b i o m a s s a n d b i o e n e r g y 5 9 ( 2 0 1 3 ) 3 1 6 e3 2 4

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Production and detailed characterization of bio-oil

from fast pyrolysis of palm kernel shell

Mohammad Asadullah*, Nurul Suhada Ab Rasid,

Sharifah Aishah Syed A. Kadir, Amin Azdarpour
Faculty of Chemical Engineering, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia

article info abstract

Article history: Bio-oil has been produced from palm kernel shell in a fluidized bed reactor. The process
Received 21 March 2013 conditions were optimized and the detailed characteristics of bio-oil were carried out. The
Received in revised form higher feeding rate and higher gas flow rate attributed to higher bio-oil yield. The
25 August 2013 maximum mass fraction of biomass (57%) converted to bio-oil at 550
C when 2 L min1 of
Accepted 26 August 2013 gas and 10 g min1 of biomass were fed. The bio-oil produced up to 500
C existed in two
Available online 19 September 2013 distinct phases, while it formed one homogeneous phase when it was produced above
500
C. The higher heating value of bio-oil produced at 550
C was found to be 23.48 MJ kg1.
Keywords: As GCeMS data shows, the area ratio of phenol is the maximum among the area ratio of
Biomass pyrolysis identified compounds in 550
C bio-oil. The UVeFluorescence absorption, which is the
Bio-oil indication of aromatic content, is also the highest in 550
C bio-oil.
Palm kernel shell ª 2013 Elsevier Ltd. All rights reserved.
Biofuel
Renewable energy

1. Introduction
Biomass is abundantly available everywhere in the world [1];
however, the suitable technology related to biomass conver-
sion to useful form of energy is yet to be developed [2].
Although it is available everywhere on the earth the majority
of it is widely distributed across the origin and difficult to
collect. Therefore, the commercial utilization of biomass for
energy requires integration of intensive logistic system, which
is one of the main obstacles of biomass energy commerciali-
zation [3]. Unlike other countries, Malaysia and Indonesia
produce large amount of accumulated oil palm biomasses
such as palm kernel shell (PKS), empty fruit bunch and
mesocarp fiber at palm oil mills. The utilization of these
accumulated biomasses can reduce the cost of complex
biomass collection system. Around 420 palm oil mills are
currently operated in Malaysia to produce crude palm oil
(CPO) and palm kernel oil [4], which generate fresh and as
received biomass of about (12e15%) fibers, (6e7%) shells, and
(21e23%) empty fruit bunches (EFB) based on fresh fruit bunch
(FFB) used [5e7]. The carbon and hydrogen contents in oil
palm biomasses are comparable with hard wood, and thus
these biomasses have inherently high energy content, which
can be converted to useful form of energy using modern
technologies, for example, pyrolysis process.
The palm kernel shell (PKS) is one of the high carbon content
solid materials, which is currently used as a combustion boiler
fuel with very limited efficiency. Utilizing pyrolysis technology,
PKS can be converted to bio-oil, a useful form of energy.
However, the technological barrier, indigenous properties of

* Corresponding author. Tel.: þ60 3 5543 6359; fax: þ60 3 5543 6300.
E-mail addresses: asadullah@salam.uitm.edu.my, asadullah8666@yahoo.com (M. Asadullah).
0961-9534/$ e see front matter ª 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.biombioe.2013.08.037
 b i o m a s s a n d b i o e n e r g y 5 9 ( 2 0 1 3 ) 3 1 6 e3 2 4
PKS, the physical and chemical properties of bio-oil from PKS
and lacking of studies slow down the commercial uptake of PKS
for bio-oil production.
Because of the physical appearance and hardness, PKS can
be considered as a natural pellet of lignocellulosic materials.
Its loose and compacted bulk density varies in the range of
500e600 kg m3 and 600e740 kg m3, respectively [8,9], while
the particle densities varies in the range of 1140e1620 kg m3
[10]. The bulk density of PKS is almost 2.5 times higher than
that of wood chips of w20 mm particle size (209e273 kg m3)
[11], while the particle density is even higher (around 4 times)
[12]. However, the thermal conductivity of PKS
(0.190 W m1 K1) [13], is almost similar to that of the hard
wood (0.168 W m1 K1) [14]. It implies that the heat transfer
from the outer surface of the rigid and lower conductive PKS to
the center is slow, like woody biomass.
In the technology development efforts for pyrolysis of
biomass to produce bio-oil, most of the research groups often
use the small particles of biomass, sometimes even powder of
biomass, especially for fluidized bed pyrolysis system [15].
However, in reality, the biomass preparation in such a small
particle, especially for PKS, is difficult and cost intensive,
reducing the cost effectiveness of the process. In our previous
pyrolysis experiments, we have clearly observed that when
big particles of biomass were used in the existing pyrolysis
processes, for example, fixed bed pyrolyzer, the yield of bio-oil
significantly decreased while the water content and the yield
of char increased [16,17]. If the volatile residence time in the
particle is comparatively longer, usually in the case of fixed
bed and slow heating process, the organic volatiles readily
repolymerize and deposit on to the solid char, leaving water
molecules in the vapor phase. Most importantly, even in the
fast heating system, when a big particle is pyrolyzed, the heat
transfer from the outer surface to the center of the particle
faces significant resistance. Therefore, the heating rate of the
central mass is much slower, allowing the slow pyrolysis to
occur, and thus yielding higher amount of char and water. In
addition, fluidized bed pyrolyzers including other pyrolyzers
need high flow of inert gas, which further adds complexity in
condensation of bio-oil in the condenser because of high
speed of vapor phase. Therefore, the traditional reactor sys-
tem contributes partly to the lack of rapid progress in the
development of economically feasible biomass conversion
technologies.
For commercial production of bio-oil, two major factors
such as yield and composition of bio-oil need to be carefully
considered. They are entirely depended on the biomass type
and operational conditions of pyrolysis, especially on the heat
transfer rate to the entire particle. Comprehensive researches
have been done to optimize the pyrolysis conditions for
different biomasses over the last years [18]. Most of the re-
searches focused to reduce the water yield and increase the
smaller organic fraction in bio-oil, so as to increase the igni-
tion properties of bio-oil [19]. Although a little contribution is
found in the literature for PKS pyrolysis to produce bio-oil
[20e22] a wide variation in product characteristics is
observed. For instance, reference [20] reported the calorific
value 17.9 MJ kg1 of bio-oil derived from Malaysian PKS, while
Refs. [21] and [22] obtained the caloric value of 26e27 MJ kg1
and 6.58 MJ kg1, respectively. The ash, volatile matter and
317
fixed carbon contents in individual biomass should be con-
stant value; however, they are widely varied in different re-
ports for PKS [20,21,23]. More investigation can reduce the gap
of different findings and can produce more consistent data. In
this study the PKS is characterized in terms of proximate and
ultimate analyses and pyrolyzed to produce bio-oil. Bio-oil is
characterized in detail to evaluate the physical and chemical
characteristics.
2. Experimental
2.1. Feedstock and chemicals
The variety of oil palm (Elaeis guineensis) in Malaysia is tenera
hybrid, which is a cross product of dura (thick shell palm) and
pisifera (shell-less palm). The location of oil palm cultivation
and palm kernel shell (PKS) collection is Selangor State
(Geographical Coordinates 3.3333
N, 101.5000
E) in Malaysia.
The PKS collected was generated from fresh fruit bunches
(FFB), which were harvested from 12 to 15 years old of tenera
variety oil palm. The PKS collected was exposed to the entire
procedure of oil extraction process such as sterilization under
145
C and 0.27 MPa for 90 min, digestion at 90e100
C for
30 min and pressing. The nuts were then separated and
crushed to separate the shell, which was collected as PKS for
our experiments. After collecting, PKS was sun-dried for two
days in order to remove unbound moisture. The PKS was then
ground using a grinding machine and sieved to obtain around
1e2 mm particle size. The final ground PKS was then stored in
a freezer bellow 0
C in order to avoid any degradation. The
processed sample was characterized by evaluating the proxi-
mate and ultimate analyses. For bio-oil analysis, analytical
grade methanol (Merck) and chloroform (Merck) were used as
solvents and for water content determination, Karl Fischer
reagent was used.
2.2. Proximate and ultimate analyses of feedstock
For proximate analysis, the volatile and fixed carbon were
determined using a Thermogravimetric Analyzer (TGA)
(Model DTA 60A), while the ash content was determined using
a Muffle furnace. In TGA, about 20 mg of sample was used and
heated from room temperature to 900
C at a rate of 10 K min1
under the flow of N2 at a rate of 200 cm3 min1. For ash content
determination, 1 g of PKS of 1e2 mm particle size was taken in
a ceramic crucible, which was then placed in a Muffle furnace.
The temperature of Muffle furnace was set at 600
C and the
sample was burned isothermally for overnight. After cooling
the crucible, it was weighed from where the ash content was
calculated.
2.3. Procedure for bio-oil production
For fast pyrolysis of PKS to produce bio-oil, a stainless steel
bench scale fluidized bed reactor was used. A conceptual
design of the pyrolysis system is shown in Fig. 1. The reactor
was made of stainless steel (grade SS316) with a configuration
of 60 cm height and 6 cm internal diameter. The reactor
consists of a feeding line, gas inlet and product outlet at the
318 b i o m a s s a n d b i o e n e r g y 5 9 ( 2 0 1 3 ) 3 1 6 e3 2 4
Fig. 1 e A conceptual diagram of a fluidized-bed pyrolyzer.
top. The feeding line is an inner tube of 2 cm internal diameter
and 40 cm length inserted into the reactor from the top. The
top part of the feeding line is connected to a screw feeder from
where the PKS particles were fed into the reactor at a constant
rate. The feeding rate was controlled by controlling the rota-
tion of screw using a DC gear motor, which is controlled by an
inverter controller. The PKS particles were fallen from the
feeder and traveled gravitationally through the tube to the
fluidized bed. Quartz sand of 400e500 mm size was used as
fluidized bed materials. The sand particles were fluidized by
the flow of nitrogen gas. The reactor was externally heated
using an electrical tube furnace. The temperature of the
furnace was controlled by a temperature controller using two
K-type thermocouples. One thermocouple was used to
monitor the furnace temperature, while the other one was
used to monitor the real temperature in the reactor.
The bio-oil vapor exited from the outlet at the top of the
reactor and traveled through a series of condensers, while it
was coalesced and collected in the container connected to
each of the condenser. The temperature of the condenser was
maintained around 70
C using dry ice bath. The liquids
collected in the containers were mixed together in order to get
one bio-oil sample from each experiment. No vapor was
visually observed in the gas stream when it was traveled
through transparent plastic tube at the outlet of the
condenser, ensuring the efficient condensation of vapor. The
non-condensable gas was burned at the end of the outlet tube.
2.4. Physical characterization of bio-oil
Bio-oil was characterized by determining the physical pa-
rameters including density, pH value, heating value, water
content, solid content, lignin content and ash content. The
density was measured with a pycnometer. The pH of bio-oil
was measured using a digital pH meter (Model e HI 8424).
The higher heating value of bio-oil was determined by means
of an oxygen bomb calorimeter (Parr Oxygen Bomb Calorim-
eter, 6400). The Karl Fischer titrimetric method determined
the water content in the bio-oil samples. For each titration,
10 mg of sample was added into the titration chamber where
upon starting the machine the reagent was pulsed intermit-
tently, while reaction was continued upon continuous agita-
tion with a magnetic stirrer.
Some solid particles usually char and metallic species were
carried over by gas stream and mixed with bio-oil. The solid
content in bio-oil is defined as the insoluble materials in
ethanol. To measure it, a certain amount (25e50 g) of bio-oil
was weighed in a beaker and about 250e300 cm3 of ethanol
was added into the beaker. After stirring the mixture for a
while with a magnetic stirrer, it was filtered with a filter paper,
followed by drying. The insoluble portion remained on the
filter paper was weighed out and determined the weight
percent of solid content in bio-oil.
The lignin portion was measured as water insoluble frac-
tion by using phase separation as described in the literature
 b i o m a s s a n d b i o e n e r g y 5 9 ( 2 0 1 3 ) 3 1 6 e3 2 4
[24,25]. For the measurement of lignin content, 5 g of bio-oil
was added dropwise into 500 cm3 of ice-cooled distilled
water with stirring. The lignin was precipitated which was
filtered, followed by drying at room temperature under vac-
uum and then weighed. The ash content was determined by
burning of 10 g bio-oil at around 600
C in a muffle furnace for
overnight. The left over solid was considered as ash.
2.5. Chemical characterization of bio-oil
2.5.1. FT-IR spectroscopy
In order to know the group of compounds in bio-oil in terms of
functional groups, the FT-IR spectra of different bio-oil sam-
ples were recorded between 4000 and 400 cm1 wavenumber
using a PerkineElmer Spectrum GX FT-IR spectrometer. Fifty
scans were recorded at 4 cm1 spectral resolution.
2.5.2. GCeMS
The chemical composition of different bio-oil samples was
evaluated using a GC-MS-QP2010 equipped with a capillary
column coated with Rtx-5MS (60 m  0.25 mm i.d., 0.25 mm film
thickness). The raw sample was dissolved in analytical grade
methanol and 1 mL of sample was injected into the column.
The GC oven was heated from 50
C (1 min) to 150
C at a rate
of 5 K min1 (5 min hold) and finally to 300
C at a rate of
5 K min1 with an isothermal period of 15 min. Each com-
pound was identified by matching of its mass spectrum with
that in the spectral library (NIST 08 database). A semi-
quantitative analysis of each compound was performed
using the peak area ratio of individual compound with total
cumulative peak area of all compounds.
2.5.3. UVeFluorescence spectra
UVefluorescence spectra of bio-oil samples produced at
different temperatures were recorded using a PerkineElmer
LS50B luminescence spectrometer with a 1 cm light path
length. For this analysis the bio-oil samples were diluted to
around 1 mg L1 concentration using methanol (Uvasol for
spectroscopy; purity (GC): 99.9%). The spectra were recorded
under a constant energy difference of 2800 cm1 together
with a scan speed of 200 nm min1 and slit widths of 2.5 nm.
The fluorescence intensity was multiplied by the bio-oil yield
in each phase and then added together make representative
data on the basis of ‘per gram of dry biomass’.
3. Results and discussion
3.1. Physical and chemical characteristics of PKS
The physical properties and chemical composition of feed-
stock greatly affect the bio-oil yield and characteristics. The
summary of the physical properties and chemical composi-
tion of PKS is presented in Table 1. The inherent particle size
of PKS usually in the range of 7e15 mm; however, for this
investigation the PKS was ground to 1e2 mm size. The mois-
ture content in PKS is one of the crucial issues for producing
bio-oil from biomass. The entire water in biomass usually
goes into bio-oil, increasing the water content in bio-oil.
319
Table 1 e Physical and chemical characteristics of palm
kernel shell.
Moisture mass fraction (%) 12
Particle size (mm) 7e15
Bulk density (kg m3) 0.56
Proximate analysis
Volatile mass fraction (%) 74
Fixed carbon mass fraction (%) 23
Ash mass fraction (%) 3
Ultimate analysis (daf)a
C 45.10
H 5.10
O 49.20
N 0.56
S 0.04
a
Ultimate analysis is calculated under dry and ash free basis.
Therefore, the raw PKS was sundried to reduce moisture
content from the mass fraction around 22e25% to 12%.
3.2. Pyrolysis behavior of PKS
The physical and chemical characteristics of agricultural
residues vary widely based on the variation of species of the
plants. Palm kernel shell is one of the agricultural residues,
contains higher fraction of lignin (44%) [21], compared to other
biomass such as EFB (15%) [20] and hard wood (20e25%) [26].
Carbon mass fraction in lignin is 59% and it is 42% in cellulose
[27]. In addition, lignin is covalently linked to hemicellulose
and cross linked to polysaccharide, and thus it is highly rigid
and hard. Because of the rigidness and low thermal conduc-
tivity, the thermal decomposition of PKS is slow, compared to
other biomasses [20,26]. The behavior of thermal decomposi-
tion of PKS, EFB and sawdust can be seen in TGA and DTA
profiles in Fig. 2a and b. As can be seen in Fig. 2a, the first
weight loss is related to the removal of bound and unbound
moisture, which is remarkable for sawdust due to its high
moisture content. The thermal decomposition of EFB, PKS and
sawdust started at 290
C, 210
C, and 220
C, respectively;
however, the major weight loss of EFB (57%) and sawdust
(67%) occurred within 390
C, which are higher than that of the
weight loss of PKS (52%). In addition, the thermal decompo-
sition of PKS components, especially hemicellulose and cel-
lulose occurred sequentially as can be seen in DTA profile in
Fig. 2b. The first peak is assigned to devolatilization of hemi-
cellulose, while the second peak is assigned to cellulose
[23,27]. The devolatilization of lignin started with hemicellu-
lose and slowly continued even until 700
C [27], and this
makes difficulties for PKS to be pyrolyzed for bio-oil produc-
tion. However, since lignin is consisted of mostly aromatic
ring system, the bio-oil produced from PKS is rich of aromatic
compounds, and thus the downstream application of PKS bio-
oil is advantageous. In addition, the indigenous compact na-
ture of PKS provides advantages in transportation, storage and
it is easy to feed in the pyrolysis reactor.
3.3. Effect of temperature on the product distribution
The product distribution of PKS pyrolysis at different tem-
peratures ranging from 350
C to 650
C is shown in Fig. 3a.
320 b i o m a s s a n d b i o e n e r g y 5 9 ( 2 0 1 3 ) 3 1 6 e3 2 4

Fig. 2 e TGA, (a) and DTA, (b) profiles of palm kernel shell,
empty fruit bunch and sawdust.

The liquid yield varied between 44 and 56%, depending on the

temperature, while char and gas yields varied between 23 and
46% and 9 and 28%, respectively. The bio-oil yield varies in a
short range, compared to char and gas yields. This is because
the major fraction of volatiles released from PKS at around
350
C, which is approximately 50% as indicated by the TGA
profile in Fig. 2a. Above 350
C, the solid char was gradually
decomposed to liquid vapor and gas and simultaneously the
organic vapor converted to gases, and thus the net liquid
formation existed in small variation. However, the char yield
was decreased and gas yield was increased with increasing
temperature remarkably.
The product distribution obtained in our investigation
Fig. 3 e Effect of temperature, (a); gas flow rate, (b) and
significantly differs from the results of previously reported
feeding rate, (c) on product distribution of PKS pyrolysis.
slow pyrolysis [21] as well as fast pyrolysis [28] of PKS. The
lower liquid and higher char yields are reasonable under slow
pyrolysis due to the repolymerization of devolatilized organic
molecules as we can observe at lower temperature product the weight of solid and liquid from the total weight of PKS fed
distribution in Fig. 3a. However, the higher gas yield w30% [28] into the reactor. In this case, the inefficient condensation can
differs from our experimental result (<20%) bellow 550
C. In provide lower liquid and higher gas yield. However, we ob-
our experiment, we have directly weighed condensed liquid tained liquid yield higher than any reported results [21,28]
bio-oil and since the char was accumulated in the reactor, it because of efficient cooling system. In addition, we obtained
was measured directly as the weight gained by the reactor bio-oil in two distinct phases bellow 500
C pyrolysis tem-
during pyrolysis. The gas was measured as the difference of peratures, while it was a single homogeneous phase at 550
C
 b i o m a s s a n d b i o e n e r g y 5 9 ( 2 0 1 3 ) 3 1 6 e3 2 4
and above. This may be due to the higher water yield and
bigger organic molecules in bio-oil, which enhanced the po-
larity difference at lower temperatures (<500
C).
3.4. Effect of gas flow rate on the product distribution
During pyrolysis, the reactive environment influences the
secondary reactions, i.e., cracking and repolymerization, due to
the longer vapor residence time in the reactor. Therefore, the
rapid mass transfer from the reactive zone in combination with
rapid quenching of the vapor phase can enhance the bio-oil
yield. Usually the inert gases such as N2 and Ar are used for
rapid purging of hot pyrolysis vapors. In this study, N2 flow in
the range of 1e2 L min1 was investigated in order to find the
optimum gas flow rate. Fig. 3b exhibits the effect of N2 flow rate
on the product distribution. Under lower gas flow rate
(1 L min1), the liquid yield is lower, while the char and gas yield
was higher. The liquid yield was slightly increased, while the
char and gas yield was decreased with increasing the N2 flow
rate. The results are quite consistent with other reported re-
sults [29,30]. Flowing N2 gas through pyrolysis zone reduces the
residence time of pyrolysis vapors in the reactive zone, inhib-
iting the possibility of repolymerization and cracking of vapors
and maximizing the liquid yield [31]. It is important to note that
the high gas flow can reduce the effective condensation of
vapor, which may cause the lower liquid yield. However, in our
experiment, rapid quenching of thermally cracked pyrolysis
vapors was used under dry ice condition. The temperature in
the dry ice bath was around 70
C, and almost all condensable
vapors were condensed under this condition.
3.5. Effect of feeding rate on the product distribution
The effect of feeding rate on the product distribution and bio-
oil characteristics entirely depends on the reactor configura-
tion. Under the confined reactor configuration used in this
investigation, the feeding rate was varied from 3 g min1 to
10 g min1 at 550
C pyrolysis temperature and the results
obtained are exhibited in Fig. 3c. Since the primary pyrolysis of
biomass is endothermic, the available transferable heat under
the constant fluidization condition would vary due to varying
biomass feeding rate. The solid to solid heat transfer rate is
assumed to be much faster when the feeding rate is lower, and
thus the primary volatile formation is assumed to be higher
compared to the solid char. However, as can be seen in Fig. 3c,
the char and gas yield was significantly higher compared to
the liquid yield when the feeding rate was 3 g min1. On the
other hand, the liquid yield was higher when the feeding rate
was 10 g min1, compared to gas and char yield. It reveals that
the faster heat transfer in the case of 3 g min1 could assist
quicker devolatilization, which led to gas and organic vapor
formation. However, since the formation of total gas phase is 3
fold lower than 10 g min1 feeding rate, the volatile residence
time is much higher for 3 g min1 feeding rate. It means that
the volatileechar interaction is much longer for 3 g min1
feeding rate, leading to the repolymerization of volatiles,
thereby forming the increasing amount of secondary char/
coke on the sand and char surface. On the other hand, the
longer vapor residence time also assisted the secondary
cracking of organic vapor to gas. Under higher feeding rate
321
(10 g min1), the vapor residence time was significantly
shorter, meaning that the secondary cracking of vapor to gas
and repolymerization to form secondary char/coke are not
favorable, and thus the char and gas yields are lower. The
effect of feeding rate is also attributed to the bio-oil charac-
teristics as discussed in the subsequent sections.
3.6. Characterization of bio-oil
3.6.1. Physical characterization of bio-oil
The typical physical properties of bio-oil derived from palm
kernel shell at 550
C were summarized in Table 2. As can be
seen from the data, the density of the bio-oil at 25
C was
1040 kg m3, which is significantly higher than that of heavy
fuel oil (typically w 855 kg m3). This is mainly due to the
presence of oxygen containing heavy organic molecules, for
instance, phenol. The pH of bio-oil was obtained to be 2.5,
much lower than bio-oils derived from soft biomasses like
bagasse [16] and jute sticks [17]; however, it is almost similar
to bio-oils derived from hard wood [29]. The acidity of bio-oil is
mainly due to the presence of organic acids like phenol and its
derivatives, which are the major ingredients in bio-oil. These
phenolic compounds mainly derived from lignin, the major
ingredient in PKS.
The lignin content is the measure of water insoluble frac-
tion in bio-oil, which was measured by the method described
in the literature [24,25] and it was found to be 0.30%. The solid
content in the bio-oil is defined as the insoluble heavy organic
materials in some specific solvents such as ethanol in addition
to the actual solids. Solid fraction in the sample of 550
C was
found to be 0.58% as shown in Table 2. This result is quite
consistent with many reported results [31]. The ash fraction in
the bio-oil was found to be around 0.01%.
The physical appearance of bio-oil produced at different
temperatures from PKS was different. In our investigation, the
bio-oil produced up to 500
C existed in two distinct phases,
while it was produced in one homogeneous phase above
500
C. During pyrolysis, water derives from the moisture
content of biomass as well as from the dehydration and
condensation reactions of organic molecules. These reactions
favorably proceed at lower temperatures, providing high yield
of water, which leads bio-oil to split into two distinct layers.
The water mass fraction in top and bottom layers of bio-oil
produced at 350
C was found to be 71 and 16%, respectively.
As Fig. 4a, the water content decreased in both layers with
increasing temperature, possibly due to the suppression of
secondary condensation reaction at higher temperatures. In
addition, the total gas volume was rather high due to higher
gas yield as well as gas expansion at higher temperatures that
Table 2 e Physical properties of bio-oil.
Density (Mg m3) 1.04
pH 2.5
Lignin mass fraction (%) 0.30
Solid mass fraction (%) 0.58
Ash mass fraction (%) 0.10
Pyrolysis conditions: Temperature, 550
C; gas flow rate, 1 L min1
and PKS feeding rate 10 g min1.
322 b i o m a s s a n d b i o e n e r g y 5 9 ( 2 0 1 3 ) 3 1 6 e3 2 4
it reduced the vapor residence time, which was unfavorable
for secondary reactions. The average water mass fraction was
around 38e42%.
The bio-oil produced at 550
C and above contained water
mass fraction of 32e34% and existed in one homogeneous
phase and this result is consistent with other studies [21,22].
Although the bio-oil produced at high temperature existed in
one homogeneous phase the water content in the top part and
bottom part of bio-oil was different as can be seen from Fig. 4b.
Interestingly, the water content in the top part decreased,
while it increased in the bottom part with increasing pyrolysis
temperature. This can be explained that the high temperature
assisted the thermal cracking of bigger molecules to produce
smaller organic compounds, which are more likely water-
phillic, and thus water can diffuse to bottom part. Since some
of the water was migrated to bottom part, the total water
content decreased at the top part.
The higher heating value (HHV) of different bio-oil samples
derived at different temperatures was determined using bomb
calorimeter. It is important to mention that the aqueous phase
of bio-oil produced below 500
C was not ignited in the calo-
rimeter due to excessive water content; hence the calorific
value of aqueous phase was unable to determine. The organic
phase of bio-oil produced below 500
C and the homogeneous
samples produced up to 650
C were ignited and the calorific
value was determined as represented in Fig. 4c. The HHV of
organic phase gradually increased from 23.13 MJ kg1 to
24.10 MJ kg1 of the samples from 350
C to 500
C. This
increment may be due to the gradual decrease of water con-
tent in organic phase as shown in Fig. 4a. The HHV is slightly
Fig. 4 e Effect of temperature on water content in bio-oil produced between 350 and 500
C, (a); 350e650
C, (b); higher
heating value, (c) and GCeMS peak area ratio of phenol, (d).
decreased from 23.48 to 23.18 MJ kg1 due to the variation of
water content of the homogeneous samples obtained from
550 to 650
C.
3.6.2. Chemical characterization of bio-oil
The bio-oil produced at 550
C was characterized by GCeMS in
order to identify the type of compounds as well as their semi
quantitative composition. The results are shown in Table 3.
Although bio-oil comprises of a mixture of various organic
compounds the phenol and its derivatives showed the major
peak area among the detected compounds. There is a wide
variety of compounds in bio-oil; however, their peak areas are
very low and not counted in this study. The compounds listed
in Table 3 are all oxygenated. High oxygen content in bio-oil is
attributed to lower heating value.
As Fig. 4d shows, the peak area ratio of phenol obtained
from the top and bottom layers as well as from the homoge-
neous phase depending on pyrolysis temperatures. It was
increased for bottom layer, while it was decreased for top
layer with increasing pyrolysis temperature up to 500
C. In
average, the peak area ratio of phenol was reduced with
elevating temperature up to 500
C. For the homogeneous bio-
oil, the peak area ratio was further reduced with increasing
temperature. It implies that the relative evolution of phenol at
higher temperature is lower. This may be due to the inhibition
of phenol formation or due to the phenol conversion to other
compounds at higher temperature than 500
C.
Bio-oil is consisted of oxygenated organic compounds,
which are evaluated by FT-IR spectroscopy as shown in Fig. 5.
The bio-oil produced at 550
C was extracted with an equal
 b i o m a s s a n d b i o e n e r g y 5 9 ( 2 0 1 3 ) 3 1 6 e3 2 4 323

phase. Both phases as well as the raw homogeneous bio-oil

Table 3 e Identification and quantification of PKS bio-oil
component by GCeMS analysis. were analyzed with FT-IR spectroscopy.
Among the compounds present, phenol is the major one
Chemical name of the component Molecular Peak
and the OeH stretching vibration between 3200 cm1 and
formula area (%)
3600 cm1 attributed to phenol and alcohol in bio-oil [21,22],
Furfural C5H4O2 1.19 which are existed in both of the phases. The broad band in-
2-hydroxy-3-methyl-2-cyclopenten- C8H8O2 0.09
dicates that the OH groups are hydrogen bonded to water
1-one
molecules especially in the aqueous phase. The bands be-
3-ethyl-2-hexene C8H16 0.56
2-methoxy phenol C7H8O2 4.01 tween 2800 cm1 and 3000 cm1 are assigned to CeH
2-methoxy-6-methylphenol C8H10O2 0.17 stretching vibration, while the bands between 1350 cm1 and
4-methoxy-3-methylphenol C8H10O2 0.16 1470 cm1 indicate the CeH bending vibrations, which are
4-methoxy-3-methylphenol C8H10O2 0.16 attributed to the presence of alkanes [21]. The C]O stretching
2-methoxy-4 methyl-phenol C8H10O2 3.16 vibrations at 1715 cm1 is indicative of the presence of ke-
1,4-dimethoxy-2-methyl-benzene C9H12O2 0.24
tones, quinones and aldehyde groups. The band between
Phenol C6H5OH 19.86
1580 cm1 and 1650 cm1 represents the aromatic group [21].
4-ethyl-2 methoxy-phenol C9H12O2 2.65
4-ethyl-phenol C8H10O 0.12 This peak is weaker for organic phase compared to aqueous
2-methyl phenol C7H8O 0.83 phase, indicating that the phenols diffused into the aqueous
3-methyl-phenol C7H8O 0.33 phase. The band between 1500 and 1510 cm1 is assigned to
2-methoxy-4-propyl-phenol C10H14O2 0.69 C]C stretching vibrations, which indicated the presence of
Eugenol C10H10O2 0.39 alkenes. The peaks in between 950 and 1300 cm1 were
2,6-dimethoxy phenol C8H10O3 4.64
attributed to the presence of different alcohols, phenols,
1,2,4-Trimethoxybenzene C9H12O3 2.36
5-tert-butylpyrogallol C10H14O3 1.49
ethers and esters with CeO stretching and OeH deformation
3,5-dimethoxy-4-hydroxyphenylacetic C10H12O5 0.63 vibration. In addition, mono and polycyclic and substituted
acid aromatic groups can be represented by the absorption peaks
1-(4-hydroxy-3-methoxyphenyl)-2- C10H12O3 1.04 between 690e900 and 1350e1450 cm1 [32].
propanone The Fig. 6 represents the UVeFluorescence spectroscopy,
2,6-dimethoxy-4-(2-propenyl)-phenol C11H14O3 1.04
which characterizes the aromatic ring systems in bio-oil. The
4-(2,3-dimethoxyphenyl)butanoic acid C12H16O4 0.90
intensity of the absorption of fluorescence is an indicator of
Methylparaben C8H8O3 1.13
1-(2,4,6-trihydroxyphenyl)-2-pentanone C11H14O4 1.04 the aromatic content in bio-oil. As Fig. 6a shows, the absorp-
tion of bio-oil was increased with increasing pyrolysis tem-
Pyrolysis conditions: Temperature, 550
C; gas flow rate, 1.5 L min1
perature. On the other hand, the aromatic concentration in
and PKS feeding rate 10 g min1. Analytical method: The GC oven
homogeneous bio-oil produced at 550
C is the highest as
was heated from 50
C (1 min) to 150
C at a rate of 5 K min1 (5 min
hold) and finally to 300
C at a rate of 5 K min1 with an isothermal shown in Fig. 6 and that was reduced with increasing tem-
period of 15 min. perature due to thermal decomposition of aromatic com-
pounds at higher temperatures.

mixture of methanol and chloroform. When bio-oil was added

into the solvent mixture, the aquaphilic compounds were
diffused into the top aqueous phase and aromatic and non
4. Conclusions
polar organic molecules were diffused into the bottom organic
The pyrolysis of PKS was investigated to produce bio-oil in a
fluidized bed reactor. The higher feeding rate and higher gas

Fig. 5 e FT-IR spectra of raw and extracted bio-oil produced Fig. 6 e UVeFluorescence spectra of bio-oils produced at
at 550
C. different temperatures.
324 b i o m a s s a n d b i o e n e r g y 5 9 ( 2 0 1 3 ) 3 1 6 e3 2 4
flow rate facilitated to enhance the bio-oil yield. The bio-oil
produced up to pyrolysis temperature 500
C formed two
distinct phases; however, they were in one homogeneous
phase when bio-oil was produced above this temperature. The
water content was reduced with increasing pyrolysis tem-
perature. The GCeMS data indicated that the peak area ration
of phenol is higher than any other detectable compound
evolved in the pyrolysis of PKS. The UVeFluorescence ab-
sorption, which is the indication of aromatic content, was also
the highest for bio-oil produced at 550
C.
Acknowledgments
This research is financially supported by the Research Man-
agement Institute, Universiti Teknologi Mara under the proj-
ect No. 600-RMI/DANA5/3/RIF(110/2012) and Ministry of
Higher Education, Malaysia under the project No. 600-RMI/
PRGS/5/3(3/20/2011).
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