Applied Energy 113 (2014) 1315–1322

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Preparation and characterization of fuel pellets from woody biomass,

agro-residues and their corresponding hydrochars
Zhengang Liu, Augustine Quek, R. Balasubramanian ⇑
Minerals, Metals and Materials Technology Center, National University of Singapore, Singapore 117576, Singapore
Department of Civil and Environmental Engineering, National University of Singapore, Singapore 117576, Singapore

h i g h l i g h t s

 The fuel pellets from raw biomass and corresponding hydrochar were prepared.
 Hydrochar pellet had increased mechanical strength and improved fuel quality.
 Liquid bridge and enhanced attractive forces were formed within hydrochar pellet.
 Hydrochar pellets were more suitable for power generation than raw biomass pellets.

a r t i c l e i n f o a b s t r a c t

Article history: Two types of biofuel pellets were prepared from raw biomass and the corresponding hydrochar. Fuel
Received 12 June 2013 qualities of the two types of pellets including pellet density, mechanical strength and combustion char-
Received in revised form 26 August 2013 acteristics were investigated. The results showed that the hydrochar pellets had higher fixed carbon con-
Accepted 30 August 2013
tents, elevated heating values and enhanced mass densities in comparison to those raw biomass pellets.
Available online 27 September 2013
The presence of extractives led to the low tensile strength of biomass pellets, while the formation of
liquid bridge and significantly enhanced attractive forces including H-bonding and van der Waal’s forces
Keywords:
mainly contributed to the strong bonding within the matrix of hydrochar pellets. The hydrochar pellets
Pelletization
Tensile strength
combusted at elevated temperatures and wide temperature ranges compared to biomass pellets. The high
Hydrochar pellet mechanical strength, low moisture uptake and improved combustion property indicated that hydrochar
Fuel quality pellets were more suitable than raw biomass pellets as solid biofuels. The present study demonstrated
that hydrothermal carbonization (HTC) combined with pelletization provides an alternative for solid bio-
fuel production from biomass resources, especially for the abundant agricultural residues.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
The utilization of renewable biomass energy is increasingly
important in response to continuously growing energy demand,
depletion of conventional fossil fuels and the need for significant
reduction of greenhouse gas emissions. However, the inherent
properties of biomass feedstocks such as high dust levels and
low bulk density together with a wide range of physical shapes cre-
ate big challenges for their handling logistics and combustion tech-
nology [1,2]. By pelletization, raw biomass can be converted into a
pellet form with improved fuel quality such as increased bulk den-
sity, and uniformed shape and size [3–5]. The increased bulk den-
sity can reduce the storage and transportation costs while the
uniformed dimensions facilitate the handling and feeding issues.
⇑ Corresponding author at: Department of Civil and Environmental Engineering,
National University of Singapore, Singapore 117576, Singapore. Tel.: +65 65165135;
fax: +65 67744202.
E-mail address: ceerbala@nus.edu.sg (R. Balasubramanian).
In addition, the improved fuel quality enables biomass pellets suit-
able for many industrial and residential applications including
combustion in grate furnace and gasification in fluidized bed fur-
nace. The global pellet market has experienced a rapid growth dur-
ing the last decade and is expected to have even a faster growth in
the near future [6].
Additionally, in view of the seasonal availability of biomass
feedstocks, the medium or long-term storage property of biomass
pellets under ambient weather conditions is one of major concerns.
Therefore, good mechanical durability such as high tensile strength
and low moisture uptake is highly desirable for biomass pellets.
For example, high moisture uptake by biomass can lead to pellet
disintegration and provide a conducive environment for microbial
and biochemical activity during the storage [7–9]. Moreover, the
evaporation of the moisture during combustion reduces the net en-
ergy output and the high moisture content is also closely associ-
ated with high emissions of air pollutants [1]. As for the bonding
forces of integrating the particles into the pellet, several
mechanisms have been proposed such as attractive forces

0306-2619/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apenergy.2013.08.087
1316 Z. Liu et al. / Applied Energy 113 (2014) 1315–1322
(H-bonding or van der Waals forces) and mechanical interlocking
between fibers and particles [10]. The mechanical strength of the
pellets is affected by many factors including compression force
and temperature, the particle size and chemical composition of
biomass feedstocks [11–13]. For example, due to the increased lig-
nin content, the pellets made from steam-exploded poplar wood
resisted higher breaking forces than untreated poplar pellets
[13]. As for the influence of pelletization conditions, the lignin in
biomass can serve as natural binder when pelletization tempera-
ture is higher than lignin’s phase transition temperature, and con-
sequently the resultant biomass pellets have high tensile strength
[14]. Generally severe conditions, such as high temperature, ele-
vated compressive force and binder addition, result in high tensile
strength of the pellets. However, the increased severity also means
increased energy consumption and is therefore not favorable for
industrial pellet production.
In comparison to raw biomass, biomass pellets have obviously
improved fuel quality. However, biomass pellets may still not be
the ideal fuels because of the high moisture affinity and the rela-
tively weak durability, especially for the pellets made from agricul-
tural residues [7–9]. In addition, raw biomass as a direct fuel suffers
from serious slagging and fouling problems and these ash-related
problems are still not addressed while converting biomass into
their pellet forms. Therefore, it is necessary to pre-treat biomass
feedstocks prior to pelletization to overcome the practical problems
mentioned above. Hydrothermal carbonization (HTC) is a promis-
ing pre-treatment method to upgrade diverse biomass feedstocks.
HTC simulates natural coalification in coal petrology, involving
the decomposition and carbonization of biomass material in water
medium at desired temperature and autogenous pressure. The fuel
quality of raw biomass can significantly be increased by HTC and
the resultant hydrochar has similar fuel quality to that of lignite
[15]. More importantly, the ash content of hydrochar is significantly
lower relative to its parent biomass, suggesting potentially miti-
gated ash-related problems by the use of hydrochar [15,16]. Com-
pared to the raw biomass pellets, the fuel quality of hydrochar
pellets is expected to be further improved due to the increased fuel
quality of the hydrochars. Therefore, HTC of biomass feedstocks,
combined with pelletization, is potential to provide a better alter-
native for the utilization of biomass feedstocks, addressing the
drawbacks of handing logistics and combustion characteristics de-
rived from raw biomass materials. Although biomass pellets have
been extensively studied in recent years, these studies have been
focused largely on woody biomass pellets, instead of the most
abundant agricultural residues which are of growing concern
[3,17,18]. In addition, the recent studies mainly concern on the
mechanical durability of biomass pellets while combustion behav-
ior of the pellets is sparsely reported [4,5]. In the case of hydrochar
pellets, only one report is available in the literature about woody
biomass-derived hydrochar pellets to date [19].
In the present study, hydrochar pellets were prepared from
woody biomass and agricultural wastes, and their corresponding
raw biomass pellets were also prepared under identical operating
conditions for comparison. The fuel qualities of hydrochar pellets
and raw biomass pellets were evaluated and compared in terms
of pellet density, mechanical strength and combustion characteris-
tics. In addition, the bonding mechanism of hydrochar pellets was
also proposed.
2. Experimental
2.1. Materials
Woody biomass (pinewood sawdust (PS)) and agro-residues
(rice husk (RH), coconut fiber (CF) and coconut shell (CS)) were
used in the present study. The hydrochar was prepared from typi-
cal HTC of biomass materials and detailed procedures can be found
elsewhere [15]. Briefly, around 10 g of biomass was loaded with
100 ml de-ionized water into a 500-ml autoclave and the reactor
was heated to 250 °C (pressure around 4.2 MPa). After maintaining
at 250 °C for 20 min, the reactor was cooled to room temperature.
The hydrochar was recovered as a solid residue by vacuum filtra-
tion, and then washed using de-ionized water. The resultant
hydrochar samples were designated as ‘‘xx-HC’’, where the xx re-
ferred to the parent biomass. Prior to pelletization, raw biomass
and the corresponding hydrochar were dried at 60 °C and milled
to less than 150 lm.
2.2. Preparation and characterization of the pellet
The pellet was prepared using a single pelletizer without any
additional binder at room temperature. The assembly consists of
two parts: (1) a piston with 13.2 mm in diameter and 30 mm in
length, (2) a cylinder with 13.5 mm inside diameter and 40 mm
length. The end of the die is closed using a removable backstop.
The biomass/hydrochar was loaded stepwise in same amounts into
the pelletizer, and then compressed at a maximum pressure of
280 MPa. After holding 5 s at the maximum pressure, the pellets
were removed from the die by removal of the backstop and pushed
out by applying pressure on the pellets. The L/D of the pellets was
around 0.9 and at least 6 pellets were made for each sample.
Proximate analysis was carried out according to the Standard
Practice for the Proximate Analysis of Coal and Coke (GB/T212-
2001) using a Kaiyuan 5E-MAG6600 Automatic Proximate
Analyzer (China). Higher heating value (HHV) was calculated
according to the equation HHV = 0.312 FC + 0.1534 VM, FC and
VM were the percent of fixed carbon and volatile matter of the fuel,
respectively [20]. The micrograph of pellet surface was recorded on
a Zeiss light microscopy (Germany).
The mechanical strength of the pellet was analyzed on an
Instron Universal Tester (USA). The cylindrical pellet was horizon-
tally placed between two anvils and compressive force was applied
to the side of the pellet. The tester was run at a compression rate of
1 mm/min, and stopped after the pellet was fractured or broken.
The tensile strength (TS) was calculated by the following equation
[13]:
2F
TS ¼ ð1Þ
pld
where F was maximum compressive force; d and l were pellet diam-
eter and length, respectively.
Prior to the moisture uptake test, the pellets were dried at
105 °C for 24 h. The moisture uptake of the pellets was measured
in a humidity chamber which was set at 25 °C and 60% relative
humidity. The weight of the sample was measured every 15 min
for the first hour followed by every 1 h for the following 8 h. Three
replicates were measured for each set of pellet samples and thin-
layer drying formulation was adopted for the kinetic analysis of
moisture uptake [18].
Thermogravimetric analysis (TGA), the most useful and quick
technique for evaluating combustion characteristics of solid fuel,
was carried out on a thermobalance TGA-Q500 (USA). All combus-
tion experiments were conducted at atmospheric pressure, using
temperature range from room temperature to 850 °C with a heat-
ing rate of 20 °C/min and an air flux of 150 ml/min. Limited by the
size of the sample pan, the pellet was broken into small parts using
a razor blade manually and a small mass (approximately 15 mg for
raw biomass pellets and 25 mg for hydrochar pellets) was used to
evaluate combustion behavior.
 Z. Liu et al. / Applied Energy 113 (2014) 1315–1322 1317

3. Results and discussion
3.1. Proximate analysis and density analysis
The proximate analyses of raw biomass, hydrochar and their
corresponding pellets are presented in Table 1. The hydrochars ex-
cept RH-HC had improved fuel quality than raw biomass including
reduced ash content and enhanced energy density. The decreased
ash content of the hydrochars is ascribed to the dissolution of con-
siderable fraction of inorganics originally contained in raw biomass
in water during HTC [21,22]. It can be seen that fuel qualities of the
hydrochars except that of RH-HC were higher than those of their
parent biomass. More importantly, by pelletization the fuel quality
was further enhanced for both raw biomass and the hydrochars:
decreased moisture content, increased fixed carbon content, re-
duced ash content and elevated HHV. For example, the fixed car-
bon ratios in all combustible carbon were 22.26% and 42.51% for
CF and CF-HC, respectively, which were increased to 33.78 and
46.56% for CF pellet and CF-HC pellet, respectively. As a result of
the increased fixed carbon ratios, the HHVs also increased by
10.94% (from 15.90 to 17.64 MJ/kg) and 4.87% (from 20.55% to
21.55%) for CF pellet and CF-HC pellet. In addition, a notable de-
crease of the ash content was also observed by pelletization, which
is possibly associated with the increased combustion temperature
of the pellets compared to that of powder fuel [23,24]. For exam-
ple, the ash content decreased by 21.14% and 32.71% for CF (from
5.65% to 4.45%) and CF-HC (from 2.14% to 1.44%), respectively.
The decreased ash contents and decreased moisture contents im-
plied that higher thermal efficiency could be achieved during the
combustion of hydrochar pellets.
The mass density of the pellets is related to its energy density
with the applied pressure was observed during densification of
palm fiber and shell [26]. Even though low pressure and room tem-
perature were used for pellets preparation, the mass densities of
hydrochar pellets prepared in the present study were similar to
those of hydrochar pellets prepared under severe pelletization con-
ditions [19]. The pelletization conditions are associated with pro-
duction costs and required pellet properties and should therefore
be optimized to achieve the maximum environmental and eco-
nomic benefits of hydrochar pellets.
The mass density and energy density of hydrochar pellets were
higher than their corresponding raw biomass pellets and these val-
ues were well above the threshold for industrial fuel pellet produc-
tion [27]. In view of extremely low ash content and significantly
high energy density, hydrochar pellets, with the exception of RH-
HC pellets, are therefore more suitable than raw biomass pellets
for their use as solid biofuels [27].
3.2. Mechanical strength
Fig. 1 shows the curves of compressive force against compres-
sive distance of raw biomass pellets and hydrochar pellets. The
maximum compressive forces and tensile strengths for all the pel-
lets are presented in Table 2. Tensile strength of raw biomass pel-
lets was in the following order: PS (3.91 MPa) > RH (2.05 MPa) > CF
2500
CF pellet
CF-HC pellet
RH pellet
2000 RH-HC pellet
CS pellet
Compressive force (N)

and mechanical strength. In the present study, the mass density CS-HC pellet
was calculated based on the volume and mass of the pellets and PS pellet
1500 PS-HC pellet
the results are shown in Table 1. As expected, the mass density
was further increased significantly for both raw biomass and the
hydrochars by pelletization (by the range from 180% to 482% for 1000
all the pellets). The hydrochars had higher mass density than par-
ent biomass and consequently, the mass density of hydrochar pel-
lets was higher than that of their parent biomass pellets. RH and
500
RH-HC pellets exhibited the highest densities of 1093 and
1334 kg/m3 among all the pellets made from the raw biomass
and the hydrochars, respectively. The high mass densities of RH
0
and RH-HC pellets can be ascribed to the presence of the silica in 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
the RH and RH-HC [25], and this explanation is consistent with Distance (mm)
high ash contents as revealed by the proximate analysis.
Pelletization pressure plays an important role in mass density of Fig. 1. Compressive force versus distance curves of the pellets prepared from raw
the pellet. As an example, an exponential increase in mass density biomass and corresponding hydrochars.

Table 1
Proximate analysis, mass and energy densities of raw biomass, hydrochars and their corresponding pellets.

Sample Volatile matter (%) Fixed carbon (%) Ash (%) Moisture (%) HHV (MJ/kg) Mass density (kg/m3) Energy density (GJ/m3)
CF 65.50 18.75 5.65 10.10 15.90 169 2.69
CF pellet 56.94 28.54 4.45 10.07 17.64 984 17.36
CF-HC 53.50 39.56 2.14 4.80 20.55 242 4.98
CF-HC pellet 50.68 44.16 1.24 3.92 21.55 1153 24.85
RH 64.48 10.18 17.12 8.22 13.07 296 3.87
RH pellet 63.73 13.23 15.01 8.03 13.90 1093 15.19
RH-HC 50.81 16.22 27.90 5.07 12.85 381 4.90
RH-HC pellet 45.93 25.77 23.28 5.02 15.08 1334 20.12
CS 75.27 18.28 1.21 5.24 17.25 310 5.35
CS pellet 74.53 19.72 1.14 4.61 17.59 1101 19.37
CS-HC 73.20 20.25 0.69 5.86 17.55 411 7.21
CS-HC pellet 50.86 43.87 0.41 4.86 21.49 1153 24.78
PS 82.19 8.77 0.88 8.16 15.34 286 4.39
PS pellet 82.82 10.97 0.75 5.46 16.13 1141 18.40
PS-HC 56.32 39.20 0.68 3.86 20.87 312 6.51
PS-HC pellet 55.31 40.47 0.36 1.86 21.74 1191 25.89
1318 Z. Liu et al. / Applied Energy 113 (2014) 1315–1322
Table 2
Maximum compressive forces, tensile strengths, length expansions and moisture uptakes of the pellets prepared from raw biomass and corresponding hydrochars.
Sample Maximum compressive Tensile strength
force (N) (MPa)
CF pellet 375 1.51
CF-HC pellet 1867 7.50
RH pellet 515 2.05
RH-HC pellet 1049 4.21
CS pellet 246 0.96
CS-HC pellet 746 2.97
PS pellet 990 3.91
PS-HC pellet 1755 7.10
(1.51 MPa) > CS (0.96 MPa). In the present study, the lignin origi-
nally contained in raw biomass cannot act as a binder due to the
low pelletization temperature. Therefore, the bonding forces in-
volved in raw biomass pellets are mainly related to attractive
forces including H-bonding, van der Waals force and mechanical
interlocking. The extractives in biomass plays a significant role in
the attractive forces of adjacent lignocellulose particles; its pres-
ence leads to a weak H-bonding and van der Waal’s forces by pre-
venting a close contact between adjacent bonding sites [12,28]. It
is obviously that the tensile strength of raw biomass pellets is con-
sistent with the content of extractives in raw biomass (the extrac-
tives contents of raw biomass were in the order: PS (4.0%) < RH
(6.2%) < CF (6.9%) < CS (8.4%)). This finding implies that the bond-
ing forces within raw biomass pellets can be mainly ascribed to
attractive forces.
Fig. 2a shows the physical appearances of the pellets made from
raw biomass and the hydrochars. As can be seen, the hydrochar
pellets had much smoother surface than that of raw biomass pel-
lets. The surface micrographs of the pellets were examined at a
magnification of 200 (shown in Fig. 3) to further investigate bond-
ing mechanism within the pellets. From the micrograph, it can be
seen that the surface of hydrochar pellets was very uniform with-
out obvious void spaces. In contrast, a substantial amount of voids
and gaps existed on the surface of raw biomass pellets. These
spaces can reduce the pellet resistance to the deformation and pro-
mote the relative movement of the particles within the pellet ma-
trix, leading to weak mechanical durability.
As shown in Fig. 2b, as a representative sample, the PS pellet de-
formed mainly in axial direction (the biomass was fed to the cylin-
der several times and the deformation implied heterogeneous
structures within PS pellet) under the application of compressive
force. In contrast to the PS pellet, the PS-HC pellet broke into two
halves in its radial direction, reaching a definite breaking force
and the broken cross sections confirmed the homogenous structure
within the PS-HC pellet. The definite maximum resistant force and
breaking pattern also suggests the strong bonding within hydro-
char pellets.
Fig. 2. Appearances of (a) the pellets prepared from raw biomass and correspond-
ing hydrochars and (b) broken PS pellet and PS-HC pellet reaching maximum
compressive forces.
Length expansion (%) Equilibrium moisture Moisture uptake
content (%) rate (103) (min)
8.70 3.43 1.0
0.52 1.79 9.9
7.26 3.26 7.1
0.71 2.29 12.6
9.73 3.20 8.7
0.69 2.31 12.2
7.77 4.08 8.1
0.55 1.16 7.1
As shown in Table 2, the tensile strength of hydrochar pellets
was significantly increased in comparison to that of raw biomass
pellets, especially for CF pellet (1.51 MPa) and CF-HC pellet
(7.50 MPa). As a direct comparison, the tensile strength of hydro-
char pellets was greatly higher than those of raw biomass pellets
and pretreated biomass pellets reported in the literature
[3,4,13,17,28]. The extremely high tensile strength suggests the
presence of strong bonding forces between hydrochar particles
within hydrochar pellets and the unique property of the hydrochar
contributes to the strong bonding forces as explained in detail
below.
Firstly, the high molecular organic compounds provided liquid
bridge between adjacent particles within hydrochar pellets. After
HTC, considerable amount of polar organic compounds (so called
bio-oil) deposits on the surface of the hydrochar [29]. Similar to
water, these organic compounds can bridge the adjacent particles
by forming liquid bridge during pelletization, resulting in high
mechanical strength of hydrochar pellets due to the formed liquid
bridge [30]. In addition, the liquid bridge is affected by capillary
pressure, surface tension and viscose force, and a stronger strength
of liquid bridge within hydrochar pellets can be expected because
of the higher viscose force of organic compounds than that of the
water [30].
Secondly, enhanced attractive forces within hydrochar pellets
were probably formed due to the increased polar functional groups
on the surface of the hydrochars, high contact surface area be-
tween hydrochar particles and the absence of the extractives in
hydrochars. HTC creates more functional groups on the surface of
the hydrochars relative to those on raw biomass and totally re-
moves the extractives originally contained in raw biomass
[31–33]. For example, the contents of total oxygen-containing
groups (hydroxyl, carboxyl and carbonyl groups) were reported
to have been increased 98% and 62% for PS and RH by
hydrothermal treatment at 250 °C, respectively [31]. Increased po-
lar functional groups entail strong electrostatic attraction includ-
ing H-bonding and van der Waal’s forces. As an example, the
bond strength of H-bonding can reach 2.5–120 kJ/mol and the
bond lengths vary between 0.12 and 0.32 nm depending on the
bond strength. Therefore, by compressing the hydrochar particles
to reach a distance of less than 0.32 nm, increased H-bonding can
occur due to increased oxygen-containing groups on the surface.
Meanwhile, the absence of the extractives in the hydrochars also
facilitated the formation of strong attractive forces between adja-
cent hydrochar particles [12,29,33]. As for the enlarged contact
surface, it was ascribed to the highly friable property of the hyd-
rochars caused by the increased lignin content [15]. As a result of
the high friability, the hydrochar broke into the small particles un-
der applied compressive force during pelletization. Consequently,
the contact area between adjacent hydrochar particles was en-
larged compared to that of raw biomass. The increased contact sur-
face area further enhanced liquid bridge and attractive forces
between adjacent particles [34]. Finally, mechanical interlocking
 Z. Liu et al. / Applied Energy 113 (2014) 1315–1322 1319

Fig. 3. Micrograph of the surface of raw biomass pellets and corresponding hydrochar pellets.

possibly also played an increased role within hydrochar pellets
than raw biomass pellets due to the increased surface area and
pore structure of hydrochar particles [32].
Some particles were detached from the surface of raw biomass
pellets during 2-week storage and the surface became coarser,
especially for CS pellet. This was probably caused by the elastic
recovery of raw biomass particles and also indicated the weak
bonding within raw biomass pellets. Fig. 4 shows the detailed
length expansion of the pellets. The length expansions for the
hydrochar pellets were far lower than those of raw biomass pellets.
For all the raw biomass pellets, there was a notable length expan-
sion within the initial 2 days, and no obvious expansion was ob-
served after 4 days of storage. For example, length expansions of
PS pellet reached 4.9% and 6.9% after 1 and 2 days, respectively
and reached the highest expansion 7.75% after 4 days. In the case
of hydrochar pellets, limited length expansions were observed (less
than 0.71%) and reached their maximum within 2 days. The limited
length expansions of hydrochar pellets confirmed the strong bond-
ing between hydrochar particles and the excellent durability of
hydrochar pellets.
It is worthily to note that agro-residues pellets suffer from weak
mechanical durability [18] and this can also be confirmed from the
lower tensile strength of CF, CS and RH pellets in comparison to
that of PS pellet. In the present study, the hydrochar pellets made
from agricultural biomass had a comparable tensile strength to
woody biomass pellets and the CF-HC pellet even had higher ten-
sile strength than PS-HC pellet. Therefore, HTC combined with pel-
letization narrows the difference between the agricultural and
1320 Z. Liu et al. / Applied Energy 113 (2014) 1315–1322

12 1.2
100
A 1.0
10
80
Length expansion (%)

0.8

DTG (%/sec)
TG (%)
8 60
CF pellet 0.6
CF-HC pellet
6 PS pellet 40
0.4
PS-HC pellet
RH pellet
RH-HC pellet 20 0.2
4 CS pellet
CS-HC pellet
CF pellet 0 0.0
2 CF-HC pellet
0 200 400 600 800
Temperature (oC)
0
0 2 4 6 8 10 12 14 16 1.0
Time (day) 100
B
0.8
Fig. 4. Moisture uptakes of raw biomass pellets and corresponding hydrochar 80
pellets at 25 °C and 60% relative humidity.

DTG (%/sec)
0.6

TG (%)
60
PS pellet
0.4
woody biomass, overcoming the existing hurdle for the agricul- 40 PS-HC pellet
tural residues pelletization. In addition, high friability of the hyd-
rochars decreases the influence of starting particle size on pellet 20 0.2
durability and is helpful to reduce the production cost of the pel-
lets compared to raw biomass [35]. 0 0.0

0 200 400 600 800

3.3. Moisture uptake o
Temperature ( C)

The moistures content of the pellets against the exposure time

are presented in Fig. 5. The raw biomass pellets exhibited higher 100 C 1.8
moisture uptake than their corresponding hydrochar pellets and
no obvious moisture adsorption was observed after 7 h for raw bio- 80 1.5
mass pellets and 4 h for hydrochar pellets. Equilibrium moisture

DTG (%/sec)
1.2
TG (%)

contents and adsorption rates are summarized in Table 2. The 60

raw biomass pellets exhibited the most hygroscopic behavior and CS pellet 0.9
had the equilibrium moisture contents higher than 3.20%. The 40 CS-HC pellet
moisture uptake of hydrochar pellets significantly decreased com- 0.6
pared to that of the corresponding raw biomass pellets and the 20
0.3
equilibrium moisture contents were around 2.0%. The biggest dif-
ference of the equilibrium moisture content between raw biomass 0
0.0
pellets and hydrochar pellets was observed for the PS pellet (4.08%)
0 200 400 600 800
and PS-HC pellet (1.16%). The lower moisture uptake of hydrochar o
Temperature ( C)

105 1.4

4.0
PS pellet
PS-HC pellet
90
D 1.2
RH pellet
RH-HC pellet 1.0
CS pellet
DTG (%/sec)

75
CS-HC pellet
Moisture content (%)

0.8
TG (%)

3.0 CF pellet
CF-HC pellet
60
RH pellet 0.6
RH-HC pellet
45 0.4
2.0
0.2
30
0.0
1.0 15
0 200 400 600 800
o
Temperature ( C)
0.0 Fig. 6. TG and DTG curves of raw biomass pellets and hydrochar pellets in an air
0 2 4 6 8 10 flow rate of 150 cm3/min at a heating rate 20 °C/min.
Time (h)

Fig. 5. Length expansions of raw biomass pellets and corresponding hydrochar pellets is mainly ascribed to the lower surface area exposed to air
pellets. in comparison with raw biomass pellets.
 Z. Liu et al. / Applied Energy 113 (2014) 1315–1322
Table 3
The characteristic combustion parameters for the pellets prepared from raw biomass and their corresponding hydrochars.
Fuel Initial combustion
temperature (°C)
CF pellet 251
CF-HC pellet 281
CS pellet 267
CS-HC pellet 369
PS pellet 290
PS-HC pellet 291
RH pellet 269
RH-HC pellet 277
The increased moisture resistance together with enhanced ten-
sile strength and decreased length expansion indicated that hydro-
char pellets had more favorable physical properties than raw
biomass pellets as a solid biofuel.
3.4. Combustion characteristics
Thermal gravimetric (TG) and differential thermal gravimetric
(DTG) profiles depicting the combustion process of raw biomass
pellets and hydrochar pellets are presented in Fig. 6. The character-
istic temperatures and peak points of the combustion process are
summarized in Table 3. From TG curves, it was clearly seen that
hydrochar pellets had decreased residues after combustion than
corresponding raw biomass pellets with the exception of RH-HC
pellet. Taking into account that the temperature value at the max-
imum weight loss rate is inversely proportional to reactivity,
hydrochar pellets had lower reactivities compared to raw biomass
pellets [36]. The combustion of hydrochar pellets shifted to higher
temperature ranges and the final combustion temperatures shar-
ply increased compared to their corresponding biomass pellets,
for example, from 466 °C for CF pellet to 643 °C for CF-HC pellet,
and from 464 °C for PS pellet to 700 °C for PS-HC pellet. The
combustion of CF pellet occurred in two separated temperature
ranges (200–325 °C and 325–466 °C), caused by the big difference
of the reactivities among different constituents. Like all hydrochar
pellets, the combustion of CF-HC pellet occurred in a continuous
temperature range of 281–643 °C (369–616 °C for CS-HC pellet;
278–700 °C for PS-HC pellet and 277–661 °C for RH-HC pellet). In
addition, the maximum weight loss rates also drastically decreased
for hydrochar pellets. As an example, the rates decreased from
1.04%/s for CF pellets to 0.13%/s for CF-HC pellets, and from
0.70%/s for PS to 0.10%/s for PS-HC pellets. The increased final tem-
peratures and the decreased maximum weight loss rates indicated
that the hydrochar pellets combusted in a more moderate way
than raw biomass pellets. The continuous and elevated combustion
temperature ranges coupled with significantly increased final tem-
peratures suggests that the higher thermal efficiency can be
achieved for combustion of hydrochar pellets [5]. Also, the low
combustion temperatures of biomass materials are associated with
high pollutant emissions. Therefore, with the elevated combustion
temperature ranges, reduced pollutant emissions are also expected
by the use of hydrochar pellets.
With increased fuel quality of hydrochar pellets, HTC combined
with pelletization provides a promising alternative for the utiliza-
tion of biomass feedstocks, especially for the most abundant agri-
cultural residues. Further investigations on hydrochar pellets
combustion in small-scale combustors are needed to achieve the
maximum combustion efficiency of such pellets.
4. Conclusions
Fuel qualities of the pellets made from raw biomass and their
corresponding hydrochars were evaluated in the present study.
1321
Temperature at maximum Final combustion Maximum weight
weight loss rate (°C) temperature (°C) loss rate (%/s)
275 466 1.04
481 643 0.13
290 340 1.64
508 616 0.14
333 464 0.70
472 700 0.10
297 345 1.18
502 661 0.08
Hydrochar pellets with the exception of RH-HC pellet had in-
creased fixed carbon contents, higher heating values and decreased
ash contents compared to those of raw biomass pellets. Hydrochar
pellets exhibited high mechanical strength, at least 1.8 times high-
er tensile strength than raw biomass pellets prepared under iden-
tical conditions. Apart from enhanced attractive forces, liquid
bridges represent the main bonding mechanism within hydrochar
pellets. The moisture uptake was decreased from more than 3.2% of
raw biomass pellets to less than 2.0% for corresponding hydrochar
pellets. In addition, the length expansions decreased by more than
90% from raw biomass pellets to corresponding hydrochar pellets.
The hydrochar pellets had improved combustion characteristics
than their corresponding raw biomass pellets: elevated combus-
tion temperature ranges, decreased maximum weight loss rates
and reduced residues, therefore high combustion efficiency and
low pollutant emissions are expected for hydrochar pellets. In
addition, hydrochar pellets made from agricultural residues had
similar fuel qualities to those of woody biomass.
The increased mechanical durability and significantly improved
combustion characteristics suggested that hydrochar pellets are
more suitable as solid fuels in comparison to raw biomass pellets.
Therefore, hydrothermal carbonization combined with pelletiza-
tion provides an alternative for biofuel production from biomass
feedstocks in the form of easily friable pellets, especially for abun-
dant agricultural residues.
Acknowledgements
This work was financially supported by the National Environ-
ment Agency of Singapore (NEA) under the Environment Technol-
ogy Research Program (Grant #302-000-001-490) and Minerals,
Metals and Materials Technology Centre (M3TC) (Grant #261-
501-010-414).
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