Rev Chem Eng 2016; aop
Sabzoi Nizamuddin, Siddhartha Shrestha, Saadia Athar, Brahim Si Ali*
and Muhammad Ahmar Siddiqui
A critical analysis on palm kernel shell from
oil palm industry as a feedstock for solid char
production
DOI 10.1515/revce-2015-0062
Received October 28, 2015; accepted December 17, 2015
Abstract: Palm kernel shell (PKS) is one of the greatly
abundant residues in the palm oil industry. It possesses
physiochemical characteristics that build in it a poten-
tial to serve the production of valuable products, namely,
bio-fuels such as char, bio-oil, and bio-gas. This paper
presents the properties of PKS as a biomass feed for the
production of char. Characterizations of PKS in terms of
proximate and ultimate analyses, chemical composition,
and higher heating value (HHV in terms of MJ/kg) are pre-
sented and consequently compared to different oil palm
biomass such as empty fruit bunch (EFB), fiber, fronds,
and trunks. To illustrate and signify stability, the afore-
mentioned characteristics are discussed for PKS-char,
along with further comparison with EFB-char and coal.
In addition, recent advances in char production meth-
ods from PKS are presented and compared. Simultane-
ously, future prospects and major challenges towards
the utilization of PKS for the production of char are also
addressed.
Keywords: hydrothermal carbonization; oil palm wastes;
palm kernel shell; pyrolysis; solid char.
*Corresponding author: Brahim Si Ali, Faculty of Engineering,
University of Malaya, 50603, Kuala Lumpur, Malaysia,
e-mail: brahim@um.edu.my
Sabzoi Nizamuddin: Faculty of Engineering, Department of Chemical
Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia;
and Department of Chemical Engineering, Dawood University of
Engineering and Technology, Karachi, Sindh, Pakistan
Siddhartha Shrestha: Faculty of Engineering, Department of
Chemical Engineering, University of Malaya, 50603 Kuala Lumpur,
Malaysia
Saadia Athar: Department of Chemical Engineering, Dawood
University of Engineering and Technology, Karachi, Sindh, Pakistan
Muhammad Ahmar Siddiqui: Department of Chemical Engineering,
University of Karachi, Karachi, Sindh, Pakistan
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1 Introduction
Oil palm (Elaeis guineensis) is one of the leading perennial
oleaginous food crops planted for the production of edible
cooking oil (Chang 2014). Currently, Malaysia ranks first
in terms of oil palm production and exportation, contrib-
uting about 40% to 60% of the total worldwide produc-
tion of oil palm (Chew and Bhatia 2008, Fan et al. 2011).
Due to higher oil yield (approximately 4.87 t/ha/year), the
demand and supply of oil palm is increasing rapidly in
comparison to other food crops. This is 6.5, 8, and 13 times
higher than that of rapeseed, sunflower, and soybean,
respectively (Tye et al. 2011, Chang 2014). As a result, the
amount of oil palm produced in Malaysia has also gone
up. The production has risen to 18.8 million tons in 2012
from 4 million tons since 1985 (Chang 2014).
However, when summed together with the produc-
tion of edible oil, oil palm industries also retain a large
amount of oil palm wastes during transportation and
processing. In fact, only 10% of oil palm trees accounts
for oil; the remaining 90% is regarded as waste (Basiron
2007, Kelly-Yong et al. 2007, Lee and Ofori-Boateng 2013).
The main goal, however, remains to be the adequate pro-
vision and supply of cheap biomass. This accomplish-
ment seeks the appropriate selection of chemicals, fuels,
and alternative materials that serve to be cost-compet-
itive in comparison to regular fuel products (Sadeghin-
ezhad et  al. 2014). Different forms of oil palm industry
biomass feedstock used for bio-fuels and chemicals pro-
duction are shown in Figure 1. Currently, environmental
concerns have risen, as these heavy amounts of oil palm
wastes are either incinerated in mills for heat production
or dumped arbitrarily. Thus, an immediate focus on the
utilization of oil palm wastes is a necessity both for the
present and for the future. Oil palm waste is a type of
biomass; it can be utilized to generate heat and energy,
along with production of biomass-based products such
as bio-oil, biodiesel, bio-gas, methanol, and solid char.
These applications can aid effectively towards minimiza-
tion of environmental pollution that is visualized to have
2      S. Nizamuddin et al.: PKS from oil palm industry as a feedstock for solid char production

Figure 1: Major types of oil palm biomass used as a feedstock for bio-fuel production. (A) Oil palm fronds, (B) oil palm trunks, (C) EFB,
(D) oil palm roots, (E) oil palm leaves, (F) oil palm fresh fruits, (G) PKS, (H) palm kernels, (I) palm kernel seeds. Reproduced from Lee and
­Ofori-Boateng (2013) with permission from Springer.

been caused by dumping or incinerating the oil palm
wastes haphazardly.
Generally, oil palm wastes are obtained as palm
kernel shell (PKS), empty fruit bunch (EFB), and palm
fiber following the palm oil extraction procedure.
Approximately 0.3 ton of PKS is produced on the extrac-
tion of 1 ton of oil. In addition to that, 0.7 ton of palm
fiber and 1 ton of EFB are produced as industrial wastes
from each ton of oil production (Dalimin 1995). Although
production of PKS is less in amount, PKS is more valu-
able due to its high energy, low ash, and low sulfur con-
tents. PKS is produced from the milling of oil palm fruits.
Annual production of PKS in Malaysia is about 2.4 million
tons, nearly equivalent to 45.84 PJ (petajoule) of energy
unit (Abnisa et al. 2011, Arami-Niya et al. 2011). Up to the
present, the possibility of using PKS as a biomass feed-
stock for the production of bio-fuels (bio-oil, bio-gas,
solid char), activated carbon, and energy recovery has
been being explored (Arami-Niya et al. 2011, Kean et al.
2013, Mubarak et  al. 2014). These efforts have intrigued
a realization towards the potential of PKS to be utilized
as a green energy fuel. Among other applications, char is
one of the promising solid bio-fuel known for its extraor-
dinary properties. These properties include high carbon
content, low fiber structure, and high-energy density.
Furthermore, it promises environmental benefits and is
henceforth also regarded as green charcoal. Char can be
produced from most biomass such as agricultural wastes,
dung, woodchips, and fire wood. Char has numerous
applications such as the following:
–– as carbon material in fertilization of soil, a substitute
to the activated carbon or carbon black, and a catalyst
(Kleinert and Wittmann 2009, Funke and Ziegler 2010,
Rillig et al. 2010, Libra et al. 2011, Du et al. 2012, Kang
et al. 2012, Berge et al. 2013, Parshetti et al. 2013);
–– as absorbent for separation and purification, catalyst
support, solvent recovery, and automobile exhaust
emission control (Zanzi 2001);
–– as fuel in boilers in the form of briquettes or mixed
with other biomass like sugar cane bagasse; and

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 S. Nizamuddin et al.: PKS from oil palm industry as a feedstock for solid char production      3
–– for production of activated carbon and carbon nano-
tubes and further can be processed as well to form
hydrogen-rich gas (Goyal et al. 2008).
In this paper, fuel characteristics such as higher heating
value (HHV), chemical composition, and proximate and
ultimate analyses of PKS are discussed. These character-
istics are further compared to the characteristics of EFB,
fibers, fronds, and trunks to justify the latter’s appro-
priateness as a feed for char production. Moreover, the
characteristics of the char produced from PKS are also
compared to those of EFB-char and coal to reveal addi-
tional advantages. The recent advances in most common
thermo-chemical methods of char production (­pyrolysis
and hydrothermal carbonization) are also addressed.
The effect of operating parameters on fuel properties and
process is also discussed in the same review to show their
influence on yield of char and its quality. Furthermore,
major challenges and future prospects for the utilization
of PKS as a biomass feed for char production are also dis-
cussed, with possible suggestions of ways to tackle the
challenges upfront.
2 S
 tatistics, background, and
­characteristics of PKS
The shell produced from milling of palm seeds is known
as PKS. The shell is an endocarp, a layer that surrounds
the palm kernels, seeds, or kernels. It is produced when
the residual nuts from the screw press are crashed
mechanically to extract the kernels. In tropical regions
such as Malaysia and Indonesia, with the increase of oil
palm production, oil palm biomass residues in the form
of PKS also increase significantly. Currently, the world’s
annual generation of PKS is about 11.1 million tons. Previ-
ously, however, it was 2.52 and 4.3 million tons in 2004
and 2006, respectively (Lee and Ofori-Boateng 2013). It is
believed that an estimated amount of only 30% of these
wastes is being utilized by oil mills for power generation.
PKS is a lingo-cellulosic type of biomass, the main
components of which include cellulose, hemicellulose,
and lignin (Abnisa et  al. 2011). Lignocellulosic materials
possess massive potential to be used as biomass feedstock
to generate heat and power and also to produce bio-fuels
(Hoekman et  al. 2011, Liu et  al. 2013). Besides lignocel-
lulosic components, PKS is also composed of extractive
components. The extractive components comprise the
soluble portion of an extract from biomass that consists
of proteins, fatty acids, oils, wax, and minerals such as
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phosphorous, magnesium, potassium, and calcium. Like
other biomass and fossil fuels, PKS is also characterized
by proximate and ultimate analysis (Unz et al. 2010). These
properties vary with growing environment, time, and age
(Lewandowski and Heinz 2003, Pordesimo et  al. 2005,
Christian et  al. 2006). The proximate analysis incorpo-
rates the quantifiable determination of fixed carbon, vola-
tile matters, ash, and moisture content in biomass or fuel
(Khan et al. 2009). The purpose of proximate analysis is to
find the ratio of combustible substances (fixed carbon and
volatile matter) to non-combustible constituents (ash and
moisture content), which enables determination of the
energy content of biomass and fuels. On the other hand,
ultimate analysis defines the elemental composition in
terms of hydrogen, carbon, nitrogen, oxygen, and sulfur
(Khan et  al. 2009). Ultimate analysis aims to determine
the composition and quantity of the gas emitted during
the combustion process as well as the amount of oxygen
required for burning biomass and fuels (Chang 2014). It
is because these properties aid in the characterization of
the fuels and lead to the design of proper applications that
they are referred to as primary properties, which need to
be identified.
The ultimate analysis, proximate analysis, chemical
composition, inorganic composition, and HHV of PKS are
listed and compared to those of EFB, oil palm trunk, oil
palm fronds, and oil palm fibers in Table 1. Compared to
EFB and palm fiber, PKS contains a higher amount of vola-
tile matter (66–78%). Therefore, it is easier to ignite (Omar
et  al. 2011). PKS has higher carbon content than that of
EFB, oil palm fibers, trunks, and fronds, making it more
suitable as a solid fuel than the rest. Moreover, the fixed
carbon in PKS is present in substantial quantity (13–23%);
this is sufficient to generate a significant amount of heat
by burning PKS. PKS has a higher fixed carbon to vola-
tile matter ratio and lower moisture to ash content ratio.
Higher ratios of fixed carbon to volatile matters and lower
ratios of moisture to ash enhance the ratio of combustible
to non-combustible substances resulting in higher HHV
(15.9–22.14 MJ/kg). The HHV of PKS is comparable to that
of hardwood (17.63–20.81 MJ/kg) and softwood (19.66–
20.63 MJ/kg) (Garcia-Perez et al. 2007, Telmo and Lousada
2011). In addition, the amount of ash present in PKS is also
small.
The small variations between elemental composition
of woods and PKS (Garcia-Perez et  al. 2007, Ghani et  al.
2013) indicate that PKS as a fuel will also consume the
same amount of air as wood consumes during combustion.
Similarly, PKS would offer same benefits as wood would
offer over fossil fuels when there is less emission of GHGs
(Estrellan and Iino 2010). A higher carbon percentage and
 Table 1: Characteristics of oil palm wastes; PKS, EFB, trunks, fibers, and fronds.

Properties   PKS   EFB   Fibers   Fronds  Trunk  References

Molecular formula   CH1.61O0.51   CH1.69O0.54   CH1.80O0.62   –  –  Yang et al. 2005

HHV (MJ/kg)   15.9–22.1  16.9–20.0  17.0–19.1  18.8  18.8  Hussain et al. 2006, Chaiyaomporn and Chavalparit 2010, Tye et al. 2011, Jamari and Howse
2012, Mohammed et al. 2012, Jamaluddin et al. 2013, Asadieraghi and Wan Daud 2014
Fuel density (kg/m3)  1430   –   750   –  –  Lee and Ofori-Boateng 2013
Proximate analysis (%)
Moisture content   2.8–30.0   8.0–63.5   4.8–36.4   14.7  13.6  Werther et al. 2000, Hussain et al. 2006, Arami-Niya et al. 2010, Chaiyaomporn and Chavalparit
2010, Yuliansyah et al. 2010, Butler et al. 2011, Jamari and Howse 2012, Mohammed et al.
2012, Abnisa et al. 2013, Asadullah, et al. 2013, Jamaluddin et al. 2013, Lee and Ofori-Boateng
2013, Salema et al. 2013, Asadieraghi and Wan Daud 2014
Volatile matter   66.1–78.0  32.6–78.2  46.3–73.7  82.5  83.9  Werther et al. 2000, Hasegawa, et al. 2004, Hussain et al. 2006, Arami-Niya et al. 2010,
Chaiyaomporn and Chavalparit 2010, Yuliansyah et al. 2010, Jamari and Howse 2012,
Mohammed et al. 2012, Abnisa et al. 2013, Asadullah et al. 2013, Jamaluddin et al. 2013, Lee
and Ofori-Boateng 2013, Salema et al. 2013, Asadieraghi and Wan Daud 2014, Lim et al. 2014
Fixed carbon   13.0–23.0  3.0–16.5   12.0–23.6  17.5  16.1  Werther et al. 2000, Hasegawa et al. 2004, Hussain et al. 2006, Arami-Niya et al. 2010,
Chaiyaomporn and Chavalparit 2010, Yuliansyah et al. 2010, Jamari and Howse 2012,
Mohammed et al. 2012, Abnisa et al. 2013, Asadullah et al. 2013, Jamaluddin et al. 2013, Lee
and Ofori-Boateng 2013, Salema et al. 2013, Asadieraghi and Wan Daud 2014, Lim et al. 2014
Ash   1.0–16.3   1.0–6.8   5.3–8.4   1.8  2.2  Minowa et al. 1998, Werther et al. 2000, Hasegawa et al. 2004, Hussain et al. 2006, Kelly-Yong
et al. 2007, Chew and Bhatia 2008, Arami-Niya et al. 2010, Chaiyaomporn and Chavalparit 2010,
Yuliansyah et al. 2010, Butler et al. 2011, Varman and Saka 2011, Jamari and Howse 2012,

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Mohammed et al. 2012, Abnisa et al. 2013, Asadullah et al. 2013, Jamaluddin et al. 2013, Lee
and Ofori-Boateng 2013, Salema et al. 2013, Asadieraghi and Wan Daud 2014, Lim et al. 2014
Elemental analysis (%)

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Carbon   36.7–56.1  43.8–49.0  47.8–51.5  47.2  47.5  Minowa et al. 1998, Werther et al. 2000, Hasegawa et al. 2004, Hussain et al. 2006, Arami-
Niya et al. 2010, Chaiyaomporn and Chavalparit 2010, Mazaheri et al. 2010, Yuliansyah et al.
2010, Butler et al. 2011, Jamari and Howse 2012, Mohammed et al. 2012, Abnisa et al. 2013,
4      S. Nizamuddin et al.: PKS from oil palm industry as a feedstock for solid char production

Asadullah et al. 2013, Jamaluddin et al. 2013, Kean et al. 2013, Lee and Ofori-Boateng 2013,
Salema et al. 2013, Asadieraghi and Wan Daud 2014, Lim et al. 2014
Oxygen   35.6–58.1  38.0–49.7  38.2–44.5  46.6  45.9  Minowa et al. 1998, Werther et al. 2000, Hasegawa et al. 2004, Hussain et al. 2006, Arami-
Niya et al. 2010, Chaiyaomporn and Chavalparit 2010, Mazaheri et al. 2010, Yuliansyah et al.
2010, Butler et al. 2011, Jamari and Howse 2012, Mohammed et al. 2012, Abnisa et al. 2013,
Asadullah et al. 2013, Jamaluddin et al. 2013, Kean et al. 2013, Lee and Ofori-Boateng 2013,
Salema et al. 2013, Asadieraghi and Wan Daud 2014, Lim et al. 2014
Hydrogen   4.6–7.5   5.5–6.1   5.6–7.4   5.9  5.9  Minowa et al. 1998, Werther et al. 2000, Hasegawa et al. 2004, Hussain et al. 2006, Arami-
Niya et al. 2010, Chaiyaomporn and Chavalparit 2010, Mazaheri et al. 2010, Yuliansyah et al.
2010, Butler et al. 2011, Jamari and Howse 2012, Mohammed et al. 2012, Abnisa et al. 2013,
Asadullah et al. 2013, Jamaluddin et al. 2013, Kean et al. 2013, Lee and Ofori-Boateng 2013,
Salema et al. 2013, Asadieraghi and Wan Daud 2014, Lim et al. 2014
 Table 1 (continued)

Properties   PKS   EFB   Fibers   Fronds  Trunk  References

Nitrogen   0.08–2.0   0.1–0.6   1.5–5.4   0.2  0.5  Werther et al. 2000, Hussain et al. 2006, Arami-Niya et al. 2010, Chaiyaomporn and Chavalparit
2010, Mazaheri et al. 2010, Yuliansyah et al. 2010, Jamari and Howse 2012, Mohammed et al.
2012, Abnisa et al. 2013, Asadullah et al. 2013, Jamaluddin et al. 2013, Kean et al. 2013, Lee
and Ofori-Boateng 2013, Asadieraghi and Wan Daud 2014, Lim et al. 2014
Sulfur   0.03–0.4   –   0.3–0.5   0.1  0.1  Minowa et al. 1998, Werther et al. 2000, Hussain et al. 2006, Chaiyaomporn and Chavalparit
2010, Mazaheri et al. 2010, Yuliansyah et al. 2010, Mohammed et al. 2012, Asadullah et al.
2013, Jamaluddin et al. 2013, Lee and Ofori-Boateng 2013, Asadieraghi and Wan Daud 2014,
Lim et al. 2014
Inorganic composition (%)
K2O   0.6–1.3   2.2–40.0   9.0–15.6   8.29  24.5  Chaiyaomporn and Chavalparit 2010, Yuliansyah et al. 2010, Mohammed et al. 2012, Lee and
Ofori-Boateng 2013, Asadieraghi and Wan Daud 2014, Lim et al. 2014
CaO   0.5   0.8 15.5   9.0–20.8   52.7  23.5  Chaiyaomporn and Chavalparit 2010, Yuliansyah et al. 2010, Mohammed et al. 2012, Lee and
Ofori-Boateng 2013, Asadieraghi and Wan Daud 2014, Lim et al. 2014
Si2O   3.0–16.5   1.5–2.3   26.0–63.2  12.2  14.9  Chaiyaomporn and Chavalparit 2010, Yuliansyah et al. 2010, Mohammed et al. 2012, Lee and
Ofori-Boateng 2013, Asadieraghi and Wan Daud 2014, Lim et al. 2014
MgO   0.8–1.8   0.5–3.7   3.8–4.2   16.0  15.6  Chaiyaomporn and Chavalparit 2010, Yuliansyah et al. 2010, Mohammed et al. 2012, Lee and
Ofori-Boateng 2013, Asadieraghi and Wan Daud 2014, Lim et al. 2014
Fe2O3   0.08–4.9   0.1–5.8   3.9–9.7   0.4  0.7  Chaiyaomporn and Chavalparit 2010, Yuliansyah et al. 2010, Mohammed et al. 2012, Lee and
Ofori-Boateng 2013, Asadieraghi and Wan Daud 2014, Lim et al. 2014
Al2O3   0.24–2.1   0.1–0.8   2.7–4.5   0.2  0.3  Chaiyaomporn and Chavalparit 2010, Yuliansyah et al. 2010, Mohammed et al. 2012, Lee and
Ofori-Boateng 2013, Asadieraghi and Wan Daud 2014, Lim et al. 2014

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P2O5   0.6–1.0   0.4–4.3   2.8–6.8   2.43  8.7  Chaiyaomporn and Chavalparit 2010, Yuliansyah et al. 2010, Mohammed et al. 2012, Lee and
Ofori-Boateng 2013, Asadieraghi and Wan Daud 2014, Lim et al. 2014

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Chemical composition (%)
Hemicellulose   21.6–22.7  28.0–65.6  22.2–38.8  17.1–24.2  21.2–34.4  Minowa et al. 1998, Rosli et al. 2004, Kelly-Yong et al. 2007, Chew and Bhatia 2008, Mazaheri
et al. 2010, Yuliansyah et al. 2010, Varman and Saka 2011, Mohammed et al. 2012, Lee and
Ofori-Boateng 2013
Cellulose   20.8–27.7  35.7–62.9  20.8–51.1  31.0–62.3  31.7–41.2  Minowa et al. 1998, Rosli et al. 2004, Kelly-Yong et al. 2007, Chew and Bhatia 2008, Mazaheri
et al. 2010, Yuliansyah et al. 2010, Varman and Saka 2011, Mohammed et al. 2012, Lee and
Ofori-Boateng 2013
Lignin   44.0–50.7  22.0–36.6  14.3–28.5  14.8–22.9  17.1–29.6  Minowa et al. 1998, Rosli et al. 2004, Kelly-Yong et al. 2007, Chew and Bhatia 2008, Mazaheri
et al. 2010, Yuliansyah et al. 2010, Varman and Saka 2011, Mohammed et al. 2012, Lee and
Ofori-Boateng 2013
Extractives   10.3   5.7   6.3–7.6   1.8–29.0  2.8–16.3  Minowa et al. 1998, Rosli et al. 2004, Kelly-Yong et al. 2007, Mazaheri et al. 2010, Yuliansyah
et al. 2010, Mohammed et al. 2012, Lee and Ofori-Boateng 2013
S. Nizamuddin et al.: PKS from oil palm industry as a feedstock for solid char production      5
6      S. Nizamuddin et al.: PKS from oil palm industry as a feedstock for solid char production
a lower oxygen percentage are considered to improve com-
bustion properties (Khan et al. 2009, Sevilla et al. 2011).
The lingo-cellulosic components (hemicellulose,
lignin, and cellulose) present in PKS signify that a number
of bio-chemical and physio-chemical conversion methods
are possible. However, due to complex structures of lingo-
cellulosic components, they are poorly understood. Lignin
is a complex polymer of phenyl propane united with an
aromatic backbone. Cellulose is a linear polysaccharide
with a number of glucose monosaccharide units bonded
together by beta-linkages. Hemicellulose is a branched
polymer of five to six carbon saccharides such as glucose,
mannose, xylose, galactose, and arabinose (Rubin 2008).
The structural strength of PKS is provided by the complex
hydrogen bonds between different layers of cellulose
together with cross-linkage of lignin with both hemicel-
lulose and cellulose (Dashtban et al. 2010). Thus, conver-
sion of PKS into valuable chemicals and bio-oil may not
result into high production and yield rates. Nevertheless,
to reduce such shortcomings, pretreatment is conducted
to break the lignin bonds and disrupt the structure of PKS.
Nevertheless, high lignin content and lower cellulose
and hemicellulose contents of PKS compared to EFB, oil
palm fronds, oil palm trunks, and oil palm fibers support
the production of char from PKS rather than PKS-based
chemicals or other forms of bio-fuels. Biomass contain-
ing a higher amount of lignin content has been shown
to produce more char (Mok et  al. 1992, Antal and Grønli
2003), whereas biomass with high content of cellulose
and hemicellulose has shown support towards the pro-
duction of liquid and gaseous products. Kang et al. (2012)
studied hydrothermal conversion with varying ratios of
lignin and cellulose. The study reported that char yields
increased and aqueous and gaseous products decreased
with increasing lignin content. The inorganic composition
of PKS in ash percentage is 0.60% K2O, 2.96% Si2O, 0.83%
MgO, 0.48% CaO, 0.59% P2O5, 0.24% Al2O3, and 0.08%
Fe2O3.
3 R
 ecent advances in conversion
processes for char production
from PKS
Two major technologies available to produce bio-fuels
from biomass are thermo-chemical and bio-chemical
conversion. The bio-chemical processes use enzymes
and micro-organisms as catalyst to convert biomass into
bio-fuels. This process includes fermentation, anaerobic
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digestion, transesterification, and composting (Lee and
Ofori-Boateng 2013). However, this technology is limited
only to produce liquid and gaseous bio-fuels rather than
solid bio-fuels. On the other hand, thermo-chemical
process is a widely accepted technology for the produc-
tion of liquid, gaseous, solid bio-fuels, and heat. On the
basis of the amount of oxygen and heat used, the thermo-
chemical methods are classified into four types: pyrolysis,
combustion, hydrothermal processes (hydrothermal gasi-
fication, liquefaction, and carbonization), and gasifica-
tion (Pramanik 2003).
Among the thermo-chemical processes, pyrolysis and
hydrothermal carbonization (HTC) are the most common
methods used to produce the solid fuel from different
biomass sources. Pyrolysis deploys dry biomass and
releases volatile matter. Therefore, it is not considered as
an economical and an environmental friendly process. In
comparison to pyrolysis, HTC is not only an environmen-
tal friendly process but also one that can handle both wet
and dry biomass, therefore saving energy, time, and cost
required for drying the biomass feed.
3.1 Pyrolysis
Pyrolysis is an endothermic reaction (Frassoldati et  al.
2006, Stehlik 2012) that converts biomass into liquid,
gaseous, and solid fuels in the absence of oxygen through
rapid heating (Goyal et  al. 2008, Harris et  al. 2013).
Depending upon the operating conditions, the ratio of
liquid, solid, and gaseous products distribution obtained
from pyrolysis differs, as shown in Table 2. A solid product
is obtained as a byproduct from pyrolysis and is known
as bio-char, which is a porous material (Arami-Niya et al.
2011). Operating parameters, mainly temperature, are
important elements in defining the quality and quantity of
solid char in its production. The yield percentage of solid
char decreases by increasing temperature and heating
rate. Smaller residence time of gas, lower temperature,
and higher heating rate support the production of liquid
products, whereas longer residence time of gas, higher
temperature, and lower heating rate support the gaseous
product formation. In addition to the operating condi-
tions, water content of biomass feed has been proven to
have an influence on the product distribution from pyroly-
sis. Higher water content in biomass results in the reduc-
tion of the gaseous and solid products (Al Arni et al. 2010,
Jahirul et al. 2012).
Pyrolysis process can be divided into 3 main cate-
gories based on the yield distribution and operating
parameters: flash pyrolysis (favoring gas product), fast
 S. Nizamuddin et al.: PKS from oil palm industry as a feedstock for solid char production      7

Table 2: Typical operating parameters and product distribution percentage for flash, fast, and slow pyrolysis (Jahirul et al. 2012).

Type of pyrolysis  Temperature  Heating  Solid residence  Particle  Yield distribution (%)
(K) rate (K/s) time (s) size (mm) 
Char  Oil  Gas

Flash pyrolysis   1050–1300   > 1000   < 0.5   < 0.2  12  75  13

Fast pyrolysis   850–1250  10–200  0.5–10   < 1  20  50  30
Slow pyrolysis   550–950  0.1–1  450–550  5–50  35  30  35

pyrolysis (favoring liquid product), and slow pyrolysis
(favoring solid char production) (Bridgwater 2012).
In flash pyrolysis, a canister containing a packed bed
of biomass feed is placed in a pressure vessel. Air is used
to pressurize the vessel up to 1–2 MPa, and finally, a flash
fire is ignited from the bottom of the packed column. After
a short period, air is supplied from the top of the packed
column and the biomass is converted into solid char. The
reaction time for flash pyrolysis is  < 30 min, but the oper-
ating temperature depends upon several factors, namely,
heating time, type of biomass feed, moisture content of
feed, and total air supplied (Antal et al. 2003). The main
product of flash pyrolysis is bio-oil. Seventy-five percent
of biomass is converted into bio-oil during flash pyrolysis
(Demirbas 2000). However, bio-oil has some technologi-
cal limitations such as corrosiveness of oil, the presence
of the solids in oil, lower thermal stability, production of
water, higher viscosity, and higher alkali concentration in
the bio-oil (Cornelissen et al. 2008).
Fast pyrolysis is carried out under operating condi-
tions of higher temperature, higher transfer rate, fine feed,
short vapor residence time, and rapid cooling of pyrolysis
vapors (Demirbas and Arin 2002, Tsai et  al. 2006) and
favors the production of liquid product. Generally, up to
75% of dry biomass is converted into bio-oil; 15–25%, into
char; and 10–20%, into gaseous products by using fast
pyrolysis process (Guillain et al. 2009, Jahirul et al. 2012).
The solid char produced from fast pyrolysis has relatively
lower Brunauer-Emmett-Teller (BET) surface area, lower
calorific value, and high oxygen content due to low resi-
dence time of solid particles during the pyrolysis process
(Yanik et al. 2007, Duman et al. 2011, Manyà 2012). Char of
lower surface area is produced by pyrolysis of corn stover
and switch grass in a fluidized bed reactor (Boateng 2007,
Mullen et al. 2010).
Slow pyrolysis is a very old process, mostly used to
enhance the production of solid char at low heating rate
and low temperature. As the vapor residence time in slow
pyrolysis process is higher than that of fast and flash
pyrolysis (Table 2), the vapor components continue to
react with each other in vapor phase, resulting in the for-
mation of solid char and bio-oil (Bridgwater et al. 2001).
However, the bio-oil produced is lower in quantity and
quality than solid char due to long residence time of solids
(Jahirul et al. 2012).
Other than the parameters discussed, namely, reac-
tion temperature, heating rate, and residence time, other
factors such as vapor residence time, peak temperature,
process time, pressure, and moisture content of biomass
feedstock also have been reported to affect the solid char
yield during pyrolysis (Antal and Grønli 2003). Peak tem-
perature is the highest temperature achieved during the
process (Antal and Grønli 2003); it has negative effects
on the char yield. An increase in the peak temperature
(especially in the range of 300–500°C) increases the fixed
carbon content of the solid char (Antal and Grønli 2003),
while an increase in peak temperature from 200°C to
650°C results in high carbon content in the solid char (Lei
et al. 2009). Pyrolysis at high pressure (1–3 MPa) enhances
the yield of solid char, as increase in pressure leads to an
increase in the vapor residence time of the solid particle
(Manyà 2012). Pyrolysis pressure affects the porosity of the
solid char. Cetin et al. (2004) reported that upon increase
in pressure during pyrolysis of different biomass, a slight
decrease in total surface area of solid char is witnessed.
The moisture content present in biomass improves the
yield percentage of the solid char. The moisture content of
biomass feed (say 42–62%) is found to improve the yield
percentage of solid char at risen pressure (Shim and Hurt
2000, Demirbas 2004, Melligan et al. 2011). Another factor
of importance is particle size distribution of biomass. The
latter imposes impact of significant importance on solid
char yield percentage. An increase in particle size results
in a higher solid char yield percentage. As the particle
size increases, the diffusion rate of volatiles through char
decreases; ultimately, the additional char is produced
through secondary reactions (Várhegyi et al. 1998, Manyà
et al. 2007). Addition of a catalyst also enhances the rate
of char production. Di Blasi et al. (2009) observed a sub-
stantial increase (from 19% to 30%) in the yield of solid
char in the presence of potassium hydroxide (KOH) as
a catalyst. Similarly, Wang et  al. (2010) observed a 10%
increase in the char yield during the pyrolysis of the pine
wood in the presence of potassium carbonate (K2CO3).

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8      S. Nizamuddin et al.: PKS from oil palm industry as a feedstock for solid char production

On the other hand, the solid char yield decreases when
catalytic pyrolysis of corncob was conducted with HZSM-5
zeolite (Manyà 2012).
3.2 H
 ydrothermal carbonization process
(HTC)
Hydrothermal carbonization (HTC) is a process that con-
verts a variety of biomass into a smokeless and high
carbon content solid fuel known as hydrochar (Kruse et al.
2013). HTC has been accepted as a promising technology
over the last decade providing inherent benefits (Titirici
et al. 2007a, Titirici et al. 2007b, Yu et al. 2007, Cakan et al.
2008, Titirici et al. 2008) by converting biomass into solid
fuel (Kleinert and Wittmann 2009, Sukaribin and Khalid
2009, Funke and Ziegler 2010) and bio-oil (Akhtar et  al.
2010, Heilmann et al. 2010, Heilmann et al. 2011a,b). The
solid char produced from HTC holds 80–90% of energy
content of the original feed and 55–90% of mass of the
original mass of biomass, making it comparable to brown
coal (Yan et  al. 2009). HTC of biomass is achieved in a
reactor by the addition of water and the application of
high pressure and temperature for several hours (Xiao
et  al. 2012). Bergius and Specht introduced HTC process
for the first time in 1913, which was able to convert cel-
lulosic material into a high carbon-containing product. In
their experiment, the mixture of cellulose and water was
heated in a closed vessel at 250–310°C producing a solid
product with lower O/C ratio. In 1932, further modification
and improvement in the HTC process were made by Berl
and Schmidt. They studied various saccharides at 150–
350°C (Jamari and Howse 2012). A summary of previous
studies on HTC process using different types of biomass at
varying parameters is given in Table 3.
In general, carbonization of biomass takes place in
four stages with respect to temperature. The first stage
is drying where moisture content is completely removed;
this occurs at temperatures lower than 200°C. The second
stage is the stage of carbonization reaction. It is the stage
in which the initial decomposition of biomass initiates;
it occurs at a temperature range of 170–270°C. The light
tar and organic acids with water vapors are also released
in this stage. The third stage is one in which biomass is
decomposed and large amounts of organic liquids and
gases are evolved with heat resulting in the production of
solid char; it falls in the temperature range of 270–350°C.
This is the stage of carbonization where significant weight
loss takes place. The fourth stage of carbonization occurs
at temperatures  > 350°C, whereby a rapid concentration
of the carbon content in solid char occurs. In this stage,
the remaining volatile components present in the char are
emitted. Char produced through carbonization consists
of poorly developed structures due to pore clogging of
tarry substances. Therefore, it has less adsorption capac-
ity. However, if carbonization is performed at higher tem-
peratures with extended time period, the pore volume
may decrease due to the rearrangement and shrinkage of
aromatic rings. Some of the original pores tend to become
excessively small for the adsorbate to penetrate during
adsorption experiments. It must be remembered that the
reactions taking place during carbonization are complex
and simultaneous depending upon the temperature, reac-
tion time, and chemical composition of the feed.
HTC process may be classified as direct and indirect
(catalytic) HTC process. In the direct HTC process, only
water and feed are heated in a reactor at different tem-
peratures in the absence of the catalyst, whereas in the
catalytic HTC process, a catalyst is used. The use of small
amount of hydrolytic agent or catalyst can considerably

Table 3: Review of synthesis of char using HTC process.

Biomass feed type   Temperature  Reaction  Reactor type   Solid yield  References
(°C) time (h) (%)

Corn stalk   250  4  Parr stirred reactor   35.5  Xiao et al. 2012
Tamarix ramosissima   250  4  Parr stirred reactor   38.1  Xiao et al. 2012
Colloidal   200  2  Stirred stainless steel reactor   71  Heilmann et al. 2011a,b
Cellulose (Aldrich)   200–250  2–4  Stainless steel autoclave reactor   30–50  Sevilla and Fuertes 2009
Eucalyptus Sawdust   250  2  Autoclave reactor   40  Sevilla et al. 2011
Barley straw 37
Digested maize sludge   190–250  2–10  Stirred pressure reactor   35–71  Mumme et al. 2011
Cellulose   280  1/4  Autoclave reactor   29.9  Karagöz et al. 2005a,b
lignin 60.0
sawdust 41.7
rice husk 40.9
Sargassum horneri   180–210  2–16  Teflon lined stainless steel autoclave reactor   32.7–52.3  Xu et al. 2013

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 S. Nizamuddin et al.: PKS from oil palm industry as a feedstock for solid char production      9
enhance the reaction level. Catalysts may differ accord-
ing to the process employed. In general, acid catalysts
are most effective and suitable for hydrolysis (Wang 2011).
The basic catalyst hinders the formation of char and sup-
ports the formation of liquid oil. Karagöz et al. (2005a,b)
studied the effect of rubidium hydroxide (RbOH) and
cesium hydroxide (CsOH) on pine wood and observed
that the liquid product has increased and solid product
has decreased by the addition of catalyst. A similar effect
was observed by using potassium carbonate (K2CO3) on
sawdust (Karagöz et al. 2005a,b). The criteria for catalyst
selection include thermal stability, cost effectiveness, and
high selectivity towards desired yield (Westermann et al.
2007). A number of catalysts such as sodium hydroxide
(NaOH), potassium hydroxide (KOH), sodium carbonate
(Na2CO3), potassium carbonate (K2CO3), propanol (C3H8O),
ethanol (C2H6O), and citric acid have been considered
by many scientists for higher conversion of biomass into
bio-fuels (Çağlar and Demirbaş 2001, Karagöz et al. 2006,
Xu et al. 2013).
Presence of water also accelerates the carbonization
process of biomass and affects product distribution (Mok
et al. 1992, Behar et al. 2003, Funke and Ziegler 2010). Water
in biomass acts as both reacting medium and reactant
(Akiya and Savage 2002, Ramsurn and Gupta 2012). Ther-
modynamically, water is completely oxidized and does not
contain any enduring heating value. In contrast to pyroly-
sis, in which the presence of water content in biomass has
a negative effect on the process, as it requires higher heat
of vaporization (Akhtar et al. 2012), water is a perfect react-
ing agent to carry out reaction like HTC. This indicates
that use of biomass feedstock through the HTC process is
advantageous. Moreover, it is expected to be economical,
as it is bound to save energy and cost required for mois-
ture removal from biomass feed and work by drying. Under
hydrothermal water conditions, nitrogen atoms present in
biomass are converted into NO2, whereas phosphorous,
chlorine, and sulfur are oxidized to their respective inor-
ganic acids. These acids are neutralized by the addition
of suitable base (Peterson et al. 2008). The basic nature of
water weakens certain bonds in the organic material. As a
result, new molecular fragments are formed; this tends to
change the reaction environment. The acidic and the basic
nature of water reveal the adequate reason why hydrolysis
is expected to exchange biomass directly into bio-fuels in
more quantity as compared to pyrolysis process (Akiya and
Savage 2002, Zhou et al. 2010).
Biomass normally contains 40–60% oxygen. Conse-
quently, the removal of oxygen from biomass is impor-
tant to increase energy density. Oxygen may be removed
from the biomass feed by either dehydration reaction
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or decarboxylation. In dehydration, oxygen is removed
from biomass feed in the form of water, while in decar-
boxylation, it is removed as carbon dioxide (CO2). Biomass
undergoes hydration reaction at higher pressure and tem-
perature, even in excess of water. However, depolymeri-
zation reaction may occur through hydrolysis at elevated
temperatures because of the greater ionization of water at
that temperature (Kumar 2010).
Table 4 shows the yield of solid char production from
HTC, slow pyrolysis, fast pyrolysis, and flash pyrolysis
of PKS, oil palm fronds, oil palm trunks, oil palm fibers,
and oil palm EFB. Maximum solid product of 67.8% is pro-
duced from HTC of oil palm trunks, followed by HTC of oil
palm fibers and PKS producing 67.5% and 63.2% of solid
fuel, respectively, whereas maximum product of only 42%
is obtained from the slow pyrolysis of oil palm trunks. It
can be concluded that higher percentage of char yield can
be produced from HTC of PKS. Besides production of solid
char and bio-oil, HTC also produces a material that can be
used for soil remediation to improve soil fertility and crop
yield (Kleinert and Wittmann 2009, Rillig et al. 2010, Libra
et  al. 2011, Du et  al. 2012) and also an activated carbon
material that can be used as an adsorbent for water puri-
fication systems or CO2 sorption (Libra et al. 2011). HTC is
also used to produce a low-cost adsorbent or permeable
reactive barrier for uranium (VI), copper, and cadmium
contaminated waters (Kumar et al. 2011, Regmi et al. 2012);
a carbon material with nanostructure (Cui et  al. 2006,
Inagaki et al. 2010, Libra et al. 2011); a carbon catalyst that
could be used in the production of fine chemicals (Xiao
et al. 2012); a high performance super-capacitor electrode
(Parshetti et al. 2013); and lastly a carbonaceous material
that could enhance the efficiency of fuel cells (Libra et al.
2011). The schematic diagram of HTC with purpose and
possible applications is shown in Figure 2.
4 C
 omparison between properties
of PKS-char and EFB-char from
HTC and pyrolysis processes
Char is a vital contender for solid fuel because of its ele-
mental composition, low fiber structure, and high heating
value, which is similar to that of lignite or sub-bitumi-
nous coal. Moreover, char possesses strong mechanical
strength, sufficient pore size distribution, and high pore
surface area.
Production of char from PKS can serve a dual purpose:
generate energy and mitigate environmental concerns. In
addition, PKS contains high percentage of lignin, which
10      S. Nizamuddin et al.: PKS from oil palm industry as a feedstock for solid char production

Table 4: Char yield percentage from HTC and pyrolysis of different wastes of oil palm industry.

  HTC   Slow pyrolysis   Fast pyrolysis   Flash pyrolysis

1. PKS (Yuliansyah and Hirajima 2012, Windeatt et al. 2014)

Reaction temperature   200–380   600   430–540   –
Reaction time   30   60   –   –
Reactor   Batch autoclave  Fixed bed   Fluidized bed   –
Char yield (%)   37.3–63.2   31.8   20–40   –
2. EFB (Abdullah et al. 2007, Sulaiman and Abdullah 2011, Wannapeera et al. 2012, Claoston et al. 2014)
Reaction temperature   250–350   350–650   400–600   425–550
Reaction time   –   120   –   –
Reactor   Batch reactor   Large chamber muffle furnace  Fluidized bed   Fluidized bed
Char yield (%)   20.4   20.9–37.6   23.9–27.6   8–19
3. Fibers (Yuliansyah and Hirajima 2012)
Reaction temperature   200–380   450–800   –   –
Reaction time   30   60   –   –
Reactor   Batch autoclave  Laboratory scale   –   –
Char yield (%)   37.3–67.5   25.9–34.8   –   –
4. Fronds (Yuliansyah et al. 2010)
Reaction temperature   200–350   –   –   –
Reaction time   30   –   –   –
Reactor   Batch reactor   –   –   –
Char yield (%)   35.1–58.3   –   –   –
5. Trunks (Lim and Lim 1992, Yuliansyah et al. 2010)
Reaction temperature   200–350   400–550   400–550   –
Reaction time   30   60–180   60–180   –
Reactor   Batch reactor   Lab-scale pyrolyser   Lab-scale pyrolyser  –
Char yield (%)   35.3–67.8   35.8–42.0   37.0–40.0   –

SOx, NOx Irrespective of the process used for the production

Co
m
CO32- Carbon sequestering biochar of char, PKS-char contains lower oxygen, moisture, and
bu
st
io
n
SOy2- (y=3,4), Gas (CO2 etc.) Soil amendment ash compared to low rank coal. Higher content of ash and
NOz1- (z=2,3) moisture is undesirable for fuels, as moisture leads to a
CO2 Dried biomass
Adsorbent reduction in the heating value and the rate of combus-
Drying Hydrothermal
tion. Likewise, higher oxygen content leads to thermal
green biomass Hydrochar Fuel
instability (Chang 2014). The moisture content in char
Ph

Carbonization
ot
os

can be further reduced through the fractional distillation

yn

Substitute or precursor for

th
es

carbon black, activated carbon,

process, while the ash content in char can be reduced by
is

Oils container nurseries, and others.

washing feed material extensively prior to its use (Capu-

Figure 2: Schematic of HTC process for possible applications.
Reproduced from Kang et al. (2012) with permission from the
­American chemical society.
supports its suitability for converting it into char. The
higher content of lignin in biomass supports char produc-
tion because lignin has complex branching. This branch-
ing is henceforth hard to degrade (Peterson et al. 2008).
Zhong and Wei (2004) investigated the effect of lignin
content present in four types of biomass including Cun-
ninghamia lanceolata, Fraxinus mandshurica, Pinus mas-
soniana Lamb, and Populus tomentosa Carr. Their study
revealed that biomass with higher lignin content produces
more char and accordingly less bio-oil.
nitan and Capareda 2013). Despite the unwanted effects
of higher moisture and oxygen contents in fuels, they also
have some positive effects. The higher moisture content
will help to maintain a uniform temperature profile in cyl-
inder as well as reduce the emissions of NOx (Oasmaa and
Czernik 1999). On the other hand, higher oxygen content
will help reduce CO2 emission because it tends to enhance
the combustion characteristics (Jacobson et al. 2013).
The carbon content in solid char produced through
pyrolysis is higher than that of coal and solid char, whereas
carbon content in solid char is lower than that of coal. The
lower carbon and hydrogen contents contribute to lower
the HHV of fuels. Additionally, the low sulfur content in
PKS-char (0–1.3%) compared to coal (0.2–4.43%) makes it

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 S. Nizamuddin et al.: PKS from oil palm industry as a feedstock for solid char production      11

both environment and health friendly. Properties includ- PKS-char is higher than that of EFB-char, whereas vola-
ing BET characteristics, elemental composition, proximate tile matter, moisture, and ash contents of the PKS-char are
analyses, and HHV of char produced from PKS by using lower than those of EFB-char. High fixed carbon and low
different methods (HTC and slow pyrolysis) are listed and moisture, volatile matter, and ash content are required for
compared with those of char produced from EFB in Table 5. high-quality fuel. This requirement shows that char pro-
It can be noticed from Table 5 that fixed carbon content of duced from the PKS is a viable fuel, better than the char
produced from EFB. Elemental analysis of EFB-char and
PKS-char shows that the carbon content of EFB-char is
Table 5: Proximate analysis, elemental composition, lignocellulosic
lower, while the oxygen content is higher than that of the
composition and HHV of EFB-char and PKS-char produced by HTC
and slow pyrolysis. PKS-char. This evidence supports the fact that PKS-char is
a competitive fuel. Table 6 lists the HHV, ultimate analy-
Properties   HTC   Pyrolysis sis, and proximate analysis of coal.
BET characteristics of the PKS-char and the EFB-char
1. PKS-char
 Proximate analysis (%) from HTC and pyrolysis processes are given in Table  5.
 Moisture content   3.1–6.7   2.2 The table shows that the PKS-char of HTC has greater
 Volatile matter   34.4–74.7   11.5 BET surface area and average pore diameter than that of
 Fixed carbon   25.3–65.6   88.5 EFB-char of HTC process. The latter supports the applica-
 Ash   1.1–2.0   6.7
tion of PKS-char over EFB-char. At the same time, the BET
Elemental analysis (%) characteristics of PKS-char of pyrolysis process are much
 Carbon   57.1–80.9   78.2–90.6
higher than those of the EFB-char produced from pyrolysis
 Oxygen   13.5–36.8   2.8–17.7
 Hydrogen   4.5–5.7   1.6–7.9 process. This outcome suggests that PKS-char, produced
 Nitrogen   0.4–0.7   0.9–1.7 either from HTC or from pyrolysis is a better absorbent
 Sulfur   0.0–0.1   0.0 than EFB-char. Other applications for materials such as
Chemical composition (%) PKS-char with higher BET-surface area are super capaci-
 Hemicellulose   5.0   – tors for electrical energy storage and hydrogen storage
 Cellulose   10.0   – (Nizamuddin et al. 2015a,b). However, the BET character-
 Lignin   30.0–45.0   –
istics of HTC-char are lower as compared to pyrolysis-char.
 Extractives     –
 HHV(MJ/kg)   22.8–32.1   26.5–33.6 The porosity and surface area can be increased by thermal
BET characteristics
or chemical activation for energetic and catalytic applica-
 BET surface area (m2/g)   12.60   34.0 tions (Nizamuddin et al. 2015a,b). High reaction times and
 Pore volume (cm3/g)   0.04   0.022 greater particle size also tend to increase the surface area
 Average pore diameter (nm)   113.41   – of materials (Xu et al. 2013).
2. EFB-char Thermal stability of EFB-char and PKS-char from
 Proximate analysis (%) the HTC and pyrolysis processes has been studied in the
 Moisture content   4.7–8.0   6
literature. Nizamuddin et al. (2016) studied the impact of
 Volatile matter   73.4–78.0   41
 Fixed carbon   12.7–16.6   –
weight changes during thermogravimetric analysis on the
 Ash   1.6–3.5   7.7 behavior of PKS-char from HTC and reported three stages
Elemental analysis (%) of weight loss. The first is removal of moisture content
 Carbon   44.0–89.5   38.7–65.9 until 200°C; second is the decomposition of cellulose and
 Oxygen   1.1–27.1   4.5–31.65 hemicellulose between the temperature range of 200°C
 Hydrogen   6.1–7.0   2.1–7.7 and 350°C (which leads to the formation of primary char,
 Nitrogen   0.0–3.2   0.5–1.08
volatiles, and gases), and the third stage is the decom-
 Sulfur     0.01–0.02
position of lignin and hydrochar beyond 350°C. Thermal
Chemical composition (%)
analysis of EFB-char from HTC at 350°C was studied by
 Hemicellulose   7.0–36.6   –
 Cellulose   33.6–61.9   – Parshetti et al. (2013). Parshetti et al. reported that there
 Lignin   20.7–33.2   – is a greatest weight loss at high temperatures in the range
 Extractives   –   – of 280–400°C, attributing towards the decomposition of
 HHV (MJ/kg)   18.9–39.3   – cellulose and hemicellulose in this range. Ma et al. (2015)
BET characteristics investigated the thermal stability behavior of PKS-char
 BET surface area (m2/g)   8.033   7.658 during pyrolysis process and reported occurrence of three
 Average pore diameter   3.77   0.0031
stages at the temperature ranges, namely, 139–323°C,

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 12      S. Nizamuddin et al.: PKS from oil palm industry as a feedstock for solid char production

323–389°C, and 390–762°C, respectively. Results showed a

Vamvuka and Sfakiotakis 2011

weight loss of 30.52% during the first stage attributing to

Yanfen and Xiaoqian 2010

the decomposition of hemicellulose present in PKS. The
second stage of temperature profile showed the weight
loss due to cellulosic decomposition of PKS. The third

Varol et al. 2010

Varol et al. 2010
Idris et al. 2012
Frau et al. 2015
Frau et al. 2015
Frau et al. 2015
Frau et al. 2015
stage of the weight loss found to be only 11.88% of mass
References

loss is reasoned to occur due to the degradation of the

lignin content of PKS. Binti et al. (2015) studied thermal
stability of EFB-char from pyrolysis process at 600°C.
It was observed that 6.62% of biochar weight was lost

42.06 
30.29 
15.8 
24.60 
22.59 
9.21 
19.46 
28.10 
– 
HHV 
(MJ/kg)

between 25°C and 100°C, indicating the presence of mois-

ture content. A significant weight loss, about 63.62% of
initial weight of biochar sample, took place from 305°C
4.43 
1.23 
0.7 
0.28 
6.63 
4.82 
0.18 
0.48 
0.92 
Ultimate analysis 

Sulfur

to 500°C, suggesting that the remaining 27.73% is carbon

compound.
0.87 
1.65 
1.1 
1.93 
1.48 
0.48 
050 
1.39 
0.78 
Nitrogen 

5 Future prospects and challenges

2.66 
2.23 
3.2 
5.06 
4.65 
3.63 
5.96 
2.66 
4.74 
Hydrogen 

Char is a renewable solid bio-fuel, which can be produced

14.54 
8.93 
43.9 
32.62 
6.83 
8.03 
17.14 
2.12 
8.20 
Oxygen 

from the different types of biomass using several pro-

cesses. Solid char is emerging as a potential contributor
to the energy sector due to its favorable chemical charac-
45.25 
33.62 
38.5 
60.4 
55.85 
25.43 
48.56 
74.50 
63.15 
Carbon 

teristics, higher HHV, and abundant availability in terms

of resources. However, it must be remembered that the
research for solid char production has been conducted at
Table 6: HHV, ultimate and proximate analysis of different types of coal from different origin.

32.25 
52.34 
12.6 
3.45 
19.86 
34.71 
10.02 
16.57 
21.57 
Proximate analysis 
 
Ash

a laboratory scale only, as the work done at the pilot scale

solid char production has not been granted recognition
– 
– 
– 
– 
4.70 
22.90 
17.64 
2.28 
– 
Volatile matter  Moisture 

yet. Over the last few years, solid char production from
oil palm biomass, mainly PKS, has been advocated to set
the economy to utilize the large amounts of PKS produced
36.07 
26.17 
53.1 
42.64 
41.22 
24.85 
41.00 
9.09 
33.12 

from oil palm mills annually, especially in Southeast Asia.

This industry has various challenges upfront: lower
quality of solid char (higher moisture, ash and oxygen
contents, lower carbon and hydrogen contents), lack of
appropriate accessible technology (feedstock prepara-
31.68 
21.49 
34.3 
53.94 
34.22 
17.54 
31.33 
72.06 
45.31 
Fixed carbon 

tion processes such as drying, grinding, and particle size

screening), higher maintenance costs (Isahak et al. 2012),
and insufficient expertise in equipment handling and
conversion processes (Chang 2014). Moreover, innumera-
 
 
 
Mukah Balingian Sub-bituminous coal 
 
 
 
 
 
 
 

ble challenges associated with oil palm industry life cycle

assessment, conservation and biodiversity (Chiew and
Shimada 2013), replantation, land use, and health issues
(Ng et  al. 2012) further jeopardize the sustainable man-
agement systems and supply chains for PKS. All the dif-
S. African bituminous

ficulties listed ultimately affect the development of char

Tuncbilek lignite
Semi-anthracite

Orhaneli lignite
Hungary lignite
Italy sub-Bitum

production from PKS of oil palm industry.

Alaska lignite

Kardia lignite

The proper upgrading of PKS and solid char can help

Coal type

to improve the quality of solid char to make it a poten-

tial substitute for coal. Attempts for the development of

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 S. Nizamuddin et al.: PKS from oil palm industry as a feedstock for solid char production      13
cost-effective PKS pretreatment and pyrolysis/HTC tech-
nologies, optimization of PKS supply chains, increase in
the local expertise in process understanding and equip-
ment handling, subsidy or financial support provision to
oil palm smallholders together with the strategic market-
ing plans may offer significant help (Chang 2014). Further-
more, proper administration and enforcement of tactical
and strategic government policies and development of
standards and mandates for promoting the sustainable
development of both oil palm and biomass industries
properly legislated and planned will offer promising aid
to PKS promotion (Umar et al. 2013).
6 Conclusion
The abundant supply (in Southeast Asia) of PKS biomass
from oil palm and favorable physiochemical characteris-
tics (higher HHV) of PKS are the major driving forces that
attract researchers and policymakers to conduct over-
whelming research in the utilization of PKS as a feedstock
for production of solid char. These parameters attract
researchers and policymakers to aid in flourishing the
research in utilization of PKS as a feedstock for production
of solid char. Pyrolysis (fast, flash, and conventional) both
in the presence and the absence of catalyst and HTC are
the foremost methods used for the conversion of biomass
into solid char.
PKS has favorable physiochemical properties that
confirm the compatibility of PKS to be converted into
solid char. Solid char produced from PKS by using pyroly-
sis process has comparatively higher HHV values, higher
fixed carbon, and carbon content. On the same plane, the
latter possesses lower oxygen, moisture, and ash content
as compared to coal and other oil palm biomass. Parallel
to it, solid char produced from HTC has lower HHV and
carbon content than that of coal and EFB.
Acknowledgments: This research is financially supported
by the University of Malaya, Ministry of Higher Education
High Impact Research (UM.C/HIR/MOHE/ENG/30).
References
Abdullah N, Gerhauser H, Bridgwater AV. Bio-oil from fast pyrolysis
of oil palm empty fruit bunches. J Phys Sci 2007; 18: 57–74.
Abnisa F, Wan Daud WMA, Husin WNW, Sahu JN. Utilization
possibilities of palm shell as a source of biomass energy in
Malaysia by producing bio-oil in pyrolysis process. Biomass
Bioenerg 2011; 35: 1863–1872.
Unauthenticated
Download Date | 4/23/16 10:34 AM
Abnisa F, Arami-Niya A, Wan Daud WMA, Sahu JN, Noor IM.
Utilization of oil palm tree residues to produce bio-oil
and bio-char via pyrolysis. Energ Conv Manage 2013; 76:
1073–1082.
Akhtar J, Kuang SK, Amin NS. Liquefaction of empty palm fruit bunch
(EPFB) in alkaline hot compressed water. Renew Energy 2010;
35: 1220–1227.
Akhtar J, Saidina Amin NA. A review on operating parameters for
optimum liquid oil yield in biomass pyrolysis. Renew Sustain
Energy Rev 2012; 16: 5101–5109.
Akiya N, Savage PE. Roles of water for chemical reactions in
high-temperature water. Chem Rev 2002; 102: 2725–2750.
Al Arni S, Bosio B, Arato E. Syngas from sugarcane pyrolysis: An
experimental study for fuel cell applications. Renew Energy
2010; 35: 29–35.
Antal MJ, Grønli M. The art, science, and technology of charcoal
production. Ind Eng Chem Res 2003; 42: 1619–1640.
Antal MJ, Mochidzuki K, Paredes LS. Flash carbonization of biomass.
Ind Eng Chem Res 2003; 42: 3690–3699.
Arami-Niya A, Wan Daud WMA, Mjalli FS. Using granular activated
carbon prepared from oil palm shell by ZnCl 2 and physical
activation for methane adsorption. J Anal Appl Pyrol 2010; 89:
197–203.
Arami-Niya A, Abnisa F, Sahfeeyan MS, Wan Daud WMA, Sahu JN.
Optimization of synthesis and characterization of palm
shell-based bio-char as a by-product of bio-oil production
process. BioResources 2011; 7: 246–264.
Asadieraghi M, Wan Daud WMA. Characterization of lignocellulosic
biomass thermal degradation and physiochemical structure:
effects of demineralization by diverse acid solutions. Energ
Conv Manage 2014; 82: 71–82.
Asadullah M, Rasid NSA, Kadir SASA, Azdarpour A. Production and
detailed characterization of bio-oil from fast pyrolysis of palm
kernel shell. Biomass Bioenerg 2013; 59: 316–324.
Basiron Y. Palm oil production through sustainable plantations. Eur J
Lip Sci Technol 2007; 109: 289–295.
Behar F, Lewan MD, Lorant F, Vandenbroucke M. Comparison of
artificial maturation of lignite in hydrous and nonhydrous
conditions. Org Geochem 2003; 34: 575–600.
Berge ND, Kammann C, Ro K, Libra J. Environmental applications of
hydrothermal carbonization technology: biochar production,
carbon sequestration, and waste conversion. Sustain Carbon
Mater Hydro Proc 2013: 295–340.
Binti Ab, Aziz NS, bin Mohd Nor MA, Abdul Manaf SF, Hamzah F.
Suitability of biochar produced from biomass waste as soil
amendment. Procedia-Soc Behav Sci 2015; 195: 2457–2465.
Boateng AA. Characterization and thermal conversion of
charcoal derived from fluidized-bed fast pyrolysis oil
production of switchgrass. Ind Eng Chem Res 2007; 46:
8857–8862.
Bridgwater AV. Review of fast pyrolysis of biomass and product
upgrading. Biomass Bioenerg 2012; 38: 68–94.
Bridgwater AV, Czernik S, Piskorz J. An overview of fast pyrolysis.
In: Bridgwater AV, editor. Progress in thermochemical biomass
conversion. IEA Bioenergy. Oxford: Blackwell Sciences,
2001:977–997.
Butler E, Devlin G, Meier D, McDonnell K. A review of recent
laboratory research and commercial developments in fast
pyrolysis and upgrading. Renew Sustain Energ Rev 2011; 15:
4171–4186.
14      S. Nizamuddin et al.: PKS from oil palm industry as a feedstock for solid char production
Çağlar A, Demirbaş A. Conversion of cotton cocoon shell to liquid
products by supercritical fluid extraction and low pressure
pyrolysis in the presence of alkalis. Energ Conv Manage 2001;
42: 1095–1104.
Cakan RD, Titirici MM, Antonietti M, Cui G, Maier J, Hu YS.
Hydrothermal carbon spheres containing silicon nanoparticles:
synthesis and lithium storage performance. Chem Commun
2008: 3759–3761.
Capunitan JA, Capareda SC. Characterization and separation of corn
stover bio-oil by fractional distillation. Fuel 2013; 112: 60–73.
Cetin E, Moghtaderi B, Gupta R, Wall TF. Influence of pyrolysis
conditions on the structure and gasification reactivity of
biomass chars. Fuel 2004; 83: 2139–2150.
Chaiyaomporn K, Chavalparit O. Fuel pellets production from
biodiesel waste. Environ Asia 2010; 3: 103–110.
Chang SH. An overview of empty fruit bunch from oil palm as
feedstock for bio-oil production. Biomass Bioenerg 2014; 62:
174–181.
Chew TL, Bhatia S. Catalytic processes towards the production of
biofuels in a palm oil and oil palm biomass-based biorefinery.
Bioresource Technol 2008; 99: 7911–7922.
Chiew YL, Shimada S. Current state and environmental impact
assessment for utilizing oil palm empty fruit bunches for
fuel, fiber and fertilizer – a case study of Malaysia. Biomass
Bioenerg 2013; 51: 109–124.
Christian DG, Yates NE, Riche AB. The effect of harvest date on the
yield and mineral content of Phalaris arundinacea L.(reed
canary grass) genotypes screened for their potential as
energy crops in southern England. J Sci Food Agri 2006; 86:
1181–1188.
Claoston N, Samsuri AW, Husni A, Mohd Amran MS. Effects of
pyrolysis temperature on the physicochemical properties of
empty fruit bunch and rice husk biochars. Waste Manage Res
2014; 32: 331–339.
Cornelissen T, Yperman J, Reggers G, Schreurs S, Carleer R. Flash
co-pyrolysis of biomass with polylactic acid. Part 1: influence
on bio-oil yield and heating value. Fuel 2008; 87: 1031–1041.
Cui X, Antonietti M, Yu SH. Structural effects of iron oxide
nanoparticles and iron ions on the hydrothermal
carbonization of starch and rice carbohydrates. Small 2006; 2:
756–759.
Dalimin MN. Renewable energy update: Malaysia. Renew Energy
1995; 6: 435–439.
Dashtban M, Schraft H, Syed TA, Qin W. Fungal biodegradation and
enzymatic modification of lignin. Int J Biochem Mol Bio 2010;
1: 36–50.
Demirbas A. Recent advances in biomass conversion technologies.
Energy Edu Sci Technol 2000; 6: 19–40.
Demirbas A. Effects of temperature and particle size on bio-char
yield from pyrolysis of agricultural residues. J Anal Appl Pyrol
2004; 72: 243–248.
Demirbas A, Arin G. An overview of biomass pyrolysis. Energy
Sources 2002; 24: 471–482.
Di Blasi C, Galgano A, Branca C. Effects of potassium hydroxide
impregnation on wood pyrolysis. Energ Fuel 2009; 23:
1045–1054.
Du Z, Hu B, Shi A, Ma X, Cheng Y, Chen P, Liu Y, Lin X, Ruan R.
Cultivation of a microalga Chlorella vulgaris using recycled
aqueous phase nutrients from hydrothermal carbonization
process. Bioresource Technol 2012; 126: 354–357.
Unauthenticated
Download Date | 4/23/16 10:34 AM
Duman G, Okutucu C, Ucar S, Stahl R, Yanik J. The slow and fast
pyrolysis of cherry seed. Bioresource Technol 2011; 102:
1869–1878.
Estrellan CR, Iino F. Toxic emissions from open burning.
Chemosphere 2010; 80: 193–207.
Fan SP, Zakaria S, Chia CH, Jamaluddin F, Nabihah S, Liew TK, Pua
FL. Comparative studies of products obtained from solvolysis
liquefaction of oil palm empty fruit bunch fibres using different
solvents. Bioresource Technol 2011; 102: 3521–3526.
Frassoldati A, Migliavacca G, Crippa T, Velata F, Faravelli T, Ranzi E.
Detailed kinetic modeling of thermal degradation of biomasses.
Proceeding of the 29th Meeting on Combustion 2006.
Frau C, Ferrara F, Orsini A, Pettinau A. Characterization of several
kinds of coal and biomass for pyrolysis and gasification. Fuel
2015; 152: 138–145.
Funke A, Ziegler F. Hydrothermal carbonization of biomass: a
summary and discussion of chemical mechanisms for process
engineering. Biofuel Biopr Bioref 2010; 4: 160–177.
Garcia-Perez M, Chaala A, Pakdel H, Kretschmer D, Roy C. Vacuum
pyrolysis of softwood and hardwood biomass: comparison
between product yields and bio-oil properties. J Anal Appl Pyrol
2007; 78: 104–116.
Ghani WAWAK, Mohd A, da Silva G, Bachmann RT, Taufiq-Yap YH,
Rashid U, Al-Muhtaseb AH. Biochar production from waste
rubber-wood-sawdust and its potential use in C sequestration:
chemical and physical characterization. Ind Crops Products
2013; 44: 18–24.
Goyal HB, Seal D, Saxena RC. Bio-fuels from thermochemical
conversion of renewable resources: a review. Renew Sustain
Energy Rev 2008; 12: 504–517.
Guillain M, Fairouz K, Mar SR, Monique F, Jacques L. Attrition-free
pyrolysis to produce bio-oil and char. Bioresource Technol
2009; 100: 6069–6075.
Harris K, Gaskin J, Cabrera M, Miller W, Das KC. Characterization and
mineralization rates of low temperature peanut hull and pine
chip biochars. Agron 2013; 3: 294–312.
Hasegawa I, Tabata K, Okuma O, Mae K. New pretreatment methods
combining a hot water treatment and water/acetone extraction
for thermo-chemical conversion of biomass. Energy Fuel 2004;
18: 755–760.
Heilmann SM, Davis HT, Jader LR, Lefebvre PA, Sadowsky MJ, Schendel
FJ, Von Keitz MG, Valentas KJ. Hydrothermal carbonization of
microalgae. Biomass Bioenerg 2010; 34: 875–882.
Heilmann SM, Jader LR, Harned LA, Sadowsky MJ, Schendel
FJ, Lefebvre PA, Von Keitz MG, Valentas KJ. Hydrothermal
carbonization of microalgae II. Fatty acid, char, and algal
nutrient products. Appl Energy 2011a; 88: 3286–3290.
Heilmann SM, Jader LR, Sadowsky MJ, Schendel FJ, von Keitz MG,
Valentas KJ. Hydrothermal carbonization of distiller’s grains.
Biomass Bioenerg 2011b; 35: 2526–2533.
Hoekman SK, Broch A, Robbins C. Hydrothermal carbonization (HTC)
of lignocellulosic biomass. Energy Fuel 2011; 25: 1802–1810.
Hussain A, Ani FN, Darus AN, Mokhtar H, Azam S, Mustafa A.
Themochemical behaviour of empty fruit bunches and oil palm
shell waste in a circulating fluidized-bed combustor (CFBC).
J Oil Palm Res 2006; 18: 210–218.
Idris SS, Rahman NA, Ismail K. Combustion characteristics of
Malaysian oil palm biomass, sub-bituminous coal and their
respective blends via thermogravimetric analysis (TGA).
Bioresource Technol 2012; 123: 581–591.
 S. Nizamuddin et al.: PKS from oil palm industry as a feedstock for solid char production      15
Inagaki M, Park KC, Endo M. Carbonization under pressure. New
Carbon Mater 2010; 25: 409–420.
Isahak WNRW, Hisham MWM, Yarmo MA, Hin TY. A review on bio-oil
production from biomass by using pyrolysis method. Renew
Sustain Energy Rev 2012; 16: 5910–5923.
Jacobson K, Maheria KC, Kumar Dalai A. Bio-oil valorization: a
review. Renew Sustain Energy Rev 2013; 23: 91–106.
Jahirul MI, Rasul MG, Chowdhury AA, Ashwath N. Biofuels
production through biomass pyrolysis – a technological review.
Energies 2012; 5: 4952–5001.
Jamaluddin MA, Ismail K, Mohd Ishak MA, Ab Ghani Z, Abdullah MF,
Safian MT, Idris SS, Tahiruddin S, Mohammed Yunus MF, Mohd
Hakimi NIN. Microwave-assisted pyrolysis of palm kernel shell:
optimization using response surface methodology (RSM).
Renew Energy 2013; 55: 357–365.
Jamari SS, Howse JR. The effect of the hydrothermal carbonization
process on palm oil empty fruit bunch. Biomass Bioenerg 2012;
47: 82–90.
Kang S, Li X, Fan J, Chang J. Characterization of hydrochars
produced by hydrothermal carbonization of lignin, cellulose,
D-xylose, and wood meal. Ind Eng Chem Res 2012; 51:
9023–9031.
Karagöz S, Bhaskar T, Muto A, Sakata Y. Catalytic hydrothermal
treatment of pine wood biomass: effect of RbOH and CsOH on
product distribution. J Chem Technol Biotechnol 2005a; 80:
1097–1102.
Karagöz S, Bhaskar T, Muto A, Sakata Y. Comparative studies of oil
compositions produced from sawdust, rice husk, lignin and
cellulose by hydrothermal treatment. Fuel 2005b; 84: 875–884.
Karagöz S, Bhaskar T, Muto A, Sakata Y. Hydrothermal upgrading of
biomass: effect of K 2 CO 3 concentration and biomass/water
ratio on products distribution. Bioresource Technol 2006; 97:
90–98.
Kean CW, Sahu JN, Wan Daud WMA. Hydrothermal gasification
of palm shell biomass for synthesis of hydrogen fuel.
BioResources 2013; 8: 1831–1840.
Kelly-Yong TL, Lee KT, Mohamed AR, Bhatia S. Potential of hydrogen
from oil palm biomass as a source of renewable energy
worldwide. Energ Policy 2007; 35: 5692–5701.
Khan AA, De Jong W, Jansens PJ, Spliethoff H. Biomass combustion
in fluidized bed boilers: potential problems and remedies. Fuel
Proc Technol 2009; 90: 21–50.
Kleinert M, Wittmann T. Carbonisation of biomass using
hydrothermal approach: state-of-the-art and recent
developments. Vortrag zur 2009; 17.
Kruse A, Funke A, Titirici MM. Hydrothermal conversion of biomass
to fuels and energetic materials. Curr Opin Chem Biol 2013; 17:
515–521.
Kumar S. Hydrothermal treatment for biofuels: lignocellulosic
biomass to bioethanol, biocrude, and biochar. Auburn
University, 2010.
Kumar S, Loganathan VA, Gupta RB, Barnett MO. An assessment
of U (VI) removal from groundwater using biochar produced
from hydrothermal carbonization. J Environ Manag 2011; 92:
2504–2512.
Lee KT, Ofori-Boateng C. Sustainability of biofuel production from oil
palm biomass. Springer, 2013.
Lei H, Ren S, Julson J. The effects of reaction temperature and time
and particle size of corn stover on microwave pyrolysis. Energy
Fuel 2009; 23: 3254–3261.
Unauthenticated
Download Date | 4/23/16 10:34 AM
Lewandowski I, Heinz A. Delayed harvest of miscanthus – influences
on biomass quantity and quality and environmental impacts of
energy production. Eur J Agron 2003; 19: 45–63.
Libra JA, Ro KS, Kammann C, Funke A, Berge ND, Neubauer Y, Titirici
M-M, Fühner C, Bens O, KernJ Emmerich K-H. Hydrothermal
carbonization of biomass residuals: a comparative review
of the chemistry, processes and applications of wet and dry
pyrolysis. Biofuels 2011; 2: 71–106.
Lim KO, Lim KS. Carbonisation of oil palm trunks at moderate
temperatures. Bioresource Technol 1992; 40: 215–219.
Lim X, Sanna A, Andrésen JM. Influence of red mud
impregnation on the pyrolysis of oil palm biomass-EFB.
Fuel 2014; 119: 259–265.
Liu Z, Quek A, Kent Hoekman S, Balasubramanian R. Production
of solid biochar fuel from waste biomass by hydrothermal
carbonization. Fuel 2013; 103: 943–949.
Ma Z. Chen D, Gu J, Bao B, Zhang Q. Determination of pyrolysis
characteristics and kinetics of palm kernel shell using
TGA–FTIR and model-free integral methods. Energ Conv
Manage 2015; 89: 251–259.
Manyà JJ. Pyrolysis for biochar purposes: a review to establish
current knowledge gaps and research needs. Environ Sci
Technol 2012; 46: 7939–7954.
Manyà JJ, Ruiz J, Arauzo J. Some peculiarities of conventional
pyrolysis of several agricultural residues in a packed bed
reactor. Ind Eng Chem Res 2007; 46: 9061–9070.
Mazaheri H, Lee KT, Bhatia S, Mohamed AR. Subcritical water
liquefaction of oil palm fruit press fiber for the production
of bio-oil: effect of catalysts. Bioresource Technol 2010; 101:
745–751.
Melligan F, Auccaise R, Novotny EH, Leahy JJ, Hayes MH, Kwapinski W.
Pressurised pyrolysis of Miscanthus using a fixed bed reactor.
Bioresource Technol 2011; 102: 3466–3470.
Minowa T, Kondo T, Sudirjoa ST. Thermochemical liquefaction of
Indonesian biomass residues. Biomass Bioenerg 1998; 14:
517–524.
Mohammed MA, Salmiaton A, Wan Azlina WA,
Mohamad Amran MS. Gasification of oil palm empty fruit
bunches: a characterization and kinetic study. Bioresource
Technol 2012; 110: 628–636.
Mok WSL, Antal MJ, Szabo P, Varhegyi G, Zelei B. Formation of
charcoal from biomass in a sealed reactor. Ind Eng Chem Res
1992; 31: 1162–1166.
Mubarak NM, KunduA, Sahu JN, Abdullah EC, Jayakumar NS.
Synthesis of palm oil empty fruit bunch magnetic pyrolytic
char impregnating with FeCl3 by microwave heating technique.
Biomass Bioenerg 2014; 61: 265–275.
Mullen CA, Boateng AA, Goldberg NM, Lima IM, Laird DA, Hicks KB.
Bio-oil and bio-char production from corn cobs and stover by
fast pyrolysis. Biomass Bioenerg 2010; 34: 67–74.
Mumme J, Eckervogt L, Pielert J, Diakité M, Rupp F, Kern J.
Hydrothermal carbonization of anaerobically
digested maize silage. Bioresource Technol 2011; 102:
9255–9260.
Ng WPQ, Lam HL, Ng FY, Kamal M, Lim JHE. Waste-to-wealth: green
potential from palm biomass in Malaysia. J Clean Prod 2012;
34: 57–65.
Nizamuddin S, Jayakumar NS, Sahu JN, Ganesan P, Bhutto AW,
Mubarak NM. Hydrothermal carbonization of oil palm shell.
Korean J Chem Eng 2015a; 32: 1–9.
16      S. Nizamuddin et al.: PKS from oil palm industry as a feedstock for solid char production
Nizamuddin S, Jaya Kumar NS, Sahu JN, Ganesan P, Mubarak NM,
Mazari SA. Synthesis and characterization of hydrochars
produced by hydrothermal carbonization of oil palm shell. Can J
Cheml Eng 2015b; 93: 1916–1921.
Nizamuddin S, Mubarak NM, Tiripathi M, Jayakumar NS, Sahu JN,
Ganesan P. Chemical, dielectric and structural characterization
of optimized hydrochar produced from hydrothermal
carbonization of palm shell. Fuel 2016; 163: 88–97.
Oasmaa A, Czernik S. Fuel oil quality of biomass pyrolysis oils state
of the art for the end users. Energy Fuel 1999; 13: 914–921.
Omar R, Idris A, Yunus R, Khalid K, Aida Isma MI. Characterization of
empty fruit bunch for microwave-assisted pyrolysis. Fuel 2011;
90: 1536–1544.
Parshetti GK, Kent Hoekman S, Balasubramanian R. Chemical,
structural and combustion characteristics of carbonaceous
products obtained by hydrothermal carbonization of palm
empty fruit bunches. Bioresource Technol 2013; 135: 683–689.
Peterson AA, Vogel F, Lachance RP, Fröling M, Antal MJ, Tester JW.
Thermochemical biofuel production in hydrothermal media:
a review of sub-and supercritical water technologies. Energy
Environ Sci 2008; 1: 32–65.
Pordesimo LO, Hames BR, Sokhansanj S, Edens WC. Variation in
corn stover composition and energy content with crop maturity.
Biomass Bioenerg 2005; 28: 366–374.
Pramanik K. Properties and use of Jatropha curcas oil and diesel fuel
blends in compression ignition engine. Renew Energy 2003;
28: 239–248.
Ramsurn H, Gupta RB. Production of biocrude from biomass by
acidic subcritical water followed by alkaline supercritical water
two-step liquefaction. Energy Fuel 2012; 26: 2365–2375.
Regmi P, Moscoso JLG, Kumar S, Cao X, Mao J, Schafran G. Removal
of copper and cadmium from aqueous solution using
switchgrass biochar produced via hydrothermal carbonization
process. J Environ Manag 2012; 109: 61–69.
Rillig MC, Wagner M, Salem M, Antunes PM, George C, Ramke H-G,
Titirici M-M, Antonietti M. Material derived from hydrothermal
carbonization: Effects on plant growth and arbuscular
mycorrhiza. Appl Soil Ecology 2010; 45: 238–242.
Rosli WD, Law KN, Zainuddin Z, Asro R. Effect of pulping variables on
the characteristics of oil-palm frond-fiber. Bioresource Technol
2004; 93: 233–240.
Rubin EM. Genomics of cellulosic biofuels. Nature 2008; 454: 841–845.
Sadeghinezhad E, Kazi SN, Badarudin A, Togun H, Zubir MNM, Oon
S, Gharehkhani S. Sustainability and environmental impact of
ethanol as a biofuel. Rev Chem Eng 2014; 30: 51–72.
Salema AA, Yeow, YK, Ishaque K, Ani FN, Afzal MT, Hassan A.
Dielectric properties and microwave heating of oil palm
biomass and biochar. Ind Crops Products 2013; 50: 366–374.
Sevilla M, Fuertes AB. The production of carbon materials by
hydrothermal carbonization of cellulose. Carbon 2009; 47:
2281–2289.
Sevilla M, Maciá-Agulló JA, Fuertes AB. Hydrothermal carbonization
of biomass as a route for the sequestration of CO 2: chemical
and structural properties of the carbonized products. Biomass
Bioenerg 2011; 35: 3152–3159.
Shim H-S, Hurt RH. Thermal annealing of chars from diverse organic
precursors under combustion-like conditions. Energy Fuel
2000; 14: 340–348.
Stehlik P. Up-to-date technologies in waste to energy field. Rev
Chem Eng 2012; 28: 223–242.
Unauthenticated
Download Date | 4/23/16 10:34 AM
Sukaribin N, Khalid K. Effectiveness of sterilisation of oil palm
bunch using microwave technology. Ind Crops Products 2009;
30: 179–183.
Sulaiman F, Abdullah N. Optimum conditions for maximising
pyrolysis liquids of oil palm empty fruit bunches. Energy 2011;
36: 2352–2359.
Telmo C, Lousada J. Heating values of wood pellets from different
species. Biomass Bioenerg 2011; 35: 2634–2639.
Titirici MM, Thomas A, Antonietti M. Back in the black: hydrothermal
carbonization of plant material as an efficient chemical process
to treat the CO 2 problem? New J Chem 2007a; 31: 787–789.
Titirici MM, Thomas A, Yu S-H, Müller J-O, Antonietti M. A direct
synthesis of mesoporous carbons with bicontinuous pore
morphology from crude plant material by hydrothermal
carbonization. Chem Mater 2007b; 19: 4205–4212.
Titirici MM, Antonietti M, Niki Baccile N. Hydrothermal carbon from
biomass: a comparison of the local structure from poly-to
monosaccharides and pentoses/hexoses. Green Chem 2008;
10: 1204–1212.
Tsai WT, Lee MK, Chang YM. Fast pyrolysis of rice straw, sugarcane
bagasse and coconut shell in an induction-heating reactor. J
Anal Appl Pyrol 2006; 76: 230–237.
Tye YY, Lee KT, Abdullah WNW, Leh CP. Second-generation
bioethanol as a sustainable energy source in Malaysia
transportation sector: status, potential and future prospects.
Renew Sustain Energ Rev 2011; 15: 4521–4536.
Umar MS, Jennings P, Urmee T. Strengthening the palm oil biomass
renewable energy industry in Malaysia. Renew Energy 2013;
60: 107–115.
Unz S, Wen T, Beckmann M. Characterization of biomass used
in thermal processes with regard to the kinetic properties.
Proceedings of the 35th International Technical Conference on
Clean Coal & Fuel Systems, 2010.
Vamvuka D, Sfakiotakis S. Combustion behaviour of biomass fuels
and their blends with lignite. Thermochimica Acta 2011; 526:
192–199.
Várhegyi G, Szabó P, Till F, Zelei B, Antal MJ, Dai X. TG, TG-MS, and
FTIR characterization of high-yield biomass charcoals. Energy
Fuel 1998; 12: 969–974.
Varman M, Saka S. A comparative study of oil palm and
Japanese beech on their fractionation and characterization as
treated by supercritical water. Waste Biomass Valor 2011; 2:
309–315.
Varol M, Atimtay AT, Bay B, Olgun H. Investigation of co-combustion
characteristics of low quality lignite coals and biomass with
thermogravimetric analysis. Thermochimica Acta 2010; 510:
195–201.
Wang WC. Development of a small scale continuous hydrolysis
process for drop-in biofuel production. North Carolina State
University, 2011.
Wang Z, Wang F, Cao J, Wang J. Pyrolysis of pine wood in a slowly
heating fixed-bed reactor: potassium carbonate versus calcium
hydroxide as a catalyst. Fuel Proc Technol 2010; 91: 942–950.
Wannapeera J, Li X, Worasuwannarak N, Ashida R, Miura K.
Production of high-grade carbonaceous materials and fuel
having similar chemical and physical properties from various
types of biomass by degradative solvent extraction. Energy Fuel
2012; 26: 4521–4531.
Werther J, Saenger M, Hartge E-U, Ogada T, Siagi Z. Combustion of
agricultural residues. Prog Energy Comb Sci 2000; 26: 1–27.
 S. Nizamuddin et al.: PKS from oil palm industry as a feedstock for solid char production      17

Westermann P, Jørgensen B, Lange L, Ahring BK, Christensen CH.
Maximizing renewable hydrogen production from biomass in a
bio/catalytic refinery. Int J Hydr Energy 2007; 32: 4135–4141.
Windeatt JH, Ross AB, Williams PT, Forster PM, Nahil MA, Singh S.
Characteristics of biochars from crop residues: potential for
carbon sequestration and soil amendment. J Environ Manage
2014; 146: 189–197.
Xiao LP, Shi ZJ, Xu F, Sun RC. Hydrothermal carbonization of
lignocellulosic biomass. Bioresource Technol 2012; 118: 619–623.
Xu Q, Qian Q, Quek A, Ai N, Zeng G, Wang J. Hydrothermal
carbonization of macroalgae and the effects of experimental
parameters on the properties of hydrochars. ACS Sustain Chem
Eng 2013; 1: 1092–1101.
Yan W, Acharjee TC, Coronella CJ, Vásquez VR. Thermal pretreatment
of lignocellulosic biomass. Environ Progr Sustain Energy 2009;
28: 435–440.
Yanfen L, Xiaoqian M. Thermogravimetric analysis of the
co-combustion of coal and paper mill sludge. Appl Energy
2010; 87: 3526–3532.
Yang H, Chen H, Zheng C, Yan R, Lee DH, Liang DT. Palm oil wastes
to biofuel-effect of temperature and gasifying agent on gas
product distribution. 2005.
Yanik J, Kornmayer C, Saglam M, Yüksel M. Fast pyrolysis of
agricultural wastes: characterization of pyrolysis products.
Fuel Proc Technol 2007; 88: 942–947.
Yu Y, Lou X, Wu H. Some recent advances in hydrolysis
of biomass in hot-compressed water and its comparisons
with other hydrolysis methods. Energy Fuel 2007; 22:
46–60.
Yuliansyah AT, Hirajima T. Efficacy of hydrothermal treatment for
production of solid fuel from oil palm wastes. In: Abrol V,
editor. Resource management for sustainable agriculture.
2012.
Yuliansyah AT, Hirajima T, Kumagai S, Sasaki K. Production of
solid biofuel from agricultural wastes of the palm oil industry
by hydrothermal treatment. Waste Biomass Valor 2010; 1:
395–405.
Zanzi R. Pyrolysis of biomass. Philosophical doctor dissertation.
2001.
Zhong C, Wei X. A comparative experimental study on the
liquefaction of wood. Energy 2004; 29: 1731–1741.
Zhou D, Zhang L, Zhang S, Fu H, Chen J. Hydrothermal liquefaction
of macroalgae Enteromorpha prolifera to bio-oil. Energy Fuel
2010; 24: 4054–4061.

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