Bioresource Technology 265 (2018) 365–371

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Upgrading agricultural wastes using three different carbonization methods: T

Thermal, hydrothermal and vapothermal
⁎
Keat-Hor Yeoha, S.A. Shafiea, K.A. Al-attabb, Z.A. Zainala,
a
School of Mechanical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
b
Department of Mechanical Engineering, Faculty of Engineering, Sana’a University, Sana’a, Yemen

G R A P H I C A L A B S T R A C T

A R T I C LE I N FO A B S T R A C T

Keywords: In this study, three different methods for high quality solid fuel production were tested and compared experi-
Hydrothermal carbonization mentally. Oil palm empty fruit bunches, mesocarp fibers, palm kernel shells and rubber seeds shells were treated
Vapothermal carbonization using thermal (TC), hydrothermal (HTC) and vapothermal (VTC) carbonization. All thermochemical methods
Thermal carbonization were accomplished by using a custom made batch-type reactor. Utilization of novel single reactor equipped with
Hydrochar
suspended internal container provided efficient operation since both steam generator and raw materials were
Energy densification
placed inside the same reactor. Highest energy densification was achieved by VTC process followed by TC and
HTC processes. The heating value enhancement in VTC and TC was achieved by the increase in fixed carbon
content and reduction in volatile matter. The formation of the spherical components in HTC hydrochar which
gave a sharp peak at 340 °C in the DTG curves was suggested as the reason that led to the increment in energy
content.

1. Introduction
In Malaysia, agricultural plantation is one of the main economic
activities where the main crops are oil palm fruit, rubber, paddy, co-
conut and coco. Huge amounts of by-products and residues are pro-
duced annually with an estimated potential of about 55,000 GWh of
electricity (Shafie et al., 2012). One of the most promising solutions for
the high carbon footprint in the large-scale coal fueled power plants is
to co-fire coal with biomass. This could drastically reduce the green-
house gas emission as biomass has no net CO2 emission throughout the
bio-cycle and also reduce harmful emission such as NOx and SOx
(Acharya et al., 2015). However, low-grade biomass solid fuel suffer
from the low energy density and high moisture that can affect com-
bustion quality. Other than that, biomass feedstock can differ con-
siderably in term of their physical, chemical and morphological char-
acteristics due to their heterogeneous natural. They are usually bulky

⁎
Corresponding author.
E-mail address: mezainal@usm.my (Z.A. Zainal).

https://doi.org/10.1016/j.biortech.2018.06.024
Received 20 April 2018; Received in revised form 8 June 2018; Accepted 9 June 2018
Available online 15 June 2018
0960-8524/ © 2018 Elsevier Ltd. All rights reserved.
K.-H. Yeoh et al.
and easily subjected to fungal attack or biodegradation as well. All
these characteristics of biomass lead to a higher complexity and cost for
feedstock preparation, handling, transportation and storage. Also, the
higher ash content in the feedstock can cause fouling and deposits on
the boiler tubes (Chen et al., 2015b; Chew and Doshi, 2011). To over-
come these problems, biomass is usually converted into various forms
of energy carriers such as ethanol, biodiesel, producer gas, biogas and
solid biofuels which are higher in energy density and can be handled
and stored with relative ease.
Biochemical and thermochemical conversions are two major routes
for enhancing biomass properties. Compared to biochemical conversion
methods, thermochemical treatment has shown several advantages
such as shorter processing time, higher conversion efficiency, ability to
convert a variety of biomass feedstock, ability to produce a diversity of
oxygenated and hydrocarbon fuel, lower cost of catalysts, ability to
recycle catalyst and does not require sterilization process (Brown, 2011;
Chen et al., 2015a; Liu et al., 2013). All these characteristics of ther-
mochemical conversion method make it more viable in treating large
amount of low-grade feedstock. Biomass torrefaction and thermal car-
bonization (TC) are some of the conventional thermochemical methods
to enhance its grindability and increase its heating value (Anuar et al.,
2017).
Hydrothermal carbonization (HTC) is another thermochemical
conversion process that has the advantage of treating wet or green
biomass material directly without any pre-dying (Park et al., 2018). In
HTC process, biomass materials are submerged in sufficient amount of
water, so that the solid materials react with liquid water at elevated
pressure and temperature (Liu et al., 2013; Kalderis et al., 2014;
Kongpanya et al., 2014; Lu et al., 2011; Novianti et al., 2014; Román
et al., 2012). HTC operates above normal water boiling temperature up
to 220 °C, followed by HT liquefaction and HT gasification at the sub-
critical and super-critical zones, respectively (Kruse and Dahmen, 2018;
Hrnčič et al., 2016). HTC process can be carried out without the ad-
dition of other chemicals or catalysts that makes it more attainable for
large-scale solid waste upgrading (Kambo and Dutta, 2015).
Another thermochemical process to upgrade wet biomass feedstock
is the vapothermal carbonization (VTC). It is also called vapor hydro-
thermal carbonization (Minaret and Dutta, 2016) or vapor-wet torre-
faction (Acharya et al., 2015). In this method, biomass materials are no
longer submerged in water but subject to high pressure saturated steam
(Novianti et al., 2014; Titirici et al., 2015; Yoshikawa, 2009). The main
difference between HTC and VTC methods is the reaction medium. In
HTC, hot compressed liquid water is the reaction medium, while in
VTC, the reaction medium is saturated steam (Quicker, 2015). It is hard
to predict whether liquid water or saturated steam are more effective in
upgrading biomass feedstock since both methods have their own ad-
vantages. Higher density of water allows higher heat transfer to the
biomass materials, while saturated steam which has a lower density is
able to penetrate the porous structure of the biomass material at a faster
rate (Minaret and Dutta, 2016).
As any other thermochemical treatment of biomass, HTC and VTC
also produce liquid and gaseous by-products beside the solid fuel as its
main products. Investigation from other researchers revealed that the
amount of by-products produced is insignificant with process para-
meter. As with the case of HTC, analysis of its liquid by-product showed
that total organic carbon is proportional with reaction severity (Funke
et al., 2013; Danso-Boateng et al., 2013). Moreover, degradation of
mineral content during HTC can also be measured from analysis of li-
quid by-product, but its trend was found out to be insignificant with
reaction severity (Basso et al., 2015). Basso D et al. also had established
presence of gaseous by-product from pressure profile of the reactor
during HTC treatment throughout the reaction time of 500 min (Basso
et al., 2015). It was claimed that pressure rise during HTC was due to
formation of gaseous products which consists of carbon dioxide (90%)
and carbon monoxide (8%), while hydrogen, methane, and traces of
light hydrocarbon build up the remaining 2% (Basso et al., 2015;
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Bioresource Technology 265 (2018) 365–371
Hwang et al., 2012). However the formation of gaseous by-product was
very low, only 2–3 bar increment in pressure was recorded for the entire
500 min treatment duration. Due to the insignificant volume of by-
products and its low relationship to reaction severity, current study
gives more emphasis on solid fuel properties produced from HTC and
VTC, and its comparison with TC. No consideration was given to their
respective liquid and gaseous by-products.
Only few experimental studies have been conducted to compare
between HTC and VTC processes (Funke et al., 2013; Minaret and
Dutta, 2016; Shafie et al., 2018). Studies showed that there are sig-
nificant differences between the two processes but it is difficult to ob-
serve a clear trend in comparing the effects of these two methods on the
product formed. In this study, HTC and VTC, additional to the con-
ventional TC processes where all experimentally compared. Wide range
of the common agricultural wastes in Malaysia were investigated. The
characteristics of the raw materials and carbonized produces were
thoroughly analysed in terms of composition, microstructure and
combustion performance.
2. Material and methods
2.1. Experimental setup
In previous study (Shafie et al., 2018), a dual-chamber test rig was
developed to evaluate the VTC process of high-moisture low-grade
biomass. The experimental set-up was modified to compare the three
carbonization methods: HTC, VTC and TC using single-chamber reactor
design. The new reactor consists of a cylindrical chamber of 150 mm
inner diameter and 400 mm height. The chamber was equipped with a
2 kW electrical heater band connected to a Type-K thermocouple and a
temperature controller for fast and accurate control of the temperature.
For steam pressure measurement, a 30 bar pressure gauge was used
with steam release and safety valves. Fig. 1 shows a schematic drawing
of the experimental test rig setup for HTC, VTC and TC processes.
2.2. Materials
In this study, four of the most abundant agricultural waste biomass
materials in Malaysia namely: oil palm empty fruit bunches (EFB), oil
palm mesocarp fibers (OPMF), oil palm kernel shells (PKS) and rubber
seeds shells (RSS) were investigated. The materials were dried at 110 °C
before the carbonization treatment process in order to ensure the con-
sistency of the quality of the feedstock throughout the experiments.
2.3. Hydrothermal carbonization (HTC)
The hydrothermal carbonization process was conducted by fully
submerging biomass in water under high temperature and pressure
inside the chamber as shown earlier in the experimental setup in Fig. 1.
Apart from reaction temperature and residence time, another factor
which influence HTC process is termed as water-to-biomass ratio (later
mention as W/B). W/B ratio can be defined as ratio of mass of water for
HTC process together with moisture inside raw materials, to the mass of
dried raw materials (Shafie et al, 2018). However this definition is
applicable if wet materials are used directly during HTC. Since current
study utilized dried raw materials for HTC process, only the mass of
water used during HTC was considered for W/B ratio determination.
Regardless of any predetermined W/B ratio, it must be ensure that all of
the materials were submerged inside the water to avoid the effect of
VTC on the non-submerged materials.
Water and biomass sample were both placed inside the 140 mm
diameter removable container before placing the container inside the
chamber and sealing the cover plate. The heater band controller was
then set to maintain the temperature inside the chamber at 220 °C for
one hour reaction period. After that, the gate valve on the cover plate
was opened to release the steam from the chamber and then it was left
K.-H. Yeoh et al.
Fig. 1. HTC, VTC and TC experimental setup.
to cool to room temperature. The product was then separated from the
water and dried in the PROTECH GOV-50 natural convection oven at
110 °C for 72 h until the weight was constant for further analysis.
2.4. Vapothermal carbonization (VTC)
In the vapothermal carbonization, biomass materials were subjected
to a high pressure steam. Biomass sample was placed inside a smaller
90 mm diameter removable container while water was filled through
the bottom gate valve. In this configuration, biomass sample inside the
removable container was surrounded by a water jacket with no contact
between the sample and water as shown earlier in Fig. 1. Similar ex-
perimental procedures to the HTC were used here and the only differ-
ence was that the sample reacts with high pressure steam instead of
water. A wire mesh was placed beneath the sample in the small con-
tainer to prevent any water accumulation inside the chamber by drip-
ping any condensed water to the bottom by gravity. The amount of
biomass materials used for each sample was the same as those in HTC.
2.5. Thermal carbonization (TC)
This is the conventional method commonly used for biomass car-
bonization by subjecting the sample material to heat in the absence of
oxidizer. All moisture and volatile materials start to vaporize first in a
conventional torrefaction process and with enough time, the carboni-
zation process extends from the outer surface of the sample to the core.
Similar procedures to the HTC and VTC processes were applied here
without the addition of water and the final drying process. A 100 g of
raw dry EFB was place in the 140 mm diameter removable container.
2.6. Product characterization
The main indicators of the product quality in this study are the
higher heating values (HHV), mass yield, energy densification and en-
ergy yield. Also, the changes in composition between the raw materials
and products in terms of fixed carbon (FC), volatiles mater (VM),
moisture content (MC) and ash content were compared. Moreover, the
enhancement in the product combustion characteristics were evaluated
and compared to the combustion of the raw materials. Finally, the
microstructure pictures of the raw and carbonized materials were
analyzed and compared using Hitachi S-3400N Scanning Electron
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Bioresource Technology 265 (2018) 365–371
Microscope (SEM).
These indicators were to evaluate the effectiveness of the carboni-
zation processes. They showed how much the carbonization processes
densify the energy content of the material and how much energy is
retained in the product after the carbonization process. These indicators
provide insights about the processes’ suitability for the purpose of en-
ergy densification. Using the dried mass of raw biomass and dried mass
of the hydrochar product, the mass yield from the carbonization process
was calculated using Eq. (1):
Mass of dried product
Mass Yield = × 100%
Mass of dried raw biomass (1)
Energy densification presents the HHV ratio of the dry product to
the dry raw materials as illustrated in Eq. (2):
HHV of dried product
Energy Densification ratio =
HHV of dried raw biomass (2)
Although the energy densification indicates the elevation in HHV
during the carbonization, considerable reduction in mass occurs as a
result of the process. Therefore, energy densification does not indicate
the true economic value of the product since is does not count for the
mass losses. Another useful indicator that includes the effect of mass
loses in the carbonization process is the energy yield as shown in Eq.
(3):
Energy yield = mass yield × energy densification ratio (3)
The HHV of the raw and carbonized materials were determined
using Nenken 1013-B Bomb Calorimeter. The weight of volatile matter,
fixed carbon and ash in the materials were determined through prox-
imate analysis using Perkin Elmer Pyris 1 Thermogravimetric Analyzer
(TGA). The TGA was also used to determine the combustion char-
acteristics of the raw and carbonized materials using thermogravimetric
(TG) and the first derivative (DTG) profiles. The TG-DTG profiles were
analyzed to determine several key combustion parameters namely: ig-
nition temperature (Ti), burnout temperature (Tb), temperature at
which maximum weight loss rate occurs (Tmax) and maximum weight
loss rate (Rmax). Tb is the temperature at which the mass stabilization
occurs while Tmax corresponds to the maximum weight loss rate which
represents the highest peak in DTG (Parshetti et al., 2013; Vamvuka
et al., 2011).
K.-H. Yeoh et al. Bioresource Technology 265 (2018) 365–371

Table 1
Effect of W/B ratio on the HTC product quality.
Properties EFB OPMF RSS

Raw WB = 150 WB = 30 % change Raw WB = 30 WB = 15 % change Raw WB = 30 WB = 15 % change

HHV (MJ/kg) 17.13 17.90 19.61 9.55 18.50 19.50 19.90 2.05 18.76 19.00 19.48 2.53
Mass yield (%) – 53.15 60.19 13.25 – 77.54 74.82 −3.51 – 73.75 70.52 −4.38
Energy densification – 1.045 1.145 9.57 – 1.054 1.076 2.09 – 1.013 1.038 2.47
Energy yield (%) – 55.53 68.88 24.04 – 81.74 80.50 −1.52 – 74.70 73.20 −2.01

Proximate analysis
Volatile matter (%) 82.244 87.555 83.534 70.604 72.660 72.896 78.331 81.050 77.962
Fixed carbon (%) 15.343 11.894 15.308 20.281 19.858 21.276 19.250 16.278 19.182
Ash (%) 2.413 0.551 1.158 9.115 7.482 5.828 2.419 2.672 2.856

3. Results and discussion
3.1. Effect of W/B ratio on product quality
For the hydrothermal carbonization, biomass material has to be
fully submerged in water, otherwise, the exposed material will have the
VTC effect instead of HTC. The shape and size of the raw biomass
governs the possible W/B ratio range. For example, for EFB with its fine
fiber form, it was possible to vary W/B ratio in a wide range from 30 up
to 150. On the other hand, for PKS with its large shell sizes, varying the
W/B ratio was not possible and only low W/B of 7.5 was tested. Table 1
shows the raw and product materials properties at different W/B ratios.
The types of materials showed considerable effect on the solid-water
reaction at elevated temperature. In terms of geometry, EFB has the
largest contact surface area with water among the tested materials al-
lowing up to 400% increment in W/B compared to 100% increment for
OPMF and RSS, thus, increasing the water-solid reaction. The dissolved
organic acids and sugars and also the degradation of cellulose and
hemicellulose, additional to the solubility of alkaline earth salts in
water, all have been reported in EFB hydrothermal reaction with high
W/B ratio (Nurdiawati et al., 2015). Therefore, high water-solid reac-
tion (i.e. high W/B ratio) affected HHV, energy densification, mass
yield and energy yield negatively, resulting in a reduced product
quality. This was also clearly indicated by considerable reduction in
FC% in the product. On the other hand, the amount of ash, metal
content and nitrogen (Novianti et al., 2015; Xu and Jiang, 2017;
Zhuang et al., 2017) were also significantly reduced by the hydro
thermal reaction and the dissolve of alkaline salts in water. Decom-
position of biomass materials during HTC caused acetic acid to be
formed as liquid by-product. This would trigger solubility of the in-
organic elements through acid solvation mechanism, which eventually
reduced overall ash content in the carbonized products (Kambo &
Dutta, 2015). This can be considered as a positive enhancement in
product quality by reducing NOx emissions and the fouling effect of
biomass combustion. In the case of OPMF and RSS, the effect of W/B
ratio was not as significant. Reducing W/B ratio resulted in a slight
elevation in HHV as FC% increased. However, the drop in mass yield
affected the overall energy densification of the product negatively. As
for the ash content, the low difference in water content resulted in a
similar alkaline salt dissolving for both cases.
3.2. Product characteristics
The effects of HTC and VTC processes on EFB, OPMF, PKS and RSS
biomass raw materials were investigated. As for the conventional
thermal carbonization (TC) process, only EFB was tested due to it fine
fiber construction with extreme surface area. While applying TC on the
other materials resulted in mild carbonization of the surface, while the
material core was still not carbonized due to the higher thickness.
Table 2 shows the properties of the raw biomass materials and the
HTC, VTC and TC products. In general, all the tested carbonization
methods were successful in upgrading the raw materials quality by
increasing their HHV values and achieving higher energy densification.
Fig. 2 illustrates the proximate analysis of the raw materials and HTC,
VTC and TC products in terms of the weight percentage of volatile
matter, fixed carbon and ash (on dry basis). The reaction mechanisms
for the different thermochemical carbonization processes are similar in
general to those of slow pyrolysis degradation of biomass. The reactions
include for example devolatilization, intermolecular derangement, ar-
omatization, polymerization, condensation, etc. (Kambo and Dutta,
2015). Moreover, these reactions can occur simultaneously if the con-
dition for the reaction was met. However, the intensity and the severity
of the reaction impact on the final product was found to be mainly
dependent on the reaction medium (i.e. compressed hot water, high
pressure saturated steam or hot gas) and the biomass raw material
shape and composition.
VTC method has achieved the highest HHV and energy densification
values for the products compared to HTC and TC methods. This can be
contributed mostly to the higher FC% in the product due to its higher
energy content as concluded in other researches (Shafie et al., 2018).
On the other hand, VTC products suffer from higher devolatilization
resulting in higher mass loss and lower mass yield %. However, as the
overall energy yield % is a balance between energy densification po-
sitive effect and energy yield % negative effect, the former was more
dominant from most of the tested material. This resulted in higher
energy yield % for most of the materials ranging from 71% up to 91%,
which indicated a higher economic value of VTC products.
TC treatment was only tested with EFB, and although it achieved
lower energy densification compared to VTC, the overall energy yield %
was 84% compared to 71% for VTC, due to the higher product mass
yield %. However, some of the downsides of TC treatment were the high
tar deposit on the reactor walls and the increment in ash content in the
product. VTC, on the other hand, resulted in a yellowish discoloration
of the walls due to the reaction of steam with tar, while HTC was the
cleanest method due to the high temperature solid-water reaction re-
sulting in tar decomposition in water. This consequently reduces the
maintenance cost and downtime if the treatment process is in-
dustrialized. As for the ash content, HTC achieved considerable re-
duction in ash content for most of the materials which reduces fouling
and deposits on boiler tubes when using HTC products as fuel.
Another observation of the HTC process was the increment of the
volatile matter content due to the high temperature solid-water reaction
causing deposition of 2,5-HMF. It also caused hydrolysis of hemi-
cellulose and cellulose which subsequently re-polymerized into sphe-
rical carbon structure found in hydrothermal treated materials (Kambo
and Dutta, 2015; Kruse et al., 2013). Therefore, the increment in HHV
in HTC products contributes to both the newly formed VM such as 2,5-
HMF (HHV = 22.06 MJ/kg) as well as the carbonized hemicellulose
and cellulose.

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K.-H. Yeoh et al. Bioresource Technology 265 (2018) 365–371

Table 2
Properties of raw and carbonized biomass materials.
Properties EFB OPMF PKS RSS

Raw HTC W/B 30 VTC TC Raw HTC W/B 15 VTC Raw HTC W/B 7.5 VTC Raw HTC W/B 15 VTC

HHV (MJ/kg) 17.13 19.61 21.92 20.79 18.50 19.90 23.25 19.64 20.19 23.42 18.76 19.48 21.37
Mass yield (%) – 60.19 55.88 69.18 – 74.82 72.78 – 86.05 72.53 – 70.52 72.64
Energy densification – 1.145 1.280 1.214 – 1.076 1.257 – 1.028 1.192 – 1.038 1.140
Energy yield (%) – 68.88 71.45 83.80 – 80.50 91.46 – 88.43 86.45 – 73.20 82.74

Fig. 2. Proximate analysis of raw and carbonized biomass materials.

3.3. Combustion analysis
There are a number of ways to determine ignition temperature of a
solid fuel such as pulse ignition technique, direct temperature mea-
surement during ignition using thermocouple, laser-induced ignition,
and ignitability test (Ahn et al., 2014), or using different equipment
such as TGA, cone calorimeter and fire propagation apparatus. In the
current study, TGA was utilized since it is not only capable of measuring
ignition temperature alone, but it also can measure other important
aspects of combustion characteristics such as burnout temperature, as
well as DTG peak (Ahn et al., 2014). TGA was proven to be capable of
measuring combustion characteristics of solid fuel effectively. It has
been reported that the error analysis of results produced by TGA can
achieve relative error below 7% (Chen et al., 2012).
From the DTG curves shown in Fig. 3, the combustion behavior of
the carbonized product showed considerable improvement compared to
their raw form. The temperature range in the DTG curve can be divided
into three distinguished zones. First zone below 200 °C indicates drying
performance while the second zone (200–400 °C) indicates decom-
position of most of the volatile materials and the third zone
(400–600 °C) indicates complete combustion of fixed carbon content
(Vamvuka et al., 2011). For EFB, the drying performance in the first
zone was similar for the raw materials and the final products due to the
fine fiber construction of EFB that allows faster and more efficient
evaporation. The reactions in second and third zones occurred at higher
temperature for all carbonization methods. VTC and TC products ex-
hibited similar combustion behavior as shown in the proximate ana-
lysis. Both VTC-EFB and TC-EFB showed lower peaks in the second zone
due to the lower VM% compared to raw materials, while multiple peaks
appeared in the third zone compared to one peak for raw materials.
For OPMF, the raw materials showed two main reaction regions at
250–350 °C and 400–470 °C. However, VTC-OPMF product showed
much lower first peak at around 330 °C, and also a broader reaction
region at temperature range from 370 °C to 500 °C. Thus, the overall
reaction region of VTC-OPMF product was shifted to higher tempera-
tures, which is in-line with the decrease of VM% and increase of FC%
observed from proximate analysis. VTC products of PKS and RSS also
showed similar combustion behavior and peak at around 250–350 °C.
Other than that, the overall reaction region of VTC for PKS and RSS
shifted towards 370–500 °C temperature range with larger area under
the curves and broader coverage of DTG curves as a result of the higher
FC% in the product.
On the other hand, HTC process exhibited totally different com-
bustion characteristics where most of the material loss (highest peak in
the DTG curves) occurred in the second zone while steady mass loss rate
extended through all the third zone with no sharp peak. This supports
the hypotheses of the formation of new VM with higher heating value
due to the high temperature solid-water reaction, which was also sup-
ported by the proximate analysis results. Sharp peak at around 340 °C
with highest mass loss rate was observed for EFB, OPMF and RSS, but it
then extended through smaller broad peaks beyond the VTC combus-
tion range up to about 540 °C.
Table 3 summarizes the main combustion characteristic parameters
of the raw and carbonized products. In general, all the tested carboni-
zation processes increased the burnout temperatures of the products
significantly compared to the raw materials. However, the shape of the
raw materials played a considerable role in product quality and com-
bustion characteristics. PKS showed lower performance due to the
higher thickness of the raw materials that limited the high temperature
reaction to the outer layers only. HTC-PKS showed low mass loss in the

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K.-H. Yeoh et al. Bioresource Technology 265 (2018) 365–371

Fig. 3. DTG curves of raw and carbonized materials (a) EFB; (b) OPMF; (c) PKS; (d) RSS.

Table 3 shape. For OPMF products, the ignition temperature of HTC product
Combustion characteristics of raw and carbonized biomass materials. was higher than VTC product but with similar burnout temperatures.
Sample Ignition Burnout Temperature at Maximum
While in the case of PKS, VTC product showed higher ignition tem-
Temperature Temperature maximum weight loss perature and burnout temperature compared to HTC product, unlike
(°C) (°C) weight loss rate rate (mg/ the RSS products that showed opposite results.
(°C) min)

EFB 259 466 427 1.282 3.4. Microstructure analysis

EFB-HTC 303 524 340 1.817
EFB-VTC 259 514 436 0.887 The scanning electron microscopy analysis of the raw and carbo-
EFB-TC 261 512 443 1.009
nized biomass materials showed spherical structures formed only in the
OPMF 256 491 295 0.659 HTC products but not the VTC. The reaction mechanism was observed
OPMF-HTC 303 542 342 1.140
to be associated with the hydrolysis of biomacromolecules in the high
OPMF-VTC 274 545 428 0.695
pressure hot water medium, followed by the dehydration and con-
PKS 257 481 451 1.348
densation of the biomaterials forming spherical char nano-particles
PKS-HTC 273 493 427 1.217
PKS-VTC 286 533 445 1.109
(Kambo and Dutta, 2015). These structures were formed by the re-
polymerization of the components dissolved into the aqueous phase.
RSS 274 485 429 1.022
RSS-HTC 316 528 341 2.131
Hydrolysis of cellulose formed glucose, and then further dehydrated
RSS-VTC 291 512 430 1.292 into 2,5-hydroxymethylfurfuraldehyde (2,5-HMF) and subsequent un-
dergo aldol condensation/addition to form these carbon spheres as
concluded by other researchers (Kruse et al., 2013). The formation of
devolatilization zone (second zone), where HTC usually excel, with the spherical structure is one of the characteristics of HTC products.
maximum value of only 0.561 mg/min compared to 1.817 mg/min in Absent of the spherical structures in VTC products indicated that the
HTC-EFB, 1.140 mg/min in HTC-OPMF and 2.131 mg/min in HTC-RSS. reaction pathway via a soluble coke did not dominate the carbonization
Also, both HTC and VTC processes resulted in lower Rmax values com- process which involved the re-polymerization of 2,5-HMF (Funke et al.,
pared to the raw PKS material, however, other parameters such as ig- 2013).
nition and burnout temperatures were enhanced, especially in VTC
process. 4. Conclusion
The comparison between HTC and VTC products showed incon-
sistent results that depended mainly on the raw material nature and All the tested carbonization methods showed significant

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K.-H. Yeoh et al.
enhancement in raw materials quality and combustion characteristics.
VTC process showed the highest energy densification followed by TC
and then HTC. However, VTC products suffered from low mass yield %
due to the high devolatilization, unlike the HTC products. Energy
densification effect was more dominant compared to mass yield % re-
sulting in higher energy yield % values for VTC product compared to
HTC. The high temperature solid-water reaction in HTC contributed to
the formation of carbon deposition of 2,5-HMF that was confirmed by
the formation of spherical components seen in SEM pictures.
Acknowledgements
The authors would like to acknowledge the financial support of
USM Fellowship provided by Universiti Sains Malaysia and RUI grant
1001/PMEKANIK/814253.
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