Biomass Conversion and Biorefinery

https://doi.org/10.1007/s13399-020-01201-2

ORIGINAL ARTICLE

Effect of acid catalysts on hydrothermal carbonization of Malaysian

oil palm residues (leaves, fronds, and shells)
for hydrochar production
Mariam Ameen 1,2 & Nohanisah Mohammad Zamri 2 & So Tsuk May 2 & Mohammad Tazli Azizan 3 & Aqsha Aqsha 4 &
Nizamuddin Sabzoi 5 & Farooq Sher 6

Received: 18 August 2020 / Revised: 4 December 2020 / Accepted: 11 December 2020

# The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature 2021

Abstract
Malaysian oil palm industry produces a significant amount of oil palm residue as solid wastes. These solid wastes are comprised of oil
palm residue which contains the stem, fronds from the farms, empty fruit bunch (EFB), mesocarp fibre (MF), and palm kernel shell
(PKS) from the oil palm–processing factories. These residues are not successfully reused for other purposes, and the current dumping
methods can possibly trigger unfavourable effects to the environment. As oil palm residues are a readily available waste biomass, it has
a high potential to be converted into valuable energy-derived products. Hydrothermal carbonization (HTC), which is a thermochemical
process, is a method used to treat biomass to produce hydrochar under hot-compressed water. Oil palm residues (palm leaves, palm
fronds, and palm shell) were used as the feedstock for producing carbonaceous hydrochar. The key objective of this study is to examine
the effect of the reaction temperature, residence time, and acid catalysts on the HTC process. HTC of oil palm residues was optimized at
different operating temperatures from 140 to 300 °C and different reaction times between 30 and 240 minutes with a biomass-to-water
ratio of 1:10 wt%. Acid catalysts such as citric acid and ascorbic acid were used for the HTC process. The hydrochar produced is further
characterized using heating value and elemental and Fourier transform infrared (FTIR) analysis. The yield of hydrochar reduces with
the rise of temperature and time but it increases in the presence of acid catalysts. The carbon content of hydrochar is observed to be
between 44.36 and 49.50%. The FTIR analysis showed that a high intensity at 1423 cm−1 indicates a high content of lignin and
cellulose in the hydrochar. A considerable decrease in the H/C and O/C atomic ratio shows that the dehydration and decarboxylation
take place during the HTC process.

Keywords Acid catalysts . HTC . Optimization . Hydrochar . Malaysian oil palm residue

Highlights
• Malaysian oil palm residue was converted into hydrochar via HTC.
• Palm shell generated a higher hydrochar yield than other residues.
• Weak acid catalyst increases the yield and carbon contents of hydrochar.

* Mohammad Tazli Azizan 3

tazli@unimap.edu.my; m_tazli@hotmail.com
1
HiCoE, Centre of Biofuel and Biochemical Research (CBBR),
Institute of Self-Sustainable Building (ISB), Universiti Teknologi
PETRONAS, Seri Iskandar, 32610, Perak, Malaysia
2
Department of Chemical Engineering, Universiti Teknologi
PETRONAS, Bandar Universiti Seri Iskandar, 32610 Seri
Iskandar, Perak, Malaysia
Faculty of Chemical Engineering Technology, University Malaysia
Perlis, Kompleks Pusat Pengajian Jejawi 3, 02600 Arau, Perlis,
Malaysia
4
Department of Chemical Engineering, Faculty of Industrial
Technology, Institut Teknologi Bandung, Kota Bandung, Jawa
Barat 40132, Indonesia
5
Department of Civil and Infrastructure Engineering, RMIT
University, Melbourne, Victoria 3000, Australia
6
School of Mechanical, Aerospace and Automotive Engineering,
Faculty of Engineering, Environmental and Computing, Coventry
University, Coventry CV1 5FB, UK

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1 Introduction
Depletion of fossil fuels, increasing oil price, anthropogenic
pollution effects caused by combustion of fossil fuel, and in-
creasing energy demand due to the ballooning of global pop-
ulation and emerging industries had driven the world to ex-
plore for renewable and sustainable energy [1]. The biomass,
which consists of forestry wastes and agricultural wastes, can
be considered renewable energy supply due to its abundance
and its high potential to deliver the global energy demands.
Several countries have set up their targets to utilize biofuels to
reduce the dependency and extend the shelf life of fossil fuels
[1, 2]. Malaysia is one of the largest oil palm–planted coun-
tries in the world after Indonesia, thus generating large
amounts of biomass wastes. Malaysia generates 168 million
tons of biomass waste annually and palm oil waste contributes
for 94% of biomass feedstock, accumulated from three million
hectares of oil palm plantations, currently [3]. Among these,
empty fruit bunches (EFB) contribute to 12.4 million tonnes
(22%) [4] and palm shell represents 5.5% of Malaysia bio-
mass waste, at approximately 2.4 million tonnes [5]. These
large amounts of oil palm waste in Malaysia either are burnt
to open atmosphere, which prompted the emission of toxins
and harmful gases, or are landfilled. The shortcoming of land-
fill sites and additional expenditure on removal of burnt resi-
dues encouraged the researchers to investigate for the efficient
and commercially beneficial deployment of the oil palm waste
[6]. Almost all of the residues of oil palms (OP) are frequently
left out at the plantation sites as nutrient substitutes, while
palm kernel shell and fronds are combusted to produce steam
and electricity to maintain the palm oil mill operation [7].
However, these waste biomasses (OP leaves, OP fronds, and
EFB) contribute to the highest share of oil palm residues,
which are abundantly available to transform into productive
materials [8, 9]. One of the possibilities is to convert oil palm
waste into good-quality hydrochar. The hydrochars produced
from various biowastes are commonly used for soil habitua-
tion [10], synthesis of lubricants[11], maintenance of
Pickering emulsions [12], transformation to solid fuels [13],
adsorbents [14, 15], and metal detection [16]. There are sev-
eral factors that play significant roles in selecting the suitable
biomass, which are calorific value, volatile matter content, ash
content, moisture content, and physicochemical and lignocel-
lulosic composition [17]. Lignocellulosic biomass is found to
be the best potential feedstock for alternative renewable ener-
gy due to its high carbohydrate content and abundance in
supply. Lignocellulosic biomass is primarily comprised of
cellulose, hemicellulose, and lignin. Oil palm shell contains
generally high contents of lignin (49%), cellulose (31%), and
hemicellulose (20%); the fronds consist of 62.3% lignin,
20.6% cellulose, and 17.1% hemicellulose, whereas the ligno-
cellulosic composition of the leaves is 32.5% lignin, 44.5%
cellulose, and 23% hemicellulose as reported in the literature
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Biomass Conv. Bioref.
[18, 19]. Consequently, higher lignin and cellulose contents of
these feed materials will be rendered in hydrochar product. It
was reported in literature that the lignin content of oil palm
biomass was 47.7%, which was increased to 49.3–57.6% and
50.1–61.0% for hydrothermally treated hydrochars and hydro-
thermally treated/washed hydrochars, respectively. Based on
the lignocellulosic composition of selected oil palm wastes, it
can be implied that these biomasses are appropriate for solid
fuel production. Therefore, all these residues can be used for
hydrothermal carbonization to produce high-quality
hydrochar depending on the operating conditions and
catalysts.
There are several methods to convert biomass into value-
added products such as pyrolysis, solvolysis, hydrothermal
liquefaction, hydrothermal gasification, and hydrothermal car-
bonization (HTC) [20, 21]. HTC is one of finest methods since
this process is environmentally friendly, versatile chemistry,
and economically viable. HTC can generate both solid and
liquid products as hydrochar and water-soluble organic liq-
uids, respectively. The solid product has coal-like characteris-
tics, high carbon content, and resistance to decomposition
compared to raw biomass. Other benefits of the HTC process
are the increase of carbon efficiency, reduced pollutant emis-
sions, and increased heating value of biomass. The HTC pro-
cess, first founded by Bergius in 1913, is a thermochemical
process in converting biomass to hydrochar in hot-
compressed water, which caught the attention of the world
in the past century due to its competence to process wet feed-
stock without the necessity of energy-intensive pre-drying
process [22]. The HTC process is performed in water at low
temperature and high pressure generally from 150 to 350 °C
for several hours [23]. Various biomasses had been studied as
the feedstock of HTC including oil palm shell [18], sewage
sludge [24], wheat straw [25], orange pomace [26], eucalyptus
bark [27], rapeseed husk [28], seaweed [29], and microalgae
[30]. However, the hydrochar produced varied significantly in
terms of thermal stability and physicochemical properties with
different types of feedstocks and operating parameters.
According to Lin et al. [25] during the HTC treatment of the
biomass, there are series of significant decomposition and
condensation reactions such as decarboxylation, dehydration,
aromatization, and polymerization, which results in formation
of solid hydrochar. There are several factors that affect the
production of the hydrochar such as type of the catalyst, reac-
tion temperature, reaction time, and substrate concentration.
For the HTC process, the surface structure, size, and shape of
the final product are depending on the initial structure and
composition of the biomass itself such as lignin and cellulose
contents [31, 32]. Zhu et al. investigated the role of hydrochar
properties in terms of porosity of carbon content. It was re-
ported that the properties of hydrochar are greatly affected by
the HTC process and porosities of hydrochar-based porous
carbon. There was a positive correlation between porosities
Biomass Conv. Bioref.
of hydrochar and the elemental composition of hydrochar ma-
terials [32].
HTC is carried out at a relatively low temperature (150–
350 °C) compared to pyrolysis (dry torrefaction), which is at
300–650 °C [33]. However, the HTC process time varies from
minutes to days, which makes it less economically viable. The
addition of catalyst is expected to enhance the reaction in
terms of higher carbon content at a shorter reaction time.
Acidic-based catalyst can enhance the hydrolysis and dehy-
dration of the biomass due to a higher concentration of H+ ion
in the solution [34, 35]. pH is one of the influential factors for
hydrothermal carbonization as supported by Reza et al. [36],
of which they investigated a wide range of pH for HTC of raw
wheat using acetic acid and KOH. The findings revealed that
HTC under acidic medium yields better results. It was also
found that initial pH greater than 7 promotes the reaction
towards more liquid products than the hydrochar [37]. Many
researchers have reported the utilization of organic acids such
as citric acid [38], acrylic acid [39], and sulfuric acid [40].
Nevertheless, the effect of weak acid such as ascorbic and
citric acid on palm oil residue is yet to be investigated. The
use of organic acid also helps to reduce the complexity of the
reaction and can be recycled to treat fresh biomass, hence
minimizing the cost effect [41].
In this study, the HTC of different oil palm biomasses
including palm leaves, palm fronds, and palm shell has been
carried out. The objective of this research is to optimize the
effect of process parameters of HTC, as well as to investigate
the impact of liquid acid catalyst on conversion of biomass
into hydrochar. Furthermore, the effects of process parame-
ters, i.e. reaction temperature, reaction time, and the presence
of catalyst, on physicochemical properties and yield of
hydrochar produced are reported.
2 Materials
The oil palm residues including palm fronds, palm leaves, and
palm shells were collected from a local palm oil mill in
Kampung Bota, Malaysia. Then, these biomass samples were
washed with distilled water in order to remove dust and im-
purities, dried in an oven at 105 °C for 24 h, and grinded into
1–5 mm size with an IMF 10 basic, IKA Labortechnik crush-
er. L-Ascorbic acid (99%), citric acid (≥ 99.5%), and anhy-
drous KBr (99%) were purchased from Merck Malaysia Sdn
Bhd.
3 Experimental
The HTC of all biomasses was conducted in a Premix auto-
clave batch reactor (1200 mm in length, 430 mm depth, and
540 mm internal diameter) with a volumetric capacity of 1 L.
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The reactor can withstand in high temperature (300 °C) and
pressure (150 bar), and it is connected with a stirrer (3000
rpm) to mix the reactants homogeneously. The experimental
procedure is shown in Fig. 1. Hydrothermal carbonization was
carried out at 140–300 °C for 30–240 min reaction time using
a 1:10 wt% biomass-to-water ratio in the presence of catalysts
(citric acid or ascorbic acid). The overall parametric condi-
tions of this study are shown in Table 1. Prior to this test,
approximately 10 g of biomass was dispersed in 100 mL of
distilled water. The prepared sample was mixed uniformly in a
batch reactor with a stirrer speed 6.8 Hz for 10 min. The
nitrogen was purged inside the reactor at 15 bars to avoid
water vaporization. Furthermore, the reactor was heated up
to reach the intended reaction temperature and the reaction
was carried out from 30 to 240 min. After completion of the
reaction, the reactor was cooled down by circulating cold wa-
ter. The liquid and solid products were transferred from the
reactor manually and separated by passing over a filter paper,
whereas the gas product was negligible and vented out. The
solid product then was kept in a drying oven at 105 °C for 4 h
for complete drying. The biomass which gives the highest
hydrochar yield then was selected for further investigation.
The yield of hydrochar was computed with the following for-
mula [23].
Hydrochar yield ð%Þ
¼ ðMass of hydrocharÞ=ðMass of FeedstockÞ  100 ð1Þ
4 Hydrochar characterization
The elemental contents of biomass and hydrochar were ana-
lyzed by a Vario Micro cube elemental analyzer (Elementar,
Germany). The samples were weighed around 1.5 to 2.0 mg in
an aluminium container before entering the analyzer. The
composition of oxygen was calculated by a difference meth-
od. The higher heating values (HHVs) of biomass and
hydrochar were measured by a bomb calorimeter (IKA
C2000 basic). According to Friedl et al. (2005), the HHV
can be predicted from the elemental analysis by using the
following equation [42].
HHVð kJ Þ ¼ 3:55C2−232C−2230H þ 51:2CH þ 131N þ 20600 ð2Þ
kg
where C, H, and N are carbon, hydrogen, and nitrogen con-
tents of the samples, respectively.
The combustion behaviours were evaluated by a STA 600
Simultaneous Thermal Analyzer (Perkin Elmer, USA). The
samples were weighed up approximately 5–10 mg and fill into
a small pan in thermogravimetric analysis (TGA). From the
TGA profile, the moisture contents, volatile materials, fixed
 Biomass Conv. Bioref.

Fig. 1 Flow diagram of the Collection of oil palm residues

experimental procedure
(palm fronds, palm leaves and palm shells)

Washing with distilled water

Dying at 105 C for 24 h

Grinding 1-5mm size in crusher

HTC in Premix autoclave batch reactor at 140-300 C, 15 bar nitrogen

pressure for 30-240 min reaction time in the presence of (citric acid and
Ascorbic acid) as catalysts at 3000 rpm using 1:10 wt.% biomass to
water ratio

Collection of liquid and solid products

and separation by filter paper

Oven drying of solid product at105 C

for 4 hours

carbon, and ash were determined. The functional groups of
biomasses and hydrochar were investigated by an FTIR spec-
trometer (Perkin Elmer) with a resolution of 4 cm−1, using a
pure KBr disc as a reference. Scanning electron microscopy
(SEM) that utilizes electrons for imaging was used to study the
surface morphology of feedstock and hydrochar. All samples
were placed onto an adhesive carbon tape on an aluminium
stub, loaded in a vacuum chamber with an accelerating volt-
age of 15 kV.

Table 1 HTC experimental

design on various operating Run Biomass Catalyst Temp. (°C) Time (min) Sample name
parameters
1 Palm leaves N/A 180 30 HC-1
2 Palm frond N/A 180 30 HC-2
3 Palm shell N/A 180 30 HC-3
4 *Palm shell Citric acid 180 30 HC-4
5 *Palm shell Ascorbic acid 180 30 HC-5
6 *Palm shell *Citric acid 140 30 HC-6
7 *Palm shell *Citric acid 180 30 HC-5
8 *Palm shell *Citric acid 220 30 HC-7
9 *Palm shell *Citric acid 260 30 HC-8
10 *Palm shell *Citric acid 300 30 HC-9
11 *Palm shell *Citric acid **180 30 HC-5
12 *Palm shell *Citric acid **180 60 HC-10
13 *Palm shell *Citric acid **180 120 HC-11
14 *Palm shell *Citric acid **180 180 HC-12
15 *Palm shell *Citric acid **180 240 HC-13

*Decided based on the highest yield of hydrochar from runs 1–5

**Based on run from HC-6-HC-9

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Biomass Conv. Bioref.
5 Results and discussion
5.1 Hydrochar yield
The effects of the biomass used, catalyst, reaction tempera-
ture, and time on hydrochar yield are shown in Fig. 2a–d. By
observing the effect of different feedstocks to the HTC, the
palm shells give a higher hydrochar yield as compared to palm
fronds and palm leaves. This is attributed to the higher lignin
content of palm shell than the rest of the materials studied. The
lignin content in lignocellulosic biomass materials is generally
measured by a two-step hydrolysis method [43]. The ligno-
cellulosic structure of biomass such as cellulose, hemicellu-
lose, and lignin influences the yield of the hydrochar.
Cellulose and hemicellulose decompose at a range between
200 and 300 °C, while lignin decomposes at a temperature
higher than 400 °C. Therefore, the biomass with higher lignin
content will generate higher hydrochar yields. Palm shells
consist of 51% lignin compared to palm fronds and palm
leaves, which have about 20% lignin in the present study.
Therefore, the palm shell was selected as the main biomass
feedstock as to further investigate the influence of catalyst,
temperature, and residence time on HTC.
Figure 2b shows the effect of different catalysts on
hydrochar yield, and it can be observed that the hydrochar
yield was 72% in absence of catalyst whereas it increased to
86.9% and 88.7% in presence of ascorbic acid and citric acid,
respectively. An increase in hydrochar yield with the addition
of acidic catalysts is due to a reason that the acidic catalysts
enhance dehydration, hydrolysis, and coalification reactions,
hence improving the hydrochar yield. It is reported that the
acidic conditions as compared to neutral environment accel-
erate hydrolysis, dehydration, and coalification [44]. It is also
stated that the weak acidic condition enhances the overall rate
of reaction in HTC [22]. From these results, it can be
Fig. 2 Yield of hydrochar: a a Yield of hydrochar from different biomass
100
different biomass feedstocks, b
different catalysts, c different 80
temperatures, and d different
60
Yield (%)
reaction times
40
20
0 0
Palm Shell
c Yield of hydrochar at different temperature
100
80
Yield (%)
60
40
20
0 0
140
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concluded that citric acid (pH ± 3.2) formed a higher
hydrochar yield than ascorbic acid (pH ± 2.2). Hence, citric
acid was selected as a catalyst for the rest of experiments.
It is proposed that the reaction temperature is an important
parameter that gives a great effect on the yield of hydrochar
from HTC. It is evident from Fig. 2c that an increase in reaction
temperature caused a significant drop in hydrochar yield,
where 89.8% hydrochar yield was produced at 140 °C, which
decreased further down to 54.5% at 300 °C, which is likely due
to hydrolysis and decomposition of cellulose, hemicellulose,
and lignin [27]. Hemicellulose is readily hydrolyzed at 180 °C,
whereas both cellulose and lignin degraded at a temperature
ranging from 200 to 300 °C [22, 33]. This can be justified that a
decrease in mass yield with an increase in temperature is ap-
plicable to all types of lignocellulosic biomass reported in a
previous experiment such as sewage sludge [24, 45, 46], grape
pomace [47], and coconut and rice husk [48]. According to
Nizamuddin et al. (2015), a sudden decrease in solid yield from
HTC of oil palm shell may be due to several reasons such as
elevated core decomposition of supplied feed at a higher tem-
perature, hence consequently resulting in the decomposition of
solid residue, and high solubility of components in hydrolysis
liquor [18]. The decreased hydrochar yield is said to be due to
thermal degradation of palm shell with an increasing tempera-
ture resulting from primary and secondary decomposition and
high solubilization of components in hydrolysis liquors [18].
Another study suggests that a decrease in hydrochar yield with
an increasing reaction temperature can be attributed to the gas
and liquid formation at higher temperatures [49]. Previous
studies also stated that hydrochar goes through secondary de-
composition, which follows gasification and liquefaction reac-
tions at a higher temperature [47]. A similar trend of reduction
in hydrochar yield with an increasing reaction temperature of
HTC of eucalyptus bark was reported in the literature [18, 22,
27, 50].
b Yield of hydrochar from different catalyst
100
80
Yield (%)
60
40
20
Palm fronds Palm leaves No Catalyst Ascorbic acid Citric acid
d Yield of hydrochar at different time
100
80
Yield (%)
60
40
20
180 220 260 300 30 60 120 180 240
Temperature (°C) Time (minutes)
 Biomass Conv. Bioref.

Reaction time is another significant parameter of HTC,
where it has a similar effect as reaction temperature. A higher
hydrochar yield can be observed at a shorter duration whereas
a lesser hydrochar yield is observed at longer reaction times as
shown in Fig. 2d. Similar observations were reported in this
study where 86.9% of hydrochar was produced at 30 min
reaction time, which decreased to 63.5% at 240 min. It is
suggested that longer reaction times may not only cause ex-
cessive polymerization, leading towards condensed products,
but simultaneously it undergoes decarboxylation reaction,
which ultimately tends to reduce the hydrochar yield.
Similar results were reported in a previous study on HTC of
palm shell [51].
5.2 Elemental analysis and HHV
The elemental analysis gives the carbon, hydrogen, nitrogen,
sulfur, and oxygen contents, which are present in biomass and
hydrochar samples as shown in Table 2. A higher carbon and
lower oxygen content is sought after because hydrochars with
high carbon contents and low oxygen contents exhibit high
fuel properties. As expected, the general trend shows that the
carbon content increases whereas oxygen and hydrogen con-
tents decrease after the HTC process. This behaviour (in-
creased carbon and decreased hydrogen and oxygen) for the
elemental analysis of hydrochars can be attributed to the pro-
cess parameters of HTC [52, 53] including reaction time, re-
action temperature, and catalyst used. An increase in carbon
and a decrease in oxygen may be attributed to the deoxygen-
ation and dehydration reactions taking place during HTC [20].
It was reported that an increase in carbon contents of
hydrochar at different processing parameters of HTC might
be attributed to the removal of oxygen and hydrogen contents,
followed by dehydration and decarboxylation processes, con-
sequently enhancing the fuel properties of hydrochar [18].
Furthermore, it was noted that both acid catalysts have a
higher carbon mass recovery compared to the hydrochar pro-
duced in the absence of catalyst, which indicates that acid
catalyst might have the tendency to prevent carbon loss.
HHV is considered one of the most significant fuel charac-
teristics of fuels, biofuels, and biomass materials, which de-
termines the amount of heat released during combustion. Both
measured and calculated HHVs of feed materials and
hydrochars are provided in Table 2. As expected, the HHVs
were improved after the HTC process. The increases in HHV
after the HTC process can be linked to the reaction pathways
of HTC, i.e. dehydration and decarboxylation [54].
Nevertheless, the effect of reaction time on HHV of hydrochar
was less significant as compared to that of the reaction tem-
perature for which similar results have been reported in a
previous study [27]. It is also stated that an increase in HHV
of hydrochar is due to an increase in carbon values of
hydrochar after the HTC process. The relationship between
HHV and carbon contents of the samples is shown in Fig. 3.
From the figure, it can be determined that carbon content is
directly proportional to HHV, which was proven in a previous
study by Nizamuddin et al. [18]. Additionally, theoretical
HHVs of these samples were calculated employing Eq. (2)
which were relatively close to the samples’ measured HHV
values, having relative inaccuracy less than 15%. Thus, HHV
also can be predicted by the elemental component of the
samples.
The results of the elemental analysis can further be elabo-
rated with the help of the van Krevelen diagram by plotting O/
C and H/C atomic ratios of all samples and comparing with
the O/C and H/C atomic ratio of coal as shown in Fig. 4.
Generally, the fuels with lower H/C and O/C atomic ratios
are preferred because a lower H/C and O/C atomic ratio indi-
cates a better fuel property due to reduction in energy loss,
water vapour, and smoke throughout the combustion process
whereas fuel with higher O/C and H/C ratios causes additional
water vapour and smoke during combustion, resulting in more
energy loss [18]. Therefore, it is anticipated that the HTC
process will tend to decrease H/C and O/C atomic ratios of
palm shell. As expected, Fig. 3 displays that the palm shell
itself shows a higher H/C and O/C atomic ratio, which de-
creases when hydrochars are formed, indicating that the
HTC process has successfully converted palm shell into

Table 2 Elemental analysis and HHV of feedstocks and hydrochar

Properties Palm Palm Palm HC- HC- HC- HC- HC- HC- HC- HC- HC- HC- HC- HC- HC-
shell fronds leaves 1 2 3 4 5 6 7 8 9 10 11 12 13

Ultimate analysis C 41.1 42.9 41.8 46.8 43.6 44.5 48.6 49.2 47.7 50.2 50.9 52.0 50.5 51.3 48.7 49.1
(%) H 5.38 5.9 5.95 5.82 5.95 6.07 6.12 6.16 6.2 5.86 5.6 5.34 8.4 8.37 5.94 5.84
N 2.39 3.16 4.86 3.35 3.16 5.06 3.43 3.31 2.67 2.63 2.78 2.92 2.97 3.15 2.49 2.63
O 50.4 47.7 47.0 43.7 47.3 43. 41.6 41.1 43.1 41.1 40.4 39.5 38 37.0 42.7 42.2
Atomic ratio H/C 1.56 1.65 1.71 1.49 1.65 1.63 1.51 1.5 1.56 1.4 1.32 1.23 2 1.96 1.47 1.43
O/C 0.91 0.83 1.71 0.7 0.82 0.74 0.64 0.63 0.67 0.6 0.59 0.57 0.56 0.54 0.65 0.64
HHV (MJ/kg) Measured 17.2 16. 17.2 19.7 17.3 18.4 19.2 19.5 17.5 20.3 21.2 23.1 21.4 21.7 21.8 22.7
Calculated 16.8 17.4 17.2 18.9 17.5 18.2 19.7 20.0 19.2 20.2 20.4 20.8 21.3 21.7 19.6 19.7

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Biomass Conv. Bioref.

HHV vs Carbon %
24
23
22 HC-13 HC-9
HC-11
21 HC-12 HC-10
HHV (MJ/kg)

HC-8
20
HC-7
19 HC-1
HC-4 HC-5
18
HC-3
17
Palm shell HC-2 HC-6
16
15
41 43 45 47 49 51 53
Carbon %
Fig. 3 Relationship between carbon % and HHV of palm shell and hydrochars

high-quality fuel. The reduction of O/C and H/C atomic ratios
after the HTC process may be correlated to dehydration, de-
oxygenation, and demethanation reactions taking place during
HTC. Similar results of decrement in O/C and H/C atomic
ratios were observed for hydrochar produced from HTC of
orange pomace [51].
5.3 FTIR analysis of feed and hydrochar
The FTIR analysis is carried out to determine functional
groups present in the sample. Therefore, FTIR bands of raw
palm shell, palm fronds, and palm leaves and their respective
hydrochars are shown in Fig. 5a–c. As indicated, there are
distinct differences shown in raw biomass and hydrochar pro-
duced, confirming the chemical conversion in course of the
HTC process. A decreased in intensity at wave number 3500–
3300 cm−1 indicates that the dehydration process took place in
the hydrochar resulting in the decrease of the OH functional
group. The peak appears at 3452–3412 cm−1 is attributed to
the OH stretching. This peak in hydrochar is less intense in
contrast to the raw biomass which is perhaps due to the dehy-
dration reaction occurring during the HTC process [27]. This
agrees with the results of the elemental analysis shown in
Table 2, which indicates the reduction of H/C and O/C as
examined earlier. Peaks between 2930 and 2810 cm−1 are
associated to the decrease of the CH bond, and peaks between
1630 and 1514 cm−1 are associated to the decrease of the CO
bond. The bands between 1744 and 1608 cm−1 are from the -
C=O stretching vibration of carboxylic groups in hemicellu-
loses and -C=C stretching vibration of aromatic rings present
in lignin [46]. A few related peaks are noticed at 2923 cm−1,
2919 cm−1, 2920 cm−1, and 2924 cm−1, which are related to
the C-H stretching vibrations of -CH, -CH2, and -CH3 groups
[55]. These peaks are found in solid product compared to the
raw palm shell. It indicates that the hydrogen has been re-
moved considerably by the HTC process.
More carbon-carbon bond is observed as well at
wavenumbers 1613 cm−1 and 1513 cm−1. A peak is noticed
at the range of 1423–1433 cm−1, which is due to the present of
-CH2 cellulose and lignin going through deformation. The
intensity of -CH2 cellulose and lignin is much lower indicating
more cellulose and lignin decomposed at a higher tempera-
ture. This matches the theory stated where lignin is yet to
decompose at a low temperature [43, 56]. Peaks at 1450
cm−1 and 1112 cm−1 illustrate the stretching of C=C that lies
under aromatic groups and C-O stretching in methoxy (-

2.20

2.00
HC-10
H/C Atomic ratio

HC-11
1.80

1.60 HC-6
HC-4 HC-3 HC-2 Palm Shell
HC-5
1.40 HC-12 HC-1
HC-7 HC-13
1.20 HC-8
Coal HC-9
1.00
0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90
O/C atomic ratio
Fig. 4 Van Krevelen diagram, H/C and O/C atomic ratios, of palm shell, hydrochars produced at different process conditions and coal

Content courtesy of Springer Nature, terms of use apply. Rights reserved.


a) Palm Shell
b Palm Frond
Palm Leaves
Fig. 5 FTIR of a palm shell and HC-1, b palm frond and HC-2, and c palm leaves and HC-3
OCH3) groups in lignin. Both peaks were spotted in raw bio-
mass and hydrochar, and it shows that the intensity is reduced
in hydrochar compared to that in the raw biomass [27].
5.4 Surface morphology
SEM was used to study the surface morphology of biomass
and hydrochar. The results of SEM for biomasses and their
respective hydrochars are shown in Fig. 6. The HTC process
changed the biomass microstructure and larger microspheres
were formed resulting in better fibrous solid after the HTC
process. As expected, considerable differences were observed
where biomass has a rough surface with fewer pores com-
pared to hydrochar, which also produces some small pores.
Small pores were observed in the hydrochar produced as a
result by gas emission from volatile matters [32]. The
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
Biomass Conv. Bioref.
HC-1
HC-2
HC-3
formation of pores on the surfaces of hydrochar is sustainably
triggered by the reaction time and reaction temperature of
HTC where the cellulose and hemicellulose are decomposed
at higher reaction times significantly, resulting in the forma-
tion of the pores on the hydrochar surface [53]. It is reported
that at higher temperatures, the biomass is significantly de-
graded because an exposure of biomass layers due to the in-
creasing temperatures improves the porosity of the hydrochar
surface. Marx et al. [57] reported that at higher temperatures,
the walls of the nearer pores are affected and destroyed, which
results in increasing the pore size diameters. The HTC split the
lignocellulosic structure of palm shell into fragments, which in
turn enhances the HTC process [27]. Hemicellulose and cel-
lulose are comparatively better to be carbonized as compared
to lignin content. Similar results of formation of pores on
hydrochar surface were reported in a previous study of orange
Biomass Conv. Bioref.

(a) HC-1

(b)
HC-2

(c) HC-3

Fig. 6 SEM images of a palm shell and HC-1, b palm frond and HC-2, and c palm leaves and HC-3

pomace by Edrogan et al. [51]. Though the porosity of
hydrochar is enhanced after HTC and is observed to be higher
than that of the raw biomass, however it still needs to be
improved; therefore, it is comprehensively demonstrated from
literature that the porosity of hydrochars is seemed to be low
because of the deposition of secondary microspheres on the
top end of the primary chars. Additionally, it is recommended
that the activation of hydrochars either by chemical or by
physical methods is vital to achieve higher degree porosity
and thus enhance the adsorption of hydrochar capacity.

Content courtesy of Springer Nature, terms of use apply. Rights reserved.


Fig. 7 TGA-DTG curves of palm shell and HC-1
5.5 TGA analysis of feed and hydrochar
The thermogravimetric analysis is recognized as an effective
way to evaluate the combustion behaviour of biomass and
hydrochar. According to Nizamuddin et al., there are four
sections of behaviour of lignocellulosic decomposition in bio-
mass, which are the removal of volatile component and water
at a temperature below 120 °C, the degradation of cellulose
between 220 and 315 °C, the degradation of cellulose and
lignin at 315–400 °C, and the deprivation of lignin, which
occurs at temperature higher than 450 °C [18]. The TGA/
DTG analysis of biomass and hydrochars is provided in Fig.
7, and it can be clearly observed that the combustion behav-
iour changes significantly between raw biomass and
hydrochar. Three major degradation phases are found in the
thermal decomposition of palm shell, palm fronds, palm
leaves, and their respective hydrochars. Between temperature
ranges from 30 to 130 °C, minor weight loss was observed,
which is caused by the removal of water absorbed during
HTC, i.e. approximately 10%. For temperature range between
200 and 750 °C, a high rate of decomposition could be no-
ticed, which shows the decomposition and pyrolysis of cellu-
lose and hemicellulose components [18]. The curve between
750 and 850 °C is observed to be constant, which indicates the
elimination of all volatiles that remain as the residues. The
changes in weight loss of hydrochar samples also can be at-
tributed to the HTC process and to the reaction temperature of
HTC. These results are in agreement with those of a previous
study indicating that carbonization reaction temperature plays
an important role in the hydrochar behaviour compared to
reaction time [27].
The peaks of DTG curves determine the temperature at
which a maximum rate of weight loss takes place. The first
DTG peak for biomass and hydrochar is around 150–300 °C,
which is probably due to the removal of water and decompo-
sition of hemicellulose. The second peak of DTG is around
350 to 400°, which could be ascribed to the decomposition of
cellulose. Similar results were reported in a previous study of
HTC of paper sludge [23].
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
Biomass Conv. Bioref.
6 Conclusion
Hydrothermal carbonization (HTC) is believed to be one of
the effective ways to convert biomass into a value-added prod-
uct, which is hydrochar with improved fuel properties.
Compared to other techniques, HTC is carried out in an aque-
ous medium, which suggests that wet biomass can be utilized,
consequently eliminates the pre-drying step prior to the HTC
process, and provides cost-saving opportunity.
Based on the obtained results, palm shell has similar
characteristics to coal as compared to palm fronds and palm
leaves. Among all three biomass types, palm shell generated
a higher hydrochar yield (72%) than others, i.e. palm frond
(54%) and palm leaves (67.2%), due to higher lignin content
present in palm shell. All three parameters including cata-
lyst, reaction time, and reaction temperature have a signifi-
cant effect on hydrochar yield and its properties. The
hydrochar yield percentage reduces with the increase of
temperature and reaction time due to the elevated rate of
liquefaction and gasification at high temperatures and lon-
ger reaction times. The optimized temperature and time for
HTC of palm shell were 180 °C and 30 min for 89.8%
hydrochar, respectively, in the presence of citric acid. The
presence of weak acid catalyst increases the yield and car-
bon contents of hydrochar, whereas oxygen and hydrogen
contents are reduced in hydrochar due to dehydration and
decarboxylation reactions taking place during the HTC pro-
cess. The elimination of oxygen and hydrogen contents in-
creases the proportion of carbon in the hydrochar.
Consequently, the HTC process converts a high moisture
feed (for instance, PKS contains up to 30% moisture con-
tent) into a high carbon content and high calorific value
product. SEM images show the production of more porous
product in comparison to biomass feed materials. The FTIR
analysis suggests that there are new peaks formed in
hydrochars and intensity of some peaks is increased. The
TGA analysis confirms that the thermal stability of
hydrochars is increased and two DTG peaks are observed
at 150–300 °C and 350–400 °C.
Biomass Conv. Bioref.
Funding The present research received funding from Yayasan Universiti
Teknologi PETRONAS, Perak, Malaysia (YUTP 015LC0-147 and
YUTP-015LC0-091).
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