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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
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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
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
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
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.
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
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
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
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
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
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
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
1
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
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%)
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
Table 4
Summary of kinetic parameters activation energy.
Sample
Temperature
range
Mechanism
Correlation coefcient
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
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
Z
0
da
A
1 an b
eE=RT dT
T0
ln
ga
T
ln
AR
2RT
E
1
bE
E
RT
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
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
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