the adsorptive [55] Salema AA, Ani FN. Microwave-assisted pyrolysis of oil palm shell biomass using
capacity of activated carbons. Microporous Mesoporous Mater 2005;85:7–15. an overhead stirrer. J Anal Appl Pyrolysis 2012;96:162–72. https://doi.org/
https://doi.org/10.1016/j.micromeso.2005.06.013. 10.1016/j.jaap.2012.03.018.
[29] Tao S, Chen S, Tang D, Zhao X, Xu H, Li S. Material composition, pore structure and [56] Tahmasebi A, Yu J, Han Y, Yin F, Bhattacharya S, Stokie D. Study of Chemical
adsorption capacity of low-rank coals around the first coalification jump: A case of Structure Changes of Chinese Lignite upon Drying in Superheated Steam,
eastern Junggar Basin. China Fuel 2018;211:804–15. https://doi.org/10.1016/j. Microwave and Hot Air. Energy Fuels 2012;26:3651–60. https://doi.org/10.1021/
fuel.2017.09.087. ef300559b.
[30] Hong Y-d, Lin B-Q, Nie W, Zhu C-J, Wang Z, Li He. Microwave irradiation on pore [57] Cunliffe AM, Williams PT. Composition of oils derived from the batch pyrolysis of
morphology of coal powder. Fuel 2018;227:434–47. tyres. J Anal Appl Pyrolysis 1998;44:131–52. https://doi.org/10.1016/S0165-
[31] Li He, Lin B, Yang W, Zheng C, Hong Y, Gao Y, et al. Experimental study on the 2370(97)00085-5.
petrophysical variation of different rank coals with microwave treatment. Int J [58] Williams PT, Besler S. Polycyclic aromatic hydrocarbons in waste derived pyrolytic
Coal Geol 2016;154-155:82–91. oils. J Anal Appl Pyrolysis 1994;30:17–33. https://doi.org/10.1016/0165-2370
[32] Xia W, Yang J, Liang C. Effect of microwave pretreatment on oxidized coal (94)00802-7.
flotation. Powder Technol 2013;233:186–9. https://doi.org/10.1016/j. [59] Cypres R. Aromatic hydrocarbons formation during coal pyrolysis. Fuel Process
powtec.2012.09.010. Technol 1987;15:1–15. https://doi.org/10.1016/0378-3820(87)90030-0.
[33] Yuan S, Liu J-Z, Zhu J-F, Zhou Q-Q, Wang Z-H, Zhou J-H, et al. Effect of microwave [60] Fairburn JA, Behie LA, Svrcek WY. Ultrapyrolysis of n-hexadecane in a novel
irradiation on the propensity for spontaneous combustion of Inner Mongolia micro-reactor. Fuel 1990;69:1537–45. https://doi.org/10.1016/0016-2361(90)
lignite. J Loss Prev Process Ind 2016;44:390–6. 90203-3.
[34] Niu Z, Liu G, Yin H, Zhou C, Wu D, Yousaf B, et al. In-situ FTIR study of reaction [61] Chen G, Zohaib M, Sun B, Lin F, Yan B, Rajput G, et al. Pollutants formation,
mechanism and chemical kinetics of a Xundian lignite during non-isothermal low distribution, and reaction mechanism during WT pyrolysis : A review. J Anal Appl
temperature pyrolysis. Energy Convers Manag 2016;124:180–8. Pyrolysis 2021;157:105218. https://doi.org/10.1016/j.jaap.2021.105218.
[35] Ge L, Zhang Y, Wang Z, Zhou J, Cen K. Effects of microwave irradiation treatment [62] Wang C, Du Z, Pan J, Li J, Yang Z. Direct conversion of biomass to bio-petroleum at
on physicochemical characteristics of Chinese low-rank coals. Energy Convers low temperature. J Anal Appl Pyrolysis 2007;78:438–44. https://doi.org/10.1016/
Manag 2013;71:84–91. https://doi.org/10.1016/j.enconman.2013.03.021. j.jaap.2006.10.016.

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