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Bioresource Technology xxx (2012) xxxxxx

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

Chemical, structural and combustion characteristics of carbonaceous products


obtained by hydrothermal carbonization of palm empty fruit bunches
Ganesh K. Parshetti a,b, S. Kent Hoekman c, Rajasekhar Balasubramanian a,b,
a

Minerals, Metals and Materials Technology Centre, National University of Singapore, EA Engineering Drive 1, Singapore 117576, Singapore
Department of Civil and Environmental Engineering, National University of Singapore, EA Engineering Drive 1, Singapore 117576, Singapore
c
Division of Atmospheric Sciences, Desert Research Institute (DRI), 2215 Raggio Parkway, Reno, NV 89512, USA
b

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

" Energy rich hydrochars were

"

"

"
"

synthesized by HTC of palm empty


fruit bunches.
Formation of hydrochars relies on a
dehydration and decarboxylation
process.
Hydrochars were characterized by
FE-SEM, FTIR, BET, XRD and
TGA-DTG.
Hydrochar presented in this work
has unique chemical properties.
Potential applications of hydrochars
include fuels, energy sources and
adsorbents.

a r t i c l e

i n f o

Article history:
Available online xxxx
Keywords:
Biomass
Co-combustion
Energy densication
Hydrochar
Hydrothermal carbonization

a b s t r a c t
A carbon-rich solid product, denoted as hydrochar, was synthesized by hydrothermal carbonization
(HTC) of palm oil empty fruit bunch (EFB), at different pre-treatment temperatures of 150, 250 and
350 C. The conversion of the raw biomass to its hydrochar occurred via dehydration and decarboxylation
processes. The hydrochar produced at 350 C had the maximum energy-density (>27 MJ kg1) with
68.52% of raw EFB energy retained in the char. To gain a detailed insight into the chemical and structural
properties, carbonaceous hydrochar materials were characterized by FE-SEM, FT-IR, XRD and Brunauer
EmmettTeller (BET) analyses. This work also investigated the inuence of hydrothermally treated
hydrochars on the co-combustion characteristics of low rank Indonesian coal. Conventional thermal
gravimetric analysis (TGA) parameters, kinetics and activation energy of different hydrochar and coal
blends were estimated. Our results show that solid hydrochars improve the combustion of low rank coals
for energy generation.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
The worlds growing population could soon require more energy than can be supplied from conventional means, especially as
living standards improve globally (Resch et al., 2008). Such an in Corresponding author at: Minerals, Metals and Materials Technology Centre &
Department of Civil and Environmental Engineering, National University of
Singapore, EA Engineering Drive 1, Singapore 117576, Singapore. Tel.: +65 6516
5135; fax: +65 6872 5483.
E-mail address: ceerbala@nus.edu.sg (R. Balasubramanian).

crease in energy generation must not be accompanied by an increase in carbon dioxide (CO2) emissions. Therefore, natural and
renewable forms of energy must be considered over the classical
fossil fuel sources which are diminishing rapidly. The preparation
of carbon-rich material from renewable resources is a growing area
of research (Lehmann, 2007). Bio-carbon materials are ubiquitous
with a wide range of technologically important applications,
including energy generation and storage applications (White
et al., 2009). However, the main disadvantage of using such
materials for energy and environmental applications is their high
production cost. Contributing to this high cost are use of expensive

0960-8524/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.biortech.2012.09.042

Please cite this article in press as: Parshetti, G.K., et al. Chemical, structural and combustion characteristics of carbonaceous products obtained by hydrothermal carbonization of palm empty fruit bunches. Bioresour. Technol. (2012), http://dx.doi.org/10.1016/j.biortech.2012.09.042

G.K. Parshetti et al. / Bioresource Technology xxx (2012) xxxxxx

fossil-based precursors and metal catalysts, along with complicated processing units that operate at high temperatures. In view
of these drawbacks, carbon materials derived from renewable resources (e.g. biomass) are expected to play an important role in
the production of biofuels and bioproducts and in biorening
(Lehmann, 2007) in the near future.
In recent years, considerable attention has been paid to making
biochar and hydrochar from pyrolysis and hydrothermal carbonization (HTC) of biomass, respectively, for a range of practical
applications (Hu et al., 2010; Lehmann, 2007; Sevilla and Fuertes,
2009a,b; Titirici et al., 2007a). HTC is a pressurized thermal conversion process conducted at relatively low temperatures (150
350 C). Under autogenous pressures, this process can be used for
treating/stabilizing waste streams while minimizing greenhouse
gas production and producing residual material having intrinsic
value (Hu et al., 2010). Titirici et al. (2007b) and Sevilla and Fuertes
(2009a,b)) reported that char formation results from a series of
hydrolysis, condensation, decarboxylation, and dehydration reactions. The HTC process can be carried out directly, or catalystassisted. In the direct HTC process, only the sample and water
are heated in a pressure vessel. Addition of catalysts, such as citric
acid and metal ions, is included in the catalyst assisted-HTC
process (Hu et al., 2008).
In contrast to standard high-temperature carbonization reactions (e.g. pyrolysis), the HTC process is an exothermic process
and energetically more favorable (Funke and Ziegler, 2010; Titirici
et al., 2007a), as it liberates about a third of the combustion energy
of the sugars through dehydration while forming condensed products. In addition to being fast and simple, HTC can handle wet feedstocks such as raw biomass, as effective dehydration occurs only in
the presence of water (Funke and Ziegler, 2010; Hu et al., 2008).
Furthermore, the nal carbonaceous product (hydrochar) can easily be ltered from the reaction solution, avoiding complicated drying schemes and costly isolation procedures. Depending upon the
process conditions used, the carbon efciency of HTC can be very
high, i.e. most of the starting carbon stays bound in the nal hydrochar product. Application of the HTC process to waste streams may
be an effective way to minimize waste, while mitigating greenhouse gas emissions (Funke and Ziegler, 2010; Sevilla and Fuertes,
2009a; Titirici et al., 2007a,b). However, a substantial amount of liquid oil and wastewater is likely to be produced from HTC of biomass. In addition, (dry) pyrolytic degradation pathways are likely
to occur, to some extent, during hydrothermal conditions. Future
research addressing these issues is warranted. The detailed chemistry of the HTC process for converting biomass into carbon rich
products is not yet completely understood. Therefore, chemical
characterization of the hydrochar is critical to understand the different reaction mechanisms of HTC processes. In addition, understanding the physical, chemical, thermal and combustion
characteristics of hydrochars is important for use of these materials as an energy source (Muthuraman et al., 2010a; Sevilla et al.,
2011b).
In the present study, the conversion of waste biomass, namely
EFB, into a solid carbonaceous product (hydrochar), was carried
out by HTC. EFB is the primary solid waste of palm oil mill processing, and is abundantly available, mainly in South-East Asia (Malaysia, Indonesia and Thailand). Malaysia has approximately 362 palm
oil mills, processing about 82 million tons of fresh fruit bunch and
producing an estimated 33 million tons of crop residue annually in
the form of empty fruit bunch, ber and shell (Goh et al., 2010).
Lignocellulosic EFB (38.159.7 wt.% cellulose, 16.822.1 wt.%
hemicelluloses, and 10.518.1 wt.% lignin) is potentially a low-cost
material for production of carbonaceous products (Abdullah and
Gerhauser, 2008). In addition, this form of carbohydrates has been
shown to react well under subcritical water conditions (250 C and
22 bar) (Mahlia et al., 2001). To the best of our knowledge, there

has been no systematic investigation on the hydrothermal conversion of EFB to hydrochar. The specic objectives of this study are
(1) to investigate the feasibility of converting EFB to a value-added
solid product (hydrochar) through the HTC process and (2) to
evaluate the chemical, structural and combustion properties of
the hydrochar for its potential use for energy generation through
co-combustion with coal.
2. Methods
2.1. Materials
In this study, EFB was obtained from an oil processing company
in Malaysia, and was manually chopped into small pieces before
use. EFB is the lignocellulosic material remaining as a by-product
of the industrial palm oil process after removal of the nuts. To promote homogeneous mixing of EFB, and to facilitate its effective
conversion to hydrochar during HTC treatment, the EFB was processed into ne pieces (16 mm) using a grinder, then air-dried
and stored in a sealed container until use. Low rank coal was
obtained from a coal mining company in Indonesia.
2.2. Hydrothermal carbonization: apparatus and procedure
HTC of EFB was carried out in a 500 mL Parr stirred pressure
batch reactor (model 4575), as shown in Fig. 1. Experiments were
conducted at different temperatures (150, 250 and 350 C) with a
constant reaction time of 20 min. In a typical run, 25 g of previously
dried EFB was dispersed in 250 mL of de-ionized water contained in
the reactor. The reactor was sealed and heated to the desired reaction temperature in an electric furnace. After the desired residence
time, the reactor was rapidly cooled to quench the reaction.
Residence time was dened as the time the reactor was held at
the desired reaction temperature, excluding preheating and cooling
time. After the reactor had cooled to room temperature, it was
opened to collect the solid carbonaceous products. The solid product (hydrochar) was recovered by ltration, washed with deionized
water and dried in air. The char product was weighed independently
and stored in a sealed container until analysis.
2.3. Characterization of hydrochar
The 5E-MAG6600 automatic proximate analyzer was used to
determine the weight percentages (wt.%) of moisture, volatile

Fig. 1. Schematic representation of the Parr reactor used for hydrothermal


carbonization of EFB biomass.

Please cite this article in press as: Parshetti, G.K., et al. Chemical, structural and combustion characteristics of carbonaceous products obtained by hydrothermal carbonization of palm empty fruit bunches. Bioresour. Technol. (2012), http://dx.doi.org/10.1016/j.biortech.2012.09.042

G.K. Parshetti et al. / Bioresource Technology xxx (2012) xxxxxx

matter (VM), xed carbon (FC) and ash in EFB biomass and hydrochars. An elemental analyzer (vario MACRO cube, ELEMENTAR,
Germany) was used to carry out ultimate analyses to determine
the weight percentages of chemical elements (carbon, hydrogen,
nitrogen, oxygen and sulfur) in the EFB biomass, coal and hydrochars. The surface morphology of the hydrochar was determined by
SEM (JEOL JSM-6700F Oxford Inca Energy 400). The hydrochar
samples were placed onto adhesive carbon tape on an aluminum
stub, followed by sputter coating of platinum using an Ion
Sputter E-1030 (Hitachi, Japan). The accelerating voltage and the
applied current were 15 kV and 20 nA, respectively. After coating
with platinum, the samples were placed under high vacuum
(103107 mbar) conditions. The scanning electron image (SEI)
resolution was 1.5 nm at 15 kV.
Wide angle X-ray diffraction (WAXD) on all samples was conducted using an X-ray diffractometer (XRD, Bruker NEW D8 ADVANCE, Germany) with Ni-ltered Cu Ka radiation (k = 1.5406 )
and operated at an accelerating voltage and an emission current
of 40 kV and 40 mA, respectively. The X-ray diffraction patterns
were acquired over the 2h range from 10 to 70. Nitrogen adsorptiondesorption isotherms were collected at 77K using a N2
adsorption analyzer (Quantachrome instruments, NOVA 4200e).
The BrunauerEmmettTeller (BET) method was utilized to calculate the specic surface areas (SBET) using adsorption data. By
using the BarrettJoynerHalenda (BJH) model, the pore size distribution in the mesoporous range was derived from the desorption
branches of isotherms, and the total pore volumes (Vt) were estimated from the adsorbed amount at relative pressure (P/P0) of
0.995. FT-IR spectra of EFB and hydrochars were recorded using a
BIO-RAD, Excalibur series spectrometer with a resolution of
4 cm1. FT-IR spectra measurements were performed with pressed
pellets that were made using KBr powder as diluent.
Thermal gravimetric analysis (TGA) measures weight changes of
a material under the temperature programmed condition in a
controlled atmosphere. The coal and hydrochar samples were dried,
and subsequently milled and sieved to particles of less than
150 lm. Thus, the particle size of the coal and hydrochar particles
and their blends was approximately 150 lm for TG analysis. TGA
represents an effective way to analyze thermal and combustion
behavior of different kinds of materials such as coal, biomass and
their blends (Idris et al., 2010; Lapuerta et al., 2004; Zheng and
Kozinski, 2000). In the present study, the sample weight loss (TG)
and the rate of weight loss (DTG) of all the samples were
performed using a Shimadzu TG/DTG-60 series (DTG-60 AH,
Thermal analyzer: TA-60WS) system operated at an air ow of
100 ml min1 while heating from 25 to 800 C at a rate of
10 C min1 at atmospheric pressure. The TG and DTG proles were
analyzed to nd the key combustion parameters. The ignition
temperature and burnout temperatures were determined using
the TG-DTG (the rst derivative of TG curve) method based on previous publications in the literature (Liu et al., in press; Muthuraman
et al., 2010a). In brief, the ignition temperature (To) was determined
based on the temperature at which the DTG had its peak value and
the corresponding slope to the intersection with respect to the TG
prole. The burnout temperature (Tf) was detected based on the
mass stabilization.

3. Results and discussion


3.1. Hydrochar characterization
The characteristics of the hydrochar produced by HTC of EFB
were investigated comprehensively to identify the changes of the
solid material, especially the carbon component. The proximate
analysis, ultimate analysis, solid yield, and heating value of the

hydrochars from EFB that was processed for 20 min at 150


(H-150), 250 (H-250) and 350 (H-350) C are shown in Table 1. A
higher recovery of hydrochar was observed at lower temperatures,
with nearly 76% of the starting dry mass recovered at a reaction
temperature of 150 C, which decreased to approximately 62% at
250 C and 49% at 350 C. A sharp decrease in the solid yield with
temperature was observed, which can either be due to greater primary decomposition of biomass at high temperatures, or through
secondary decomposition of the solid residue, as reported earlier
(Xiu et al., 2010). As expected, the mass of volatile carbon in the solid decreased signicantly as a result of carbonization, while the
xed carbon percentage increased with increasing operating temperature. Similar observations were reported earlier (Mumme
et al., 2011; Hoekman et al., 2011) for municipal waste streams
and lignocellulosic biomass. The xed carbon yield resulting from
carbonization was 16.41%, 27.41%, and 42.41% for H-150, H-250
and H-350, respectively. Liu et al. (2010) reported a xed carbon
content of hydrothermally carbonized (300 C, 20 min) pinewood
to be 43%.
The elemental composition of the solid material changed significantly as a result of carbonization (Table 1). The carbon content of
the hydrochar increased, while the hydrogen and oxygen contents
decreased steadily with increasing operating temperature, consistent with the removal of O and H substances during the HTC process. H/C and O/C atomic ratios, calculated for the initial biomass,
and the resulting hydrochars, were displayed using a Van Krevelen
diagram, which is useful for representing the conversion of carbohydrate material to carbon-rich material (Fuertes et al., 2010). This
diagram offers a clear insight into the chemical transformations of
the carbon rich material, which are demethanation (production of
methane), dehydration (production of water) and decarboxylation
(production of carbonyls including carboxylic acids), taking place
during the process (Fuertes et al., 2010). The Van Krevelen plot of
the EFB biomass and hydrochars is illustrated in Fig. 2. In general,
both the H/C and O/C ratios decreased when the temperature was
raised. At higher operating temperatures, the dehydration trend
became more obvious as compared to the one at the lower operating temperatures. A shift in the O/C ratio suggests that decarboxylation also occurs during the HTC process. Similar results were
observed for the hydrothermal carbonization of glucose, cellulose,
sucrose, starch and agricultural biomass (Sevilla and Fuertes,
2009a,b; Sevilla et al., 2011b).
Another important characteristic of hydrochars is their high heating value (HHV). In all cases, the calculated caloric value of the hydrochars increased with increasing HTC temperature (Table 1). The
caloric value is an indication of the degree of coalication achieved.
Higher HTC temperatures promote the dehydration, decarboxylation, and condensation reactions of the coalication process, thereby resulting in energy densication (Hoekman et al., 2011). The
energy densication factors associated with the hydrochars range
from 1.02 (H-150) to1.40 (H-350). Energetic retention efciencies
provide a means for comparing the energy remaining within the char
and range from 78% (for H-150) to 68% (for H-350) (Table 1).
3.2. Structural properties of hydrochar
A close inspection of the hydrochars by means of microscopy
techniques revealed interesting changes in their morphology in
relation to the raw biomass. For example, the SEM images show
(data not shown) a very clear difference among the hydrochars obtained at different temperatures, suggesting the rupturing of the
lignocellulosic structure in response to the HTC process. The
hydrochar H-150 has a brown color, consistent with a partially carbonized product, whereas the hydrochars H-250 and H-350 were
black in color. The SEM image of the EFB biomass shows a cellular
structure of lignocellulosic materials. However, the hydrochars

Please cite this article in press as: Parshetti, G.K., et al. Chemical, structural and combustion characteristics of carbonaceous products obtained by hydrothermal carbonization of palm empty fruit bunches. Bioresour. Technol. (2012), http://dx.doi.org/10.1016/j.biortech.2012.09.042

G.K. Parshetti et al. / Bioresource Technology xxx (2012) xxxxxx

Table 1
Chemical characteristics and properties of the low rank coal, EFB biomass and the hydrochar materials resulting from the hydrothermal treatment of EFB at 150, 250 and 350 C.
Property
a

a
b
c
d

Coal

EFB

H-150

H-250

H-350

Yield (wt.%)

76

62

49

Elemental analysis (%)


Carbon
Hydrogen
Nitrogen
Sulfur
Oxygen
HHVb (MJ kg1)

55.38
5.86
2.48
2.21
34.07
22.54

48.30
6.66
1.00
0.34
43.70
19.45

49.58
5.91
0.92
0.22
43.37
20.01

54.30
4.17
1.02
0.24
38.29
22.07

66.02
4.15
1.12
0.28
28.43
27.20

Proximate analysis (%)


Moisture
Volatiles
Ash
Fixed carbon
Energy yieldc
Energy densicationd

15.13
34.84
9.33
40.73

4.20
82.21
3.0
10.41

4.40
74.48
4.01
17.41
78.18
1.02

5.30
63.11
4.16
27.41
70.35
1.13

5.21
47.52
4.32
42.41
68.52
1.40

Yield = % Weight of the biomass was measured before and after the HTC.
HHV = 0.4373C  1.6701.
(Mchar HHVchar)/(Mfeedstock HHVfeedstock).
HHVchar/HHVfeedstock.

1.8
1.6

-CH4
-H2O

Atomic H/C ratio

1.4
1.2
1.0
0.8
0.6

EFB
H-150
H-250
H-350

0.4
-CO2

0.2
0.0
0.0

0.1

0.2

0.3

0.4

0.5

Atomic O/C ratio

0.6

0.7

0.8

Fig. 2. Van Krevelen diagram of the EFB biomass and the carbonized samples
(hydrochar) resulting from hydrothermal treatment. Each arrow represents the
direction of loss of a particular gas molecule in the course of evolution.

show considerable changes in the surface morphology of the treated EFB, resulting from hydrothermal carbonization. The SEM image of H-150 hydrochar indicates some breakdown of the
lignocellulosic material. Numerous sphere-like microparticles can
be seen on the surface of the H-250 hydrochar. These microparticles are thought to be formed by degradation of the cellulosic components during HTC, and subsequent precipitation and growth as
spheres (Fuertes et al., 2010). On the other hand, the lignin component probably underwent only partial degradation (owing to its
greater thermal stability), causing a rough texture as observed in
the SEM image of H-350 hydrochar.
Further insights into chemical composition of the EFB biomass
and solid hydrochar materials may be obtained by FTIR (data not
shown). Table S1 (see Supplementary Information) presents the
assignment of peaks to major functional groups for a given wavenumber using FTIR, adapted from previous reports (Monthioux and
Landais, 1988; Sevilla et al., 2011b). Raw EFB biomass comprises
cellulose, hemicellulose and lignin. The single bonds such as OH
(30003700 cm1), CH (1378, 1465 and 1427 cm1), CO
(1101 cm1), and COC (1163 cm1) are characteristic of cellulose
and hemicellulose. The peaks of C@O (1720 cm1) and C@C

(1620 cm1) bonds in the FTIR spectra provide further support


for the existence of cellulose, hemicellulose and also lignin in the
EFB biomass. The spectra of the EFB biomass and H-150 hydrochar
were similar as conrmed by the presence of absorption bands at
1040, 1101 and 1160 cm1. This similarity indicates that the EFB
biomass was not decomposed completely under the mild HTC
reaction conditions of 150 C. The hydrochars, H-250 and H-350,
gave FTIR spectra with features that are different from those of
EFB biomass and H-150. The FTIR spectra of H-250 and H-350 do
not show the characteristic cellulose bands, such as 1163 cm1
(COC vibration). In contrast, the bands that are characteristic
of lignin (aromatic structure) are still preserved, although they
are shifted to slightly lower or higher wavenumbers. The band at
1660 cm1 attributed to non-conjugated ketocarbonyl groups has
almost disappeared. The bands at 30002830 cm1 and 2300
2350 cm1 which correspond to stretching vibrations of aliphatic
CH and C@O, respectively are still present in the hydrochar, suggesting the presence of aliphatic and hydroaromatic structures. On
the other hand, new bands appear in the 875750 cm1 region,
which are assigned to aromatic CH bending vibrations. These
new bands suggest that aromatic rings formed and/or recombined
at the higher temperatures. Moreover, the presence of oxygenated
functional groups is suggested by the bands at: 30003700 cm1 (a
wide band attributed to OH stretching vibrations in hydroxyl or
carboxyl groups) (Araujo-Andrade et al., 2005), 23002350 cm1,
1710 cm1 (C@O vibrations corresponding to carbonyl, quinone,
ester or carboxyl) (Kabyemela et al., 1999) and 10001460 cm1
(CO stretching vibrations in hydroxyl, ester or ether and OH
bending vibrations) (Kabyemela et al., 1999).
The decrease (in relation to the raw EFB) in intensity of the
bands at 10001460 cm1 and the broad band at 3000
3700 cm1 suggests that dehydration and decarboxylation processes occurred during HTC treatment of the EFB, consistent with
our analysis of the evolution of the O/CH/C atomic ratios based
on the Van Krevelen diagram (see Fig. 2). Taking into account the
chemical characteristics of hydrochar products (i.e. the high concentration of oxygenated functional groups and the low degree of
aromatization), it can be envisaged that this type of material may
constitute an excellent precursor for the preparation of activated
carbons via controlled chemical activation (Wang et al., 2011).
The XRD patterns (data not shown) for the raw EFB and hydrochars are also compared. The distinct, sharp crystalline cellulosic
peak (at 2h = 22.7) due to the crystal structure of cellulose (Kumar
et al., 2011) is present in EFB. Mild HTC treatment at 150 C

Please cite this article in press as: Parshetti, G.K., et al. Chemical, structural and combustion characteristics of carbonaceous products obtained by hydrothermal carbonization of palm empty fruit bunches. Bioresour. Technol. (2012), http://dx.doi.org/10.1016/j.biortech.2012.09.042

G.K. Parshetti et al. / Bioresource Technology xxx (2012) xxxxxx


Table 2
BET characteristics of hydrochar resulting from hydrothermal treatment of raw EFB.

1

BET surface area (m g )


Pore volume (cm3 g1)
Average pore diameter (nm)

EFB

H-150

H-250

H-350

1.478
0.035
6.097

6.079
0.019
5.48

8.033
0.043
3.77

2.043
0.007
3.75

produced a hydrochar that exhibited an XRD pattern similar to that


of the raw EFB, indicating that the microcrystalline structure of the
cellulose had been preserved. In contrast, the hydrochars obtained
at 250 and 350 C were no longer crystalline, as can be deduced
from the absence of reections (at 2h = 22.7) in the XRD pattern.
These results provide evidence that the cellulose microcrystalline
feature was converted to non-crystal structures during the HTC
process. With the breakdown of lignocellulosic structure and removal of some oxygen from the structure, the moisture retention
capacity of the product hydrochar was signicantly reduced. Qualitatively, it was observed that the hydrochar was a uffy and high
energy density powder, which can be easily compacted.
According to the IUPAC classication for adsorption isotherms,
the isotherms for hydrochars in this study showed characteristics
that are representative of Type II (Fig. S1, see Supplementary
Information). Moreover, non-porous, or macroporous solids are
associated with Type-II isotherm. Thus, the hydrochar samples
have relatively small BET surface areas due to low porosity
(Table 2). Under such conditions, the specic surface area values
calculated only correspond to the external surface (Fuertes et al.,
2010). Thus, the surface areas of the BET are 6.079, 8.033 and
2.043 m2/g for hydrochar samples H-150, H-250 and H-350,
respectively. It has also been reported previously that the porosity
of hydrochars is low (Fuertes et al., 2010; Sevilla and Fuertes,
2009a,b). Improvements in the porosity of hydrochars and the
surface area are therefore necessary to enable their use as
hydrogen storage or electrical energy storage (supercapacitors).
Such improvements have been achieved with a combination of
thermal and chemical activation that resulted in a surface area of
>2000 m2 g1 (Sevilla et al., 2011a).
3.3. Thermal and co-combustion analysis
The decomposition of biomass was assessed using thermogravimetry. Fig. S2a and b (see Supplementary Information) show the TG
and DTG proles of EFB, coal and hydrochars obtained at 150, 250
and 350 C. The TG curves below 150 C, which are related to
moisture and volatile release, are almost similar for all EFB, coal
and hydrochars. The EFB biomass combustion takes place two
stages: between 250 and 380 C and second combustion stage from
410 to 500 C in contrast coal is characterized by only one combustion stage from 280 to 500 C. The cellulose and hemicellulose
contents of EFB are consistent with the dened peak in the temperature range 200400 C, and this stage usually represents the
decomposition of cellulose and hemicellulose (Lapuerta et al.,
2004; Mohammed et al., 2012). In this temperature range, the
chemical bonds in EFB began to break and the lightest volatile compounds were released (Lapuerta et al., 2004). Also, the lower lignin
content of EFB is inferred from the less marked decomposition at
higher temperatures (Mohammed et al., 2012). Fig. S2a and b show
that the HTC process caused substantial changes in the TG and DTG
proles. The H-150 hydrochar combustion takes place in two
stages: between 290370 C and 420520 C and H-250 hydrochar
combustion also takes place two stages: between 300350 C and
380550 C. In contrast H-350 hydrochar was characterized by only
one major combustion stage from 310 to 590 C. At higher temperatures (280400 C), the TG curves exhibit the highest weight loss
rate, which is consistent with the decomposition of hemicellulose

and cellulose during HTC treatment. Above 400 C, the DTG proles
exhibit smaller, poorly-shaped peaks, which shift to a single
broad peak in the case of H-350. These DTG proles above 400 C
are indicative of lignin weight loss (Romn et al., 2012). To
determine the interactive effect of hydrochars obtained at various
operating temperatures on combustion characteristics of low
rank Indonesian coal, co-combustion experiments were conducted
in three different hydrochar blending ratios of 5%, 10%, and 20%
with coal. All studied blends were characterized by only one
combustion stage. As shown in Table 3, as the blending ratios of
H-150, H-250 and H-350 increased, the ignition temperature (To)
of the blended solid fuels was reduced. The ignition temperature
of the Indonesian coalhydrochar blend follows the weighted
percentage of hydrochar and hence exhibits an additive behavior.
A higher blending ratio with the Indonesian coal will result in a
very low ignition temperature causing a potential re hazard, and
the fuel may get burned well ahead of a point where it is expected
to burn. Hence, while using EFB hydrochars to blend with the
Indonesian coal, care must be taken to ensure that reduction in
the ignition temperature is within the allowable range for the
presently available equipment (Muthuraman et al., 2010a).
However, an increase in the burnout temperature (BOT (Tf)) of
the coal/H-150, coal/H-250 and coal/H-350 blends was observed
with an increase in hydrochars percentage. A similar observation
with an increase in the burnout temperatures was found by other
researchers for co-combustion of biomass with coal (Muthuraman
et al., 2010a,b). In the blended fuel, hydrochar and coal burned
independently. The hydrochar reacted faster, and reduced the oxygen concentration required for coal, thus reducing the incremental
effect of improvement in the burnout, when the blending ratio was
increased. Further, Table 3 shows that the DTG mass loss rate (DTG
Rmax) for all blended fuels gradually increased with an increase in
the hydrochar blend fraction. Also the temperature at which the
peak weight loss rate occurred was reduced when the blending ratio was increased. In general, the reactivity is directly proportional
to the height of the DTG peak and inversely proportional to the
peak temperature (Zheng and Kozinski, 2000). In this case, the
DTG Rmax increased and the peak temperature decreased upon
blending hydrochars with coal, which conrms an increase in reactivity compared to coal. These results also show that the combustion behavior of the coal-hydrochar blends was greatly inuenced
by the quantity of hydrochars added.
3.4. Kinetic analysis
Studies on TGA proles contribute to enhancing the knowledge
of the kinetics of this thermal process and, therefore, to establishing the optimum operational conditions for better utilization of
Table 3
Combustion parameters of coal, hydrochars and their blends.
Sample

To
(C)

Tf
(C)

DTG peak
temperature (C)

DTG Rmax
(mg/s)

Coal
150
250
350
Coal + H-150
Coal + H-150
Coal + H-150
Coal + H-250
Coal + H-250
Coal + H-250
Coal + H-350
Coal + H-350
Coal + H-350

316
321
340
420
305
289
295
338
327
300
407
378
347

490
505
538
576
533
534
547
548
553
560
577
580
592

363
337
477
480
338
336
332
521
484
476
529
526
522

0.040
0.130
0.039
0.025
0.050
0.067
0.105
0.016
0.033
0.039
0.020
0.025
0.028

(5%)
(10%)
(20%)
(5%)
(10%)
(20%)
(5%)
(10%)
(20%)

To = Ignition temperature, Tf = Burnout temperature, DTG Rmax = maximum weight


loss rate.

Please cite this article in press as: Parshetti, G.K., et al. Chemical, structural and combustion characteristics of carbonaceous products obtained by hydrothermal carbonization of palm empty fruit bunches. Bioresour. Technol. (2012), http://dx.doi.org/10.1016/j.biortech.2012.09.042

G.K. Parshetti et al. / Bioresource Technology xxx (2012) xxxxxx

Table 4
Summary of kinetic parameters activation energy.
Sample

Temperature
range

Mechanism

Correlation coefcient

Pre-exponential factor (min1)

Activation energy (kJ mol1)

Coal
H-150

280
290
420
300
380
310
295
280
285
329
313
291
390
365
332

F1
F1
D1
F1
D1
D1
F1
F1
F1
F1
F1
F1
F1
F1
F1

4.2599
7.8898
10.324
11.834
11.093
8.2513
3.8219
7.5797
8.4393
11.007
8.1601
8.4844
11.136
10.968
9.7558

5935.9
3637.2
2488.8
1906.7
1553.8
4536.6
6016.6
3828.8
3244
1972.1
3681.7
3352.7
1540.4
1939.5
2728.1

0.96
0.98
0.92
0.90
0.97
0.98
0.99
0.97
0.98
0.97
0.97
0.98
0.97
0.96
0.99

838.26
13.75
0.817
0.138
0.236
11.83
1316.62
19.54
7.08
0.327
10.52
6.96
0.224
0.334
1.6

49.35
30.24
20.70
15.85
12.91
37.71
50.02
31.83
26.97
16.40
30.61
27.87
12.80
16.13
22.68

H-250
H-350
Coal + H-150
Coal + H-150
Coal + H-150
Coal + H-250
Coal + H-250
Coal + H-250
Coal + H-350
Coal + H-350
Coal + H-350

(5%)
(10%)
(20%)
(5%)
(10%)
(20%)
(5%)
(10%)
(20%)

500
370
520
350
550
590
545
546
556
555
560
570
586
590
602

hydrochars. Combustion kinetic parameters were calculated for


the temperature ranges as mentioned in Table 4. The mass change
vs. temperature can be described as

da A E=RT
1  an
e
dT b

where n stands for the reaction order and A and E represent the preexponential factor and the activation energy of the reaction, respectively and mass change a is dened as,

m0  mt
m0  mf

where m0 represents the initial sample mass in an experiment, mt


denotes the current sample mass, and mf species the nal sample
mass.
Eq. (1) can be expressed in an integral form as follows:

Z
0

da
A

1  an b

eE=RT dT

T0

Using the approximation introduced by (Coats and Redfern,


1964), Eq. (3) can be integrated and rearranged into the following
logarithmic form

ln



ga
T

ln

 

AR
2RT
E
1

bE
E
RT

Eq. (4) can be transformed to a linear relation as:

Y a bx

h 
i
where a stands for ln AR
1  2RT
, b is  RE and x is 1T . According
bE
E
to Eq. (5), a plot of ln[g(a)/T2] against reciprocal of temperature
should give a straight line with a slope equal to E/R. g(a) is the
integral function of conversion. Apparent activation energy E and
the pre-exponential factor A can be calculated by using the slope
and intercept obtained from Eq. (5). The function g(a) depends
on the mechanism controlling the reaction, the size and the shape
of the reacting particles. Table S2 (see Supplementary Information)
shows the expressions of g(a) for the basic model functions usually
employed for the kinetic study of solid-state reactions. By means of
these functions it was possible to roughly identify the reaction
mechanisms governing the process of thermal oxidation of the
samples from the TG curves. The form of g(a) that gives a straight
line with the highest correlation coefcient will be considered the
function of the model that best represents the kinetics of mass loss
for each separate reaction. Model F1 presented the highest correlation coefcients for the coal and blends, indicating that the chemical rst order reaction is the most effective mechanism for

combustion. However, effective solid-state mechanisms were


found to be F1 for the rst stage of combustion and D1 for the
second stage combustion for the hydrochar H-150 and H-250
(Table 4). In the case of H-350 effective solid-state mechanisms
were found to be D1 since the highest correlation coefcients for
this mechanism was obtained (Table 4).
Activation energies associated with the combustion of coal and
H-350 were found to be 49.35 and 37.71 kJ mol1, respectively. The
activation energy in the rst stage combustion of H-150 showed a
value equal to 30.24 kJ mol1 and in the second stage of the combustion process it was 20.70 kJ mol1. However, the activation energy in the rst stage combustion of H-250 was 15.85 kJ mol1 and
in the second stage of the combustion process it was
12.91 kJ mol1. The lower activation energy can be explained
partly by unique properties of the hydrochar, such as its highly
amorphous carbonaceous structure and high surface area (Mumme
et al., 2011; Liu et al., in press). The inorganic species may have a
catalytic effect on the thermal decomposition of lignocellulosic
biomass resulting in lower activation energy (Yurdakul-Yorulmaz
and Atimtay, 2009). Activation energies of the coal-hydrochar
blended samples (coal/H-150 (5%, 10% and 20%)) were found to
be in the range of 50.0226.97 kJ mol1. As reported in Table 4,
the activation energies of the blend samples were lower than that
of coal (49.35 kJ mol1), except for the blend coal/H-150 (5%,
50.02 kJ mol1) which was almost similar to the coal. This trend
again shows synergistic interactions between coal and hydrochar
components, leading to the decrease of activation energy of combustion. As for other coal-hydrochar blends (coal/H-250 and coal/
H-350), activation energies were in the range of 16.4027.87 and
12.8022.68 kJ mol1, respectively. The activation energy of the
coal/H-350 (5%, 12.80 kJ mol1) blend shows the lowest activation
energy. However, unlike the maximum weight loss change with
temperature, the activation energy of the coal-hydrochar blend
did not show a linear relationship with the proportion of hydrochar
added to coal. As the activation energy represents the critical
energy needed to start combustion (Idris et al., 2010), the
oal-hydrochar with the lowest activation energy is recommended.

4. Conclusions
The hydrothermal carbonization of EFB provided carbonaceous
solid products containing around 5066% of the carbon originally
present in the raw material, depending upon the process temperature used. The composition of the hydrochars suggests that both
dehydration and decarboxylation occurred during hydrothermal
carbonization. The results show that, the combustion behavior of

Please cite this article in press as: Parshetti, G.K., et al. Chemical, structural and combustion characteristics of carbonaceous products obtained by hydrothermal carbonization of palm empty fruit bunches. Bioresour. Technol. (2012), http://dx.doi.org/10.1016/j.biortech.2012.09.042

G.K. Parshetti et al. / Bioresource Technology xxx (2012) xxxxxx

the coal/hydrochar blends was greatly inuenced by the fraction of


hydrochar in the blend. This work suggests that the HTC process
has potential for conversion of waste EFB to densied solid fuels
and carbonaceous functional materials for use in a variety of applications, including energy generation through co-combustion with
coal.
Acknowledgements
The authors are thankful to the Singapore Economic Development Board (EDB) and the Minerals, Metals and Materials Technology Centre (M3TC), National University of Singapore for the
nancial support extended to this project.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.biortech.2012.
09.042.
References
Abdullah, N., Gerhauser, H., 2008. Bio-oil derived from empty fruit bunches. Fuel 87,
26062613.
Araujo-Andrade, C., Ruiz, F., Martinez-Mendoza, J.R., Terrones, H., 2005. Infrared and
Raman spectra, conformational stability, ab initio calculations of structure, and
vibrational assignment of alpha and beta glucose. J. Mol. Struct. Theochem 714,
143146.
Coats, A.W., Redfern, J.P., 1964. Kinetic parameters from thermogravimetric data.
Nature 201, 6869.
Fuertes, A.B., Arbestain, M.C., Sevilla, M., Macia-Agullo, J.A., Fiol, S., Lopez, R.,
Smernik, R.J., Aitkenhead, W.P., Arce, F., Macias, F., 2010. Chemical and
structural properties of carbonaceous products obtained by pyrolysis and
hydrothermal carbonisation of corn stover. Aust. J. Soil Res. 48, 618626.
Funke, A., Ziegler, F., 2010. Hydrothermal carbonization of biomass: a summary and
discussion of chemical mechanisms for process engineering. Biofuels, Bioprod.
Biorg. 4, 160177.
Goh, C.S., Tan, K.T., Lee, K.T., Bhatia, S., 2010. Bio-ethanol from lignocellulose: status,
perspectives and challenges in Malaysia. Bioresour. Technol. 101, 48344841.
Hoekman, S.K., Broch, A., Robbins, C., 2011. Hydrothermal carbonization (HTC) of
lignocellulosic biomass. Energy Fuels 25, 18021810.
Hu, B., Yu, S.H., Wang, K., Liu, L., Xu, X.W., 2008. Functional carbonaceous materials
from hydrothermal carbonization of biomass: an effective chemical process.
Dalton Trans. 40, 54145423.
Hu, B., Wang, K., Wu, L.H., Yu, S.H., Antonietti, M., Titirici, M.M., 2010. Engineering
carbon materials from the hydrothermal carbonization process of biomass. Adv.
Mater. 22, 813828.
Idris, S.S., Rahman, N.A., Ismail, K., Alias, A.B., Rashid, Z.A., Aris, M.J., 2010.
Investigation on thermochemical behaviour of low rank Malaysian coal, oil
palm biomass and their blends during pyrolysis via thermogravimetric analysis
(TGA). Bioresour. Technol. 101, 45844592.
Kabyemela, B.M., Adschiri, T., Malaluan, R.M., Arai, K., 1999. Glucose and fructose
decomposition in subcritical and supercritical water: detailed reaction
pathway, mechanisms, and kinetics. Ind. Eng. Chem. Res. 38, 28882895.
Kumar, S., Loganathan, V.A., Gupta, R.B., Barnett, M.O., 2011. An assessment of U(VI)
removal from groundwater using biochar produced from hydrothermal
carbonization. J. Environ. Manage. 92, 25042512.

Lapuerta, M., Hernandez, J.J., Rodriguez, J., 2004. Kinetics of devolatilisation of


forestry wastes from thermogravimetric analysis. Biomass Bioenergy 27, 385
391.
Lehmann, J., 2007. Bio-energy in the black. Front. Ecol. Environ. 5, 381387.
Liu, Z.G., Zhang, F.S., Wu, J.Z., 2010. Characterization and application of chars
produced from pinewood pyrolysis and hydrothermal treatment. Fuel 89, 510
514.
Liu, Z.G., Quek, A., Hoekman, S.K., Srinivasan, M.P., Balasubramanian, R., in press.
Thermogravimetric investigation of hydrochar-lignite co-combustion.
Bioresour. Technol. (http://dx.doi.org/10.1016/j.biortech.2012.06.063).
Mahlia, T.M.I., Abdulmuin, M.Z., Alamsyah, T.M.I., Mukhlishien, D., 2001. An
alternative energy source from palm wastes industry for Malaysia and
Indonesia. Energy Convers. Manage. 42, 21092118.
Mohammed, M.A.A., Salmiaton, A., Wan Azlina, W.A.K.G., Mohamad Amran, M.S.,
2012. Gasication of oil palm empty fruit bunches: a characterization and
kinetic study. Bioresour. Technol. 110, 628636.
Monthioux, M., Landais, P., 1988. Natural and articial maturations of a coal series
infrared spectrometry study. Energy Fuels 2, 794801.
Mumme, J., Eckervogt, L., Pielert, J., Diakite, M., Rupp, F., Kern, J., 2011.
Hydrothermal carbonization of anaerobically digested maize silage. Bioresour.
Technol. 102, 92559260.
Muthuraman, M., Namioka, T., Yoshikawa, K., 2010a. Characteristics of cocombustion and kinetic study on hydrothermally treated municipal solid
waste with different rank coals: a thermogravimetric analysis. Appl. Energy 87,
141148.
Muthuraman, M., Namioka, T., Yoshikawa, K., 2010b. A comparison of cocombustion characteristics of coal with wood and hydrothermally treated
municipal solid waste. Bioresour. Technol. 101, 24772482.
Resch, G., Held, A., Faber, T., Panzer, C., Toro, F., Haas, R., 2008. Potentials and
prospects for renewable energies at global scale. Energy Policy 36, 40484056.
Romn, S., Nabais, J.M.V., Laginhas, C., Ledesma, B., Gonzlez, J.F., 2012.
Hydrothermal carbonization as an effective way of densifying the energy
content of biomass. Fuel Process. Technol. 103, 7883.
Sevilla, M., Fuertes, A.B., 2009a. Chemical and structural properties of carbonaceous
products obtained by hydrothermal carbonization of saccharides. Chem. Eur. J.
15, 41954203.
Sevilla, M., Fuertes, A.B., 2009b. The production of carbon materials by
hydrothermal carbonization of cellulose. Carbon 47, 22812289.
Sevilla, M., Fuertes, A.B., Mokaya, R., 2011a. High density hydrogen storage in
superactivated carbons from hydrothermally carbonized renewable organic
materials. Energy Environ. Sci. 4, 14001410.
Sevilla, M., Macia-Agullo, J.A., Fuertes, A.B., 2011b. Hydrothermal carbonization of
biomass as a route for the sequestration of CO(2): chemical and structural
properties of the carbonized products. Biomass Bioenergy 35 (7), 31523159.
Titirici, M.M., Thomas, A., Antonietti, M., 2007a. Back in the black: hydrothermal
carbonization of plant material as an efcient chemical process to treat the CO2
problem? New J. Chem. 31, 787789.
Titirici, M.M., Thomas, A., Yu, S.H., Muller, J.O., Antonietti, M., 2007b. A direct
synthesis of mesoporous carbons with bicontinuous pore morphology from
crude plant material by hydrothermal carbonization. Chem. Mater. 19, 4205
4212.
Wang, L.L., Guo, Y.P., Zou, B., Rong, C.G., Ma, X.Y., Qu, Y.N., Li, Y., Wang, Z.C., 2011.
High surface area porous carbons prepared from hydrochars by phosphoric acid
activation. Bioresour. Technol. 102, 19471950.
White, R.J., Budarin, V., Luque, R., Clark, J.H., Macquarrie, D.J., 2009. Tuneable porous
carbonaceous materials from renewable resources. Chem. Soc. Rev. 38, 3401
3418.
Xiu, S.N., Shahbazi, A., Shirley, V., Cheng, D., 2010. Hydrothermal pyrolysis of swine
manure to bio-oil: effects of operating parameters on products yield and
characterization of bio-oil. J. Anal. Appl. Pyrol. 88, 7379.
Yurdakul-Yorulmaz, S., Atimtay, A.T., 2009. Investigation of combustion kinetics of
treated and untreated waste wood samples with thermogravimetric analysis.
Fuel Process Technol. 90, 939946.
Zheng, G., Kozinski, J.A., 2000. Thermal events occurring during the combustion of
biomass residue. Fuel 79, 181192.

Please cite this article in press as: Parshetti, G.K., et al. Chemical, structural and combustion characteristics of carbonaceous products obtained by hydrothermal carbonization of palm empty fruit bunches. Bioresour. Technol. (2012), http://dx.doi.org/10.1016/j.biortech.2012.09.042