Energy 36 (2011) 2352e2359

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Energy
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Optimum conditions for maximising pyrolysis liquids of oil palm

empty fruit bunches
F. Sulaiman*, N. Abdullah
School of Physics, Universiti Sains Malaysia, 11800 Minden, Penang, Malaysia

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

Article history: As production of palm oil is expanding, a more efficient use of oil palm biomass to obtain more energy
Received 23 June 2010 from oil palm plantations is investigated. The work was carried out on a fluidised bed bench scale fast
Received in revised form pyrolysis unit, with the objective of determining the important conditions and key variables which are
23 December 2010
required to maximise the liquid yield and its quality. The investigation on the impact of reactor
Accepted 30 December 2010
temperature, varying residence time by changing the nitrogen flow rate and combined impact of ash
Available online 26 February 2011
content and particle size on the product yields is presented. The properties of the liquid product were
analysed and compared with wood derived bio-oil and petroleum fuels. It was found that in all cases the
Keywords:
Empty fruit bunches
liquid product separated into two phases presenting difficulties for fuel applications, which are critically
Fast pyrolysis discussed. Potential solutions are also proposed which include upgrading of the liquid for fuel applica-
Oil palm tions and other useful applications.
Bio-oil Ó 2011 Elsevier Ltd. All rights reserved.
Biomass

1. Introduction
Palm oil and related products represented the second largest
export of Malaysia in the first nine months of 2005, after elec-
tronics, but just ahead of crude oil [1]. In 2005, Malaysian palm oil
production is projected to reach approximately 15 million tonnes
(301,000 barrels per day) [2]. By comparison, Malaysian petroleum
production in 2004 is estimated at 43 million tonnes (855,000
barrels per day), of which 16 million tonnes (321,000 barrels per
day) were exported. Domestic petroleum demand of 26 million
tonnes represented 44% of total energy demand of 60 million
tonnes of oil equivalent [3].
One way to obtain more energy from oil palm plantations, and
the one investigated in this research, is the more efficient use of oil
palm biomass other than the palm oil [4]. There are no detailed
statistics for oil palm dry matter production. Such statistics are only
compiled for palm oil, palm kernel and FFB (fresh fruit bunches).
Rough extrapolations, however, can be made based on estimates of
the ratio of palm oil to other dry matter. For each kg of palm oil
roughly another 4 kg of dry biomass are produced, approximately
a third of which is found in FFB derived wastes and the other two
thirds is represented by trunk and frond material [5e7]. On an
energy basis, the palm oil represents roughly a third of the biomass
* Corresponding author. Tel.: þ60 46533654; fax: þ60 46579150.
E-mail address: fauziahsulaiman@usm.my (F. Sulaiman).
yield, as it has roughly twice the heating value of the other oil palm
dry matter, which therefore amounts to approximately 2 kg on
a palm oil equivalent basis. Based on projected 2005 production
around 30 million metric tonnes of oil equivalent of non palm oil
dry biomass matter were therefore theoretically available for
energy production from Malaysian palm oil plantations, or in other
words approximately half of 2004 total primary energy demand.
Only a small fraction of this potential was used, and that very
inefficiently. Open burning, while being discouraged, is still too
common and responsible for substantial air pollution problems in
South East Asia. Some of the biomass is used for mulching and as
fertiliser, though this use is limited by labour and logistical limi-
tations and concerns about encouraging oil palm pests [8].
To illustrate the kinds of waste available, the process flow of
a palm oil mill is summarised in Fig. 1 (simplified from [9]) and
a typical product stream distribution is shown in Table 1 (adapted
from Ref. [6]). A particularly interesting waste by-product are EFB
(empty fruit bunches). Currently palm oil mills typically use shell
and the drier part of the fibre product stream, rather than EFB, to
fuel their boilers, as the raw EFB contains nearly 60% water [10]. As
can be seen in Table 1, the moisture content of fresh EFB is very
high. Consequently, it is a poor fuel without drying and presents
a considerable emissions problem that its burning is discouraged by
the Malaysian government. Palm oil mills therefore typically use
shell and the drier part of the fibre product stream, rather than EFB,
to fuel their boilers [10]. POME (Palm Oil Mill Effluent) is so wet that

0360-5442/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.energy.2010.12.067
 F. Sulaiman, N. Abdullah / Energy 36 (2011) 2352e2359 2353

Fresh Fruit Bunches (FFB)

Sterilisation and stripping

Palm Oil Mill Fresh fruits

Effluent (POME) Empty Fruit Bunches (EFB)

Digestion, clarification and pressing

Palm oil Press cake

Depericarping
Nuts
Fibre
Nut cracking

Kernel Shell

Fig. 1. Simplified process flow diagram of an oil palm mill (main waste streams in bold).

it is usually treated by anaerobic digestion before discharge of the size and sweep gas flow rate on the pyrolysis product yields and
effluents [11]. their chemical compositions. They conducted the fast pyrolysis
Fast pyrolysis represents a potential route to upgrade the EFB experiments in a well-swept, resistively-heated, fixed-bed reactor.
waste to value added fuels and renewable chemicals. For woody They found that the liquid yield reached a maximum of 68% by
feedstock, temperatures around 500  C together with short vapour employing the higher heating rate of 300  C min1 at temperature
residence times are used to obtain bio-oil yields of around 70%, and of 550  C for particle size range of 0.6e1.25 mm. Tsai et al. [16]
char and gas yields of around 15% each [12]. Bio-oil is a high density examined the effect of temperature, heating rate, holding time,
oxygenated liquid, which can be burned in diesel engines, turbines nitrogen gas flow rate, condensation temperature and particle size
or boilers, though further work is still required to demonstrate long on the pyrolysis product yields and their chemical compositions.
term reliability [13]. It is also used for the production of speciality They prepared a series of pyrolysis liquids and chars from rice husk
chemicals, currently mainly flavourings. Renewable resins and slow by the lab-scale fix-bed induction heating system. As a result, over
release fertilisers are other potential applications, which have been 40% of pyrolysis oil could be achieved at temperature 500  C,
the subject of research [14]. At this stage, fast pyrolysis is a novel heating rate of 200  C/min, holding time of 2 min, condensation
and relatively untested technology. There are several pilot plants in temperature of 10  C and particle size of 0.5 mm. However, the
North America and Europe, but no consistent track record yet effect of nitrogen flow rate on the yield of pyrolysis oil was not seen.
outside of the manufacture of flavourings. The chemical characterisation by elemental, calorific, spectroscopic
Numerous researches have investigated the study on fast and chromatographic studies showed that the pyrolysis oils con-
pyrolysis of different types of biomass in different reactor systems. tained considerable amounts of carbonyl groups and oxygen
Onay and Kockar [15] studied the fast pyrolysis of rapeseed to content, resulting in low pH and low heating values.
determine the effect of pyrolysis temperature, heating rate, particle The fast pyrolysis of three agricultural wastes such as corncob,
straw and oreganum stalks was investigated by Yanik et al. [17] at
a temperature of 500  C in a fluidised bed reactor. The pyrolysis
Table 1 liquids produced were in two separate phases; aqueous phase and
Typical product stream distribution in oil palm mills [6]. oil phase. Oil yields varied between 35 and 41% depending on
biomass type, whereas the yields of aqueous phase were almost
Wet FFB basis Dry FFB basis
similar, around 6%, for all feedstock. The gas products obtained with
(tonnes per hectare) % FFB (tonnes per hectare) % FFB a yield around 30e40% were composed mostly of carbon oxides. In
FFB 20.08 100 10.6 100 general the pyrolysis gas can be burned to provide process heat
Palm oil 4.42 22.0 4.42 41.7
even though the higher heating value of the gas in their study was
Palm kernel 1.20 6.0 1.20 11.4
EFB 4.42 22.0 1.55 14.6 quite low.
POME 13.45 67.0 0.67 6.3 Heo et al. [18] carried out the fast pyrolysis experiment of waste
Shell 1.10 5.5 1.10 10.4 furniture in a fluidised bed in order to evaluate the technical
Fibre 2.71 13.5 1.63 15.4 feasibility of applying this technology to waste furniture. They
Total 27.3 136.0 10.6 99.7
investigated the effect of reaction temperature, particle size, flow
2354 F. Sulaiman, N. Abdullah / Energy 36 (2011) 2352e2359
rate, feeding rate, and fluidising medium on product yields. They
found that the optimal reaction temperature for production of bio-
oil from waste furniture sawdust was 450  C with a particle size of
0.77 mm. A higher gas flow and higher feeding rates were found to
be more favourable for the production of bio-oil due to the reduced
vapour residence times. The use of the noncondensable product gas
as fluidising medium had maximised the production of bio-oil at
about 65 wt.%.
Pattiya [19] studied the fast pyrolysis of cassava stalk and cas-
sava rhizome using a bench scale continuous fluidised bed reactor.
The aims of his work were to investigate the yields and properties
of pyrolysis products produced from both feedstock and to identify
the optimum pyrolysis temperature for obtaining the highest bio-
oil yields. He found that at the pyrolysis temperatures in the range
of 475e510  C, the maximum yields of the bio-oils derived from the
stalk and rhizome were 62 wt.% and 65 wt.% on dry basis, respec-
tively. He also found that the bio-oil derived from cassava rhizome
showed better quality than that derived from cassava stalk as the
former had lower oxygen content, higher heating value and better
storage stability.
The slow and fast pyrolysis of cherry seeds and cherry seeds
shells at different pyrolysis temperature, using a fix-bed and flui-
dised bed reactor, respectively were investigated [20]. The effects of
reactor type and temperature on the yields and composition of
products were investigated. The maximum bio-oil yield was about
44 wt.% at pyrolysis temperature of 500  C in the case of fast
pyrolysis for both feedstock, whereas the bio-oil yields were of 21
and 15 wt.% obtained at 500  C from slow pyrolysis of cherry seeds
and cherry seeds shells, respectively. They also found that bio-oils
derived from slow pyrolysis of both feedstock can be used as fuel for
combustion systems in industry and the bio-oil produced from fast
pyrolysis can be evaluated as a chemical feedstock.
Fast pyrolysis of biomass has to date received very limited
attention by researchers in Malaysia. Normally, fibre and shells are
burnt in the palm oil processing plants to generate fuel to produce
power for running the mill (self sufficient) [21,22]. So far, research
involving fast pyrolysis has been carried out by Universiti Teknologi
Malaysia on oil palm shells [23]. The palm shells were pyrolysed in
an externally heated fluidised bed pyrolysis reactor at a tempera-
ture between 400e600  C. They studied the effects of reactor
temperature, particle size and fluidisation gas flow rate on product
yields. The maximum liquid product was about 58 wt.% at reactor
temperature of 500  C with particle size of 212e425 mm. The
percentage mass of char product yield was decreasing with
increasing reactor temperature and the liquid oil produced on
pyrolysis was single liquid phase with a significant aqueous
content. One of the authors of this paper also studied on the fast
pyrolysis of EFB [24] using a 150 g/h fluidised bed bench scale fast
pyrolysis unit. The results confirmed the shape of the yield curve for
EFB and indicated the significant difference when comparing the
literature values for yields with the results obtained in her study
along with the systems being used. Of special significance for the
work here reported is that the first commercial bio-oil plant by
Genting Bio-oil has already started production in Malaysia [25].
The present work was carried out on a fluidised bed reactor with
a nominal capacity of 150 g/h, with the objective of determining the
important conditions and key variables which are required to
maximise the liquid yield and its quality.
2. Feedstock and method
2.1. Feedstock preparation
The EFB used in the experiments was supplied by MPOB
(Malaysian Palm Oil Board). Samples received were relatively dry,
less than 10 mf wt.% moisture, and were in the form of whole
bunches. The samples were presumed dried in the oven to prevent
growth of fungus or microorganism before packed and sent as it
took many days to reach its destination. Particle size reduction was
required before carrying out the fast pyrolysis of the EFB. The fruit
bunches were first manually chopped into smaller pieces and then
shredded. After that, a Fritsch grinder with a screen size of 500 mm
was used in order to further reduce the feedstock size to less than
500 mm. The samples were tested for the content of cellulose,
hemicellulose and lignin using the hydrolysis method. The samples
were then tested using the combustion analysis method for carbon,
hydrogen, nitrogen and sulphur. The proximate analysis was used
to determine the moisture content, volatiles matter and fixed
carbon in the EFB. The HHV (higher heating value) of the EFB was
determined using a bomb calorimeter, Series 1341 Plain Oxygen
Jacket Calorimeters. TGA (Thermogravimetric analysis) was carried
out on the feedstock of size 250e355 mm in order to evaluate the
qualitative composition of the feedstock, in particular with regards
to hemicellulose, cellulose, lignin and their thermal degradation
behaviour. Each TGA was performed with a flow rate of under
100 ml/min nitrogen with a heating rate of 10  C/min. These
analyses were carried out with a computerised PerkineElmer Pyris
1 thermogravimetric analyser.
2.2. Experimental procedure and plan
The reactor is the heart of a fast pyrolysis process [26]. The flui-
dised bed reactor has been selected for this study as it is relatively
easy to construct and operate and often present good results [12].
This type of reactor also has been popularly used by other researchers
in similar work on fast pyrolysis [17e20,23]. In this work, a fluidised
bed bench scale fast pyrolysis unit operating at atmospheric pressure
was employed for all runs. Fig. 2 shows a schematic diagram of this
unit, which consists of the feeder, reactor and product collection
system. The reactor is a stainless steel (type 316) cylinder with
a length of 260 mm and a diameter of 40 mm. The heating medium in
the reactor is inert sand of size between 355 and 500 mm. The sand
fills the reactor to a depth of approximately 8 cm and expands during
fluidisation to 12 cm. The fluidising gas is nitrogen, which is pre-
heated prior to entering the base of the reactor.
The char is carried out of the reactor body by the fluidising gas
flow known as ‘blow-through’ mode [27]. The char is then sepa-
rated from the product stream in a cyclone. The condensable
vapours are collected in the liquid products collection system,
which consists of two cooled condensers, an electrostatic precipi-
tator and a cotton wool filter. The incondensable gases leave the
system through a gas meter and are then sampled by GC (gas
chromatography) to assess the quantity and type of gas produced.
The distribution of feed particle size after grinding is given in
Table 2. The ash content of each size fraction was determined using
the NREL (National Renewable Energy Laboratory) Standard
Analytical Method LAP005, and the mass average of the size frac-
tions of 5.39% compares well, within the accuracy of the
measurements, with the original sample sent by MPOB, which had
an ash content of 5.36%.
To investigate the effect of temperature, fast pyrolysis experi-
ments were carried out at a vapour residence time of 1.02e1.05 s on
feedstock of size 250e355 mm over the temperature range of
400e600  C in 25  C increments.
The impact of varying vapour residence time in the range of
0.79e1.32 s by changing the nitrogen flow rate was investigated in
six experiments employing a fluidised bed temperature of 500  C
and a feedstock size range of 300e355 mm.
The combined effect of ash content and particle size was
assessed through a further four experiments considering the
 F. Sulaiman, N. Abdullah / Energy 36 (2011) 2352e2359 2355

Electric motor (stirrer)

Vent

Gas
Electrostatic Condenser 2 Analysis
Feeder Precipitator (Dry ice)
Nitrogen
cooling
water in

Cotton Wool Filter

Condenser 1

Cyclone

Oil pot 1 Oil pot 2

Charpot
Gas meter

Fluidised Bed Reactor

Products Collection System

Furnace

Fig. 2. Diagram of the 150 g/h fluidised bed pyrolysis system.

varying size fractions of less than 150 mm, 150e250 mm, run. The samples were analysed for their volumetric content of the
250e300 mm and 355e500 mm. major pyrolysis gases, which were carbon monoxide, carbon
dioxide, hydrogen, methane, ethane, ethylene and propane. It was
2.3. Products characterisation assumed that the remainder of the pyrolysis gas was nitrogen. From
this analysis, the volume of the gas constituents was known and
A Metrohm 758 KFD Titrino instrument that is accurate to their weight can be calculated using their densities.
0.01 mf wt.% was used to measure the water content of each of the
pyrolysis liquid samples. A filtration method was used to define the 3. Results and discussion
char content in pyrolysis liquids. In order to enable the pyrolysis
liquids to pass through the filter they were diluted with either 3.1. Feedstock preparation
methanol, ethanol or acetone.
The pyrolysis liquid was analysed using FTIR (Fourier Transform Key properties of EFB measured from this research are given in
Infra-Red) spectroscopy to obtain a qualitative impression of the Table 3. The samples were tested using the hydrolysis method for
basic functional groups present in the oil. The system used was cellulose, hemicelluloses and lignin; and it was found that the
a PerkineElmer Spectrum RX I. Analysis of FTIR spectra at wave measured values were 59.7 mf wt.%, 22.1 mf wt.% and 18.1 mf wt.%,
numbers from 4000 cm1 to 500 cm1 of pyrolysis liquids provides respectively. For the proximate analysis, the high ash and potas-
a quick and simple qualitative technique by using the standard sium values are noteworthy, as it is well known that ash, and in
IR-spectra to identify the functional group of the components of the
derived pyrolysis liquids. A small amount of the pyrolysis liquids was Table 3
mounted on a potassium bromide disc that had been previously Properties of EFB (mf wt.%).
scanned as a background.
Component/Property Measured Method
A Schlumberger Remus3 G1.6 total gas meter was used to
Component
measure the total volumetric throughput (processing force) of the Cellulose 59.7 Hydrolysis analysis
fluidised bed reactor system in cubic metres to three decimal places Hemicellulose 22.1
with an accuracy of 2.0% of the total hourly flow rate. The gas Lignin 18.1
samples were analysed in the gas chromatograph (CP-4900 Micro Extractives 0.1
Elemental analysis
Gas Chromatograph) every 5e10 min throughout the course of the
Carbon 49.07 Combustion analysis
Hydrogen 6.48
Table 2 Nitrogen 0.7
Particle size distribution of EFB. Sulphur <0.10
Oxygen 38.29 By difference
Feed particle size Mass fraction Average ash K 2.00 Spectrometry
[mm] [mf wt%] Proximate analysis
Less than 250 22 7.44 Moisture 7.95 ASTM E871
250e355 30 5.29 Volatiles 83.86 ASTM E872
355e500 42 4.82 Ash 5.36 NREL LAP005
More than 500 6 4.72 Fixed carbon 10.78 By difference
Mass average e 5.39 HHV [MJ/kg] 19.35 Bomb calorimeter

Note: mf wt.% e moisture free weight percentage or weight percentage dry basis. Note: mf wt.% e moisture free weight percentage or weight percentage dry basis.
2356 F. Sulaiman, N. Abdullah / Energy 36 (2011) 2352e2359
particular potassium, lead to reduced liquid yields in fast pyrolysis
[13]. The volatiles, fixed carbon, moisture content and ash content
of EFB were 83.86 mf wt.%, 10.78 mf wt.%, 7.95 mf wt.% and
5.36 mf wt.%, respectively. From the elemental analysis, it was
found that the EFB contained 49.07 mf wt.% of Carbon, 6.48 mf wt.%
of Hydrogen, 38.29 mf wt.% of Oxygen, 0.7 mf wt.% of Nitrogen and
less than 0.1 mf wt.% of Sulphur. These analyses indicated that EFB
is environment friendly, with a trace content of nitrogen and
sulphur. The carbon and hydrogen content are comparable to
woody biomass, as is the measured heating value. The lowest HHV
in the literature [28] may be due to confusion between values
quoted on a dry basis as opposed to a wet basis, a problem apparent
elsewhere in the literature, for example [6] e a value of 10 MJ/kg is
quoted for dry oil palm matter, which is clearly too low for a ligno-
cellulosic biomass on a dry basis e or [7] e values for wet FFB are
used for dry FFB.
The thermal degradation behaviour of EFB is displayed in Fig. 3
using TG (thermogravimetry) and DTG (differential thermog-
ravimetry) curves. From 100 to 220  C, as is also suggested by
Ref. [29], it may show mainly weight loss through evaporation of
extractives, which are present in minor quantities in EFB [30]. There
is a single peak for cellulose and hemicellulose in the DTG curve
with the maximum rate of weight loss occurring at 354  C. This is in
good agreement with other studies for high ash, high potassium
ligno-cellulosic feedstocks, for example see Refs. [31,32], which
also find a single peak at a lower temperature than for low ash
feedstocks. This is argued to be due to the catalytic effect of the ash.
Only two studies investigating EFB by TGA [33,34] could be
identified in the literature. Their DTG curve also shows a single
peak, though the peak temperature is even lower at approximately
300  C. They also analysed two other oil palm wastes, namely fibre
and shell, and found separate peaks for hemicelluloses, just below
300  C, and cellulose, just above 300  C. They employed the same
heating rate of 10  C/min as for the work here reported. It is
possible that their thermocouple was not properly calibrated to
measure the actual sample temperature, as the peak temperatures
they found are consistently lower than for other works available in
the literature. Another feature of their analysis bears mentioning,
namely the use of a 5 min holding time at 150  C. Because the
authors plot the weight loss rate per degree Celsius, the small peak
obtained by them at 150  C may be an artefact. On the other hand, it
may be hiding a small, but real, extractives peak that would appear
in the analysis, if it was performed as in the work here reported.
3.2. Experimental procedure and plan
Feeding test for a 150 g/h reactor was carried out and it was found
that only particles of a size less than 500 mm would be suitable. It is
desirable to have a particle size distribution as narrow as possible;
Fig. 3. Thermogravimetric analysis of EFB.
therefore, feedstocks were sieved using standard test sieves of mesh
size 150 mm, 250 mm, 300 mm, 355 mm and 500 mm. Feedstock of six
narrow ranges was obtained: less than 150 mm, 150e250 mm,
250e300 mm, 300e355 mm and 355e500 mm. After extensive
feeding trials, it was found that only particles between 250 and
355 mm were easily fed. Both the size fractions below and above this
range frequently led to blockage of the available feeder. Further
details can be found in Ref. [24]. The results of the investigation on
the impact of reactor temperature, varying residence time through
changing the nitrogen flow rate and combined impact of ash content
and particle size on the product yields is presented as below.
3.2.1. Impact of reactor temperature
GC is an analytical technique which relies on the comparison of
gas concentrations. Thus for every gas analysed a standard gas, with
a known concentration and of similar concentration to that
expected in the pyrolysis system exit gas, has to be injected into the
column and the peak residence time and area noted. This residence
time corresponds to that particular gas under the specific condi-
tions for that gas chromatography system and column. Thus when
a gas sample was injected only the gases that have been previously
analysed and calibrated can be identified and quantified. By using
several standard gases the concentrations of all of the major
pyrolysis gases can be identified and quantified. The mass of
pyrolysis vapours produced can then be calculated from the total
volume measured by the gas meter.
The experimentally obtained product yields are shown in Figs. 4
and 5. The maximum liquid and organics yields were obtained at
450  C. As is typical of biomass feedstock, for example [35], gas
yields increase at higher temperatures, while char yields decrease.
The yield trends for carbon monoxide and carbon dioxide were
similar to those reported by Scott and Piskorz [36] for aspen-poplar,
a woody feedstock. They also showed carbon dioxide yields levelling
off over 550  C and a sharp rise in carbon monoxide yields. Their data
extended to 700  C and indicated that at temperatures above 600  C
carbon monoxide yields overtook carbon dioxide yields.
3.2.2. Impact of varying residence time through changing the
nitrogen flow rate
The yields resulting from varying the fluidising flow rate are
presented in Table 4. It is noted that the fluidising flow rate is given
as litres per minute measured at the prevailing room temperature.
The hot gas residence time is calculated from the volumetric gas
55
50 total liquids
P ro duct yields , w t.% dry b as is
45
40
organics
35
30 char
gas
25
20
water
15
10
400 450 500 550 600
Reactor bed temperature, °C
Fig. 4. Impact of temperature on pyrolysis yields.
 F. Sulaiman, N. Abdullah / Energy 36 (2011) 2352e2359 2357

25 75
Results from this work

Organics yield, mf wt.%

20 65 Results from the literature

carbon dioxide
Gas yield, mf wt.%

55
15

45
10

35
carbon monoxide
5
methane 25
0 5 10
0
1 2 3 4 5 6 7 8 9 Ash content, mf wt.%
Temperature, °C Fig. 6. Comparison of data for EFB with other biomass feedstock.

Fig. 5. Impact of temperature on individual gas yields.

Due to feeding difficulties, two of the experiments, for particles

flow rate at operating temperature and pressure and the empty hot
space volume, that is the volume of the reactor, cyclone, char pot
and pipe work up to the first condenser which is less than the
volume of the sand contained in the reactor. Consequently, halving
the flow rate does not exactly double the residence time.
It is apparent that there is a maximum liquids yield and
a minimum char yield at a residence time of 1.03 s. This is in
agreement with similar results obtained by Nurul Islam et al. [23] for
palm shell. For very high fluidising rates it is likely that some of the
biomass is blown out of the reactor before it can fully pyrolyse. While
the char pot is at the same temperature as the reactor, any vapours
released in there will have extensive contact with char, which is well
known to lead to increased char yields [37]. In addition, any tars
sticking to the char would contribute to the measured char yield. For
longer residence times secondary reactions will result in decom-
position of the volatile vapours [12]. This clearly shows the sensi-
tivity of yields to variations in fluidising flow and the need to
optimise this variable. As this work was performed first, all other
experiments were carried out at a constant fluidising flow.
3.2.3. Combined impact of ash content and particle size
The results obtained are plotted and compared with literature
data [12,35,38e41] for a variety of biomass feedstock in Fig. 6. The
low organics yields found in this work compare well with those for
other high ash content ligno-cellulosic materials, particularly
considering the high potassium content of EFB. In an earlier full
paper that had been presented elsewhere [42] by the authors of this
paper, the fast pyrolysis of washed EFB was considered, which
obtained results that was similar to that of woody feedstocks, when
the alkali content had been sufficiently reduced.
sized <150 mm and 150e250 mm, only had a closure of 90%, while
all other experiments had closures above 95%. The low organic yield
obtained for the highest ash content for the size range of <150 mm,
is nevertheless not believed to be an artefact of the low closure as
all other yields were higher than those obtained for the size range
of 300e355 mm, while the organic yield was more than ten
percentage points lower.
It should also be said that ash content is not the only variable of
importance that is impacted by the sieving into size ranges. Particle
size itself may also have an effect on pyrolysis yields, which for
particles this small would, however, generally be expected to be
minor [35,43]. It is also possible that the cellulose to lignin ratio of
the size fractions differs.
3.3. Physical and chemical properties of liquid product
The pyrolysis liquids produced separated into two phases;
a phase predominated by tarry organic compounds and an aqueous
phase. The relative shares of the total liquid product yield of the
two phases are approximately 60% for the former and 40% for the
latter. A comparison of key properties for the two phases with those
of wood derived bio-oil, light fuel oil and heavy fuel oil is given in
Table 5, which also contains the ultimate analysis of the char
product. The value for sulphur was not determined, as there is very
little sulphur in the EFB itself. Due to its high water content, the
higher heating value of the aqueous phase was not measured.
The viscosity of the aqueous phase is close to that of water, while
the organics phase hardly flows at all and, at room temperature,
clearly has a viscosity above 10,000 cP, the limit for the measuring
equipment available to the authors of this research.

Table 4
Yield impact of varying fluidising flow.

Run no Vapour residence Ratio of fluidising to minimum Fluidisation gas flow Product yields
time (s) fluidising velocity rate (l/min) (mf wt.%)

Liquid Char Gases

1 0.79 4.3 7.0 50.58 27.24 17.90
2 0.96 3.7 6.0 51.50 26.45 17.71
3 1.03 3.0 5.0 55.14 23.93 18.57
4 1.16 2.7 4.5 50.16 25.92 19.06
5 1.23 2.4 4.0 47.77 27.49 22.37
6 1.32 2.1 3.5 45.32 27.60 25.06

Note: mf wt.% e moisture free weight percentage or weight percentage dry basis.
2358 F. Sulaiman, N. Abdullah / Energy 36 (2011) 2352e2359

Table 5 Thermochemical upgrading is another possibility, either via

Characteristics of pyrolysis oil compared to petroleum fuel [13]. gasification and FischereTropsch, where it may be advantageous to
EFB Wood derived Light Heavy gasify a bio-oil char slurry rather than the biomass itself [46], or via
bio-oil fuel oil fuel oil catalytic steam reforming of the aqueous phase to obtain the
Organics Aqueous Char
phase phase hydrogen for hydrogenation of the organics phase [47].
C 69.35 13.83 71.43 32e48 86.0 85.6 The organic phase may also be used directly in engines, turbines
H 9.61 11.47 1.80 7e8.5 13.6 10.3 and boilers, if it is first pre-heated to reduce its viscosity, though its
N 0.74 0.14 0.63 <0.4 0.2 0.6 thermal instability might limit the temperature it can be brought
O 20.02 74.56 8.72 44e60 0 0.6
up to. The aqueous phase could potentially be co-fired to reduce
S e e e <0.05 <0.18 2.5
Moisture content 7.9 64.01 e 20e30 0.025 0.1
thermal NOx and enable efficient burning of its dissolved dry
HHV (MJ/kg) 36.06 e e e e e matter. As mentioned in the introduction, it might also be possible
LHV (MJ/kg) e e e 13e18 40.3 40.7 to obtain useful chemicals, such as phenolic compounds for resin
making, as a commercial by-product.
Due to the low liquid yield, not all of the char and gas would be
The empirical formula of the organics in the organics phase is required for internal process heat. Some might be used to dry the
CH1.51O0.14. By comparison carbohydrates have an empirical formula very wet fresh EFB. Burning the char, which contains nearly all the
of CH2O, phenol of CHO0.17 and longer chain straight alkanes minerals, would allow recovery of the ash, which is useful as
approach an empirical formula of CH2. It is possible that the organics a fertiliser [6]. The gas is very high in carbon dioxide and has
phase contains a small amount of palm oil, as the organics in the a higher heating value of only approximately 4 MJ/kg. It might
organic phase have a significantly higher hydrogen to carbon ratio potentially be utilised for carbon sequestration enhanced oil
than is the case for wood derived slow pyrolysis tars [44]. The recovery schemes [48].
absorption frequency spectra representing the functional group As the fresh EFB is very wet, washing of the EFB prior to fast
composition of the pyrolysis liquid is shown in Table 6. The strong pyrolysis represents another interesting avenue to enhancing the
absorbance peaks of CeH vibrations of between 3000 and value of the fuel products obtained, as drying is required already
2800 cm1 and the CeH deformation vibrations of between 1500 and would therefore add little extra expense [24].
and 1450 cm1 indicate the presence of alkanes. The absorption peak
between 1750 and 1625 cm1 representing the C]O stretching 4. Conclusion
vibration is suggestive of the presence of carboxylic acids, ketones
and aldehydes. The absorbance peaks between 1675 and 1600 cm1 The fibre analysis for the EFB were found to be 59.7 mf wt.% for
representing C]C stretching vibrations. The peaks between 1300 cellulose, 22.1 mf wt.% for hemicelluloses and 18.1 mf wt.% lignin.
and 1000 cm1 are due to the presence of phenols and alcohols. The volatiles, fixed carbon, moisture content and ash content of EFB
Finally the absorption peaks between 900 and 650 cm1 indicate the were found to be 83.86 mf wt.%, 10.78 mf wt.%, 7.95 mf wt.% and
presence of single, polycyclic or substituted aromatic groups. 5.36 mf wt.%, respectively. It was also found that the EFB contained
49.07 mf wt.% of Carbon, 6.48 mf wt.% of Hydrogen, 38.29 mf wt.%
of Oxygen, 0.7 mf wt.% of Nitrogen and less than 0.1 mf wt.% of
3.4. Possible solutions and uses of liquid product
Sulphur.
The thermal degradation behaviour of EFB using TG and DTG
The phase separated liquid product would represent a chal-
curves showed a single peak for cellulose and hemicellulose in the
lenging fuel for boilers and engines, due to the high viscosity of the
DTG curve with the maximum rate of weight loss occurring at
organics phase and the high water content of the aqueous phase.
354  C which is in good agreement with other studies.
These could be overcome by upgrading. The addition of polar After oil palm empty fruit bunches have been pyrolysed in
solvents such as methanol or ethanol represents one of the easiest a bench scale fluidised bed system, the maximum yield for liquids
routes [13] and it was established by the authors of this research was determined to be around 55%, depending on size fraction ash
that the two phases both readily dissolve in methanol giving content, at reactor temperature of 450  C utilising a residence time
a homogeneous single phase product with a low viscosity. Further of 1.03 s. This showed the sensitivity of yields to variations in flu-
research would be required to establish how much methanol would idising flow and the need to optimise this variable.
have to be added at a minimum to obtain a single phase liquid. The The low organic yield obtained for the highest ash content for
addition of ethanol may also reduce corrosivity and allow removal the size range of less than 150 mm, is not believed to be due to the
of the water through low temperature vacuum distillation [45], low closure as all other yields were higher than those obtained for
which is otherwise difficult due to the thermal instability of the size range of 300e355 mm.
pyrolysis liquids. The phase separated pyrolysis liquid produced would present
a challenging fuel due to the high viscosity of the organics phase
Table 6 and the high water content of the aqueous phase which could be
FTIR functional group composition of pyrolysis liquid. overcome by upgrading or by addition of polar solvents. The
Frequency Group Class of compound empirical formula of the organics in the organics phase was found
range (cm1) to be CH1.51O0.14 for which it may contain a small amount of palm
3000e2800 CeH stretching Alkanes oil. Table 6 shows the range of frequencies in relation to the iden-
1750e1625 C]O stretching Aldehydes, carboxylic tification of its functional groups and compound.
acids, ketones,
1675e1600 C]C stretching Alkenes
Acknowledgements
1500e1450 CeH bending Alkanes
1300e1000 CeO stretching Alcohol
OeH bending Phenol The authors would like to thank Universiti Sains Malaysia for
900e650 Aromatic compounds fully funding the work described in this publication. Most of the
Note: The values given used the standard IR-spectra of hydrocarbons to identify the experimental work was performed at the University of Aston in
functional groups of the component of the derived pyrolysis liquid. Birmingham, while Nurhayati Abdullah was simultaneously a PhD
 F. Sulaiman, N. Abdullah / Energy 36 (2011) 2352e2359
student of the University of Aston in Birmingham and a full time
employee of USM.
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