Sludge palm oil as a renewable raw material for biodiesel production

by two-step processes
Adeeb Hayyan
a
, Md. Zahangir Alam
a,
*
, Mohamed E.S. Mirghani
a
, Nassereldeen A. Kabbashi
a
,
Noor Irma Nazashida Mohd Hakimi
b
, Yosri Mohd Siran
b
, Shawaluddin Tahiruddin
b
a
Bioenvironmental Engineering Research Unit (BERU), Department of Biotechnology Engineering, Faculty of Engineering, International Islamic University Malaysia,
P.O. Box 10, Kuala Lumpur 50728, Malaysia
b
Processing and Engineering, R&D Center Downstream, Sime Darby Research Sdn Bhd, Lot 2664 Jalan Pulau Carey, 42960 Pulau Carey, Kuala Langat, Selangor, Malaysia
a r t i c l e i n f o
Article history:
Received 3 March 2010
Received in revised form 11 May 2010
Accepted 17 May 2010
Available online 11 June 2010
Keywords:
Biodiesel
Sludge palm oil
Free fatty acid
Toluene-4-sulfonic monohydrate acid
Transesterication
a b s t r a c t
In this study, biodiesel was produced from sludge palm oil (SPO) using tolune-4-sulfonic monohydrate
acid (PTSA) as an acid catalyst in different dosages in the presence of methanol to convert free fatty acid
(FFA) to fatty acid methyl ester (FAME), followed by a transesterication process using an alkaline cata-
lyst. In the rst step, acid catalyzed esterication reduced the high FFA content of SPO to less than 2%
with the different dosages of PTSA. The optimum conditions for pretreatment process by esterication
were 0.75% (w/w) dosage of PTSA to SPO, 10:1 M ratio, 60 C temperature, 60 min reaction time and
400 rpm stirrer speed. The highest yield of biodiesel after transesterication and purication processes
was 76.62% with 0.07% FFA and 96% ester content. The biodiesel produced was favorable as compared
to EN 14214 and ASTM 6751 standard. This study shows a potential exploitation of SPO as a new feed-
stock for the production of biodiesel.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
Biodiesel production from abundant bio-sources has drawn the
attention of the academic as well as the industrial community in
recent years (Hayyan et al., 2010). In many countries, biodiesel is
receiving an upsurge interest as an alternative and renewable en-
ergy due to diminishing petroleum reserves, increasing fuel prices
and rising environmental concerns. Biodiesel can be made from
renewable biological sources such as vegetable oils, animal fats,
etc. The main merits of using biodiesel as engine fuel are reducing
the reliance on petroleum fuel and reducing air pollutant emis-
sions from diesel engines (Ma and Hanna, 1999; Wang et al.,
2000; Durn et al., 2005; Demirbas, 2009). However, in spite of
the favorable impact, the economic aspect of biodiesel production
is still a barrier for its development, mainly due to the current
lower price of petroleum fuel (Antolin et al., 2002). Usually, edible
vegetable oils, such as palm oil, soybean, rapeseed, corn, sesame
and sunower, are the prevalent feedstocks for biodiesel produc-
tion. The high value of edible vegetable oils as a food product
makes production of biodiesel fuel very challenging as the cost of
raw materials accounts for 6070% of the total production cost of
biodiesel fuel (Krawczyk, 1996; Ma and Hanna, 1999). Therefore,
exploring ways to reduce the cost of raw material is the main inter-
est in recent biodiesel research.
Many attempts have been made to produce biodiesel from non-
edible plant oils such as mahua (Ghadge and Raheman, 2005),
tobacco (Veljkovic et al., 2006), rubber seed oil (Ramadhas et al.,
2005), waste oils such as waste cooking oils (Leung and Guo,
2006), waste tallow (Bhatti et al., 2008) and animal fats (Canakci
and van Gerpen, 2001) as cheap feedstocks for biodiesel produc-
tion. The sustainability of these feedstocks is a major drawback
to their potential for commercialization due to the limited quantity
of generation. Therefore, an abundant resource (feedstock) is
essential to be economically and commercially feasible for biodie-
sel production.
Malaysia, as one of the biggest palm oil producers and exporters
in the world, is producing large amounts of low-grade oil such as
sludge palm oil (SPO) from palm oil industries. The SPO is a by-
product of the milling process and its annual production reaches
41 million tonnes (Hayyan et al., 2008). The current applications
of the SPO are to use in the low-grade soap production and boiler
fuels. Some developing countries import for further renery to
making animal feed supplementary, non-food application, etc.
The use of SPO can lower the cost of biodiesel production signi-
cantly, which makes SPO a highly potential alternative feedstock
for biodiesel production. The SPO usually contains high amounts
of free fatty acid (FFA) that cannot be converted to biodiesel using
an alkaline catalyzed process. A number of researchers have
0960-8524/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.05.045
* Corresponding author. Tel.: +60 3 61964571; fax: +60 3 61964442.
E-mail addresses: zahangir@iium.edu.my, zahangir@yahoo.com (Md.Z. Alam).
Bioresource Technology 101 (2010) 78047811
Contents lists available at ScienceDirect
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j our nal homepage: www. el sevi er . com/ l ocat e/ bi or t ech
worked with feedstocks that have elevated FFA content and they
mentioned that the oil should not contain more than 1% FFA for
alkaline catalyzed transesterication reaction (Freedman et al.,
1984; Liu, 1994; Canakci and van Gerpen, 2003; Lu et al., 2009).
Due to high FFA content in SPO, the alkali catalyzed transesteri-
cation to produce biodiesel gives low biodiesel yield because FFA
reacts with alkali to form soap, resulting in serious emulsication
and separation problems (Canakci and van Gerpen, 2001; Demir-
bas, 2009). To resolve this problem, an alternative process using
an acid catalyst has been proposed and used as a pretreatment step
in different studies (Freedman and Pryde, 1982; Liu, 1994; Canakci
and van Gerpen, 2001; Naik et al., 2008). The most commonly pre-
ferred acid catalysts are sulfuric acid, hydrochloric acid, sulfonic
acid and organic sulfonic acid such as p-toluene sulfonic acid
(PTSA) (Ma and Hanna, 1999). The PTSA showed the highest cata-
lytic activity as compared to benzenesulfonic acid and sulfuric acid
(Guan et al., 2009). Ferric sulfate as solid acid has been used in
esterication of waste cooking oil, and results show high activity
and conversion of FFA to FAME compared to sulfuric acid (Wang
et al., 2006). The main drawback of using solid acid or heteroge-
neous acid is the high cost. Therefore, in order to produce high
quality biodiesel with low-cost and safer operating conditions,
PTSA was proposed in this study to treat the SPO by an esterica-
tion process followed by a transesterication process using potas-
sium hydroxide as an alkaline catalyst.
The objectives of this study were to investigate the potential of
SPO as a low-cost feedstock in biodiesel production; to study the
effect of dosage of PTSA as a strong organic monohydrate acid with
other reaction variables such as molar ratio, reaction time, temper-
ature and stirrer speed on esterication reaction; and to evaluate
the biodiesel quality to be produced after transesterication
reaction.
2. Methods
2.1. Raw materials and chemicals
The sludge palm oil (SPO) was collected from West Oil Mill, Car-
ey Island, Selangor, Malaysia and was stored at 4 C. Methyl alcohol
anhydrous 99.8% commercial grade was purchased from Mallinck-
rodt Chemicals, USA; laboratory grades of toluene-4-sulfonic
monohydrate acid (C
7
H
8
O
3
SH
2
O) 99%, potassium hydroxide
(KOH) 85% and magnesium sulfate (MgSO
4
) were purchased from
Merck Sdn Bhd, Malaysia.
2.2. Production of biodiesel from SPO by two-step catalyzed processes
The production of biodiesel from SPO was carried out by two-
step catalyzed processes i.e. esterication and transesterication
reactions followed by the separation and purication processes.
First the SPO was preheated because it usually exists in a semisolid
phase at room temperature (30 2 C). The SPO was melted in an
oven at 80 C and the preheated SPO was then transferred into
the reactor for pretreatment of SPO using PTSA (esterication),
followed by an alkaline catalyzed transesterication process. The
nal step was separation and purication of biodiesel obtained
from the two reactions. A complete ow diagram on the processes
for biodiesel production from SPO is shown in Fig. 1.
2.2.1. Pretreatment of SPO by esterication reaction using PTSA
The acid catalyst PTSA was added into the preheated SPO at
different dosages in the presence of methanol to reduce the free
fatty acid (FFA) of SPO by converting it into fatty acid methyl ester
(FAME) (Fig. 1). A batch esterication process was carried out
using single factor optimization to study the effect of PTSA in the
dosage range (0.2510% wt/wt), molar ratio of methanol to SPO
(6:120:1), reaction temperature (4080 C), reaction time (30
120 min) and stirrer speed (200800 rpm). The effects of those
parameters on FFA content, yield of treated SPO and FFA to FAME
conversion were measured to evaluate the esterication process.
2.2.2. Alkaline catalyzed transesterication reaction
The treated SPO by acid catalyzed esterication was considered
as the pre-treated material for transesterication process (Fig. 1).
The process conditions for transesterication reaction were
maintained to the molar ratio of methanol to SPO 10:1, reaction
temperature 60 C, reaction time 60 min, stirrer speed 400 rpm
and 1% wt/wt KOH. All experiments were performed in 1.5 L of
batch reactor with reux condenser and all parameters were con-
trolled by digital controller (Sartorius Stedim Biotech Malaysia Sdn
Bhd).
2.2.3. Separation and purication of biodiesel obtained from two-step
catalyzed processes
In order to remove excess methanol in the biodiesel, the wet
crude biodiesel was dried under vacuum with a rotary evaporator.
The product was allowed to cool and equilibrate which resulted in
separation into two layers in a separating funnel. After 24 h sepa-
ration time, the upper phase consisted of biodiesel, while the lower
layer contained the glycerol. Finally, the biodiesel was washed
Dosage
of PTSA
0.5%
0.75%
1.0%
1.5%
2.0%
Biodiesel by
EP at 0.5%
Biodiesel by
EP at 0.75%
Biodiesel by
EP at 1%
Biodiesel by
EP at 1.5%
Biodiesel by
EP at 2%
Purified
Biodiesel
Pre-esterification process (EP) Transesterification
process (TEP)
Separation and
Purification
Biodiesel by
TEP (0.5%)
Biodiesel by
TEP (0.75%)
Biodiesel by
TEP (1%)
Biodiesel by
TEP (1.5%)
Biodiesel by
TEP (2%)
Fig. 1. A complete ow diagram of the esterication, transesterication, purication processes for biodiesel production from sludge palm oil (SPO).
A. Hayyan et al. / Bioresource Technology 101 (2010) 78047811 7805
with hot water and dried in the oven. For further purication, mag-
nesium sulfate was used in order to absorb the residues of water
after washing. The puried biodiesel was analyzed with various
parameters to evaluate the quality of the biodiesel produced.
2.3. Analytical analysis
The fatty acid compositions of the SPO were determined using
GC/MS (Agilent Technologies 7890A gas chromatograph equipped
with 5975C mass spectrometer); the capillary column was DB-
wax 1227032 with a length of 30 m, lm thickness of 0.25 lm
and an internal diameter of 0.25 mm. Helium was used as carrier
gas with a ow rate of 1 ml/min, measured at 50 C; the run time
was 35 min. One microliter of neat sample was diluted in hexane
prior injection into GC. Ester content was analyzed using GC/FID
(Perkin Elmer Clarus 500), splitsplitless mode of injector, capillary
column-polyethylene glycol wax phase, isotherm oven at 250 C.
Monoacylglycerols, diacylglycerols, triacylglycerols, free and total
glycerol content were determined using GC/FID (Perkin Elmer Cla-
rus 500). An on-column injector, a high temperature column with
polysiloxy divynil benzene phase (DB-HT type), a mega bore type
column, and the temperature program of the oven up to 350 C set-
ting were used to detect trace compounds. Free fatty acid was
determined in this study according to American Oil Chemists Soci-
ety (AOCS) ofcial method Ca 5a-40 commercial fats and oils
(AOCS, 1997). Characteristics of SPO were determined according
to the Malaysian Palm Oil Board (MPOB) test methods (Ainie et
al., 1995).
Yield of treated SPO after esterication process was calculated
using Eq. (1). Product yield is dened as the weight percentage of
the nal product relative to SPO weight at the beginning of exper-
iment. Conversion was calculated using Eq. (2) which is dened as
the converted FFA (%) divided by the initial content of FFA (%). Cat-
alyst consumption was determined using Eq. (3). The catalyst con-
sumption (CC) is dened as the mass of catalyst consumed per
mass of synthesized product.
Yield
wt of product
wt of SPO
1
Conversion
Nso Ns
Nso
2
where conversion, conversion of FFA to FAME; Nso, FFA content at
the start of reaction (%); Ns = FFA content at the end of reaction (%).
CC
Mcat
Mp
3
where CC, catalyst consumption; Mcat, mass of catalyst used to give
the synthesized mass of product, biodiesel (mg); Mp, mass of syn-
thesized product, biodiesel (g).
3. Results and discussion
3.1. Characteristics of SPO
Table 1 illustrates the characteristics of SPO that were used in
this study. Based on saponication value, the average molecular
weight calculated was 823.9 and the FFA content of the SPO used
was 22.33%. The SPO is characterized by its moisture content (be-
low 2%), FFA (545% as palmitic acid), peroxide value (1.36
21.81 meq/kg), iodine value (4055.9), saponication value
(173.82197.9 mg KOH/g) and unsaponication matter (0.082
0.910%). It was found that the characteristics of SPO used in this
study are within the ranges of other feedstocks (Ainie et al., 1995).
Fatty acid compositions of SPO are very important in identify
the carbon chains and its properties. Table 2 shows fatty acid com-
position of SPO. The results showed that the highest fatty acids
were oleic, palmitic, linoleic and stearic acid. Saturated fatty acids
in SPO were 47.17 wt% while unsaturated fatty acids were
52.83 wt%. According to Canakci and van Gerpen (2001), higher
saturated fatty acids in oils give a higher cetane number and the
oil is less prone to oxidation. Due to its high percentage of satu-
rated fatty acids and free fatty acids, SPO exists in semisolid phase
or solid phase at room temperature (30 2 C). Hence SPO has
higher pour and cloud points as compared to normal crude palm
oil.
3.2. Acid catalyzed esterication process for biodiesel production
Esterication process was used in order to pretreat the SPO by
converting the high content of FFA to FAME using an acid catalyst.
The initial content of FFA of the SPO used in this study was 22.33%,
which would not be favorable for biodiesel production as the study
by Canakci and Van Gerpen (2001) indicated that transesterica-
tion reaction will not occur if the FFA content in oil is more than
3%. Therefore, the limit of FFA was set to a maximum of 2% for
all esterication experiments. The major factors affecting the ester-
ication process were dosages of PTSA, molar ratio of methanol to
SPO, reaction temperature, reaction time and stirrer speed.
3.2.1. Effect of PTSA dosage
To nd the FFA content in SPO at target level (<2% w/w) with
maximum conversion and yield of treated SPO, an optimum
amount of catalyst loading needed to be used. The dosage of PTSA
catalyst was varied in the range of 0.2510 wt%. The results
showed that the dosage of PTSA catalyst used in the esterication
process affected the conversion of FFA to FAME and the yield of
treated SPO, as well as the yield of the nal product (biodiesel).
Fig. 2 shows the effect of different dosages of PTSA on the FFA con-
tent of SPO. The FFA content decreased from 22.33% to less than 2%
in the ranges of 0.7510 wt%. However, based on the yield of
Table 1
Characteristics of sludge palm oil (SPO).
Parameters Test method Values
Free fatty acid, FFA (%) AOCS 1997 (Ca 5a-40) 22.33 0.77
Peroxide value (ml mol/kg) Ainie et al. (1995) 1.52 0.40
Moisture content (%) Ainie et al. (1995) 1.20 0.06
Iodine value, IV Ainie et al. (1995) 53.40 0.71
Impurities (%) Ainie et al. (1995) 0.05 0.007
Saponication value (mg KOH/g oil) Ainie et al. (1995) 190.00 1.41
Unsaponication matter (%) Ainie et al. (1995) 1.47 0.26
Phosphorus (mg/kg) Ainie et al. (1995) 11.10 0.11
Ash (%) Ainie et al. (1995) 0.015 0.001
Acid value (mg KOH/mg) Ainie et al. (1995) 48.88 1.70
DOBI (index) Ainie et al. (1995) 0.55 0.03
Table 2
Fatty acid compositions of sludge palm oil (SPO).
Fatty acids Structure Fatty acids (wt%)
Caproic acid C6:0 0.02 0.0
Caprylic acid C8:0 0.096 0.05
Capric acid C10:0 0.08 0.01
Lauric acid C12:0 1.2 0.95
Myristic acid C14:0 1.42 0.23
Palmitic acid C16:0 42.84 3.92
Palmitoleic C16:1 0.13 0.01
Stearic acid C18:0 4.21 0.25
Oleic acid C18:1 39.58 1.57
Linoleic acid C18:2 9.92 1.39
Arachidic acid C20:0 0.38 0.01
Alpha-linolenic acid C18:3 0.12 0.02
7806 A. Hayyan et al. / Bioresource Technology 101 (2010) 78047811
treated SPO, 0.75 wt% of PTSA gave the FFA content of 2%, the yield
with 96% of treated SPO, and conversion of FFA to FAME was 90.9%.
At lower PTSA dosage (0.250.5%), the residual FFA content is high-
er (46%) than the limit of 2% which would not be favorable to the
conversion of pre-treated SPO into biodiesel. The excessive dosage
of PTSA did not show any improvement of biodiesel yield and con-
version of FFA, as the reaction might take place at equilibrium. In
addition, the low strength of the catalyst might not be sufcient
to provide enough catalytic activity to convert triacylglycerols to
methyl ester.
It was reported that using 6.4 10
5
mol of PTSA as acid cata-
lyst can decrease the FFA content in soybean oil from 20.5% to 1.1%
and the yield obtained after reaction obtained was only 48% with
the reaction conditions of 12:1 M ratio, 180 C reaction tempera-
ture, and 60 min reaction time (Di Serio et al., 2008). Guan et al.
(2009) claimed that PTSA has a higher catalyst activity than other
acid catalysts such as benzenesulfonic acid and sulfuric acid, where
the obtained yield was 97.1% using 4 wt% of PTSA in the presence
of dimethyl ether. In both studies, the consumption of PTSA and
other reagents were high to obtain an acceptable yield as com-
pared to the present study.
The economic feasibility of using PTSA has been calculated in
order to minimize the production cost. Catalyst consumption
(CC) is a factor which plays an important and essential role in
the overall production cost of the biodiesel. The results of CC with
dosage of catalyst and yield are shown in Table 3. The ndings
showed that the high yield was achieved with a proportionally in-
crease of catalyst dosage and CC at 0.75% and 7.81 mg/g, respec-
tively. After that, the yield was found to slightly increase with
maximum catalyst dosage (10%) and CC (110.1 mg/g), which indi-
cates a higher production cost of biodiesel. It was found that
7.8 mg of PTSA is required to produce 1 gm of treated SPO at
0.75 wt% of PTSA, which consider a low amount of catalyst to give
an acceptable yield of treated SPO and decrease the cost of the pre-
treatment process.
3.2.2. Effect of molar ratio
Molar ratio is one of the important factors affecting the conver-
sion of FFA to FAME, as well as the overall production cost of bio-
diesel. The esterication process needs more methanol than
transesterication; however, in practice, the molar ratio should
be higher than that of the stoichiometric ratio (3:1) or (1:1) in or-
der to drive the reaction towards completion (Ramadhas et al.,
2005). In this study, the molar ratio of methanol to SPO was varied
from 6:1 to 20:1. Fig. 3 shows the effect of the molar ratio on the
reduction of the FFA content in SPO, yield of treated SPO and con-
version of FFA to FAME. The yield of treated SPO slightly increased
when the molar ratio increased from 6:1 to 10:1, and no signicant
change was observed with a higher molar ratio. An excess of meth-
anol is used in order to obtain a higher yield but too large an
amount of methanol would not be able to contribute to the reac-
tion process due to the mass transfer limitation. On the other hand,
a minimum of 10:1 M ratio was required to reduce the FFA content
of SPO from 22.33% to 2%, which is the limit of FFA for transesteri-
cation reaction in this study. With an insufcient amount of
methanol in the reaction, the reaction process tends to be slower,
thus decreasing the amount of conversion. Therefore, 10:1 was
considered for the optimum ratio of methanol to SPO.
Di Serio et al. (2008) have used 12:1 M ratio to decrease the FFA
content in soybean oil from 20.5% to 1.1% using PTSA as acid cata-
lyst. Another study by Chongkhong et al. (2007) showed an 8:1 M
ratio of methanol to palm fatty acid distillate with 1.8 wt% of sul-
furic acid at 60 C and a retention time of 60 min. Veljkovic et al.
(2006) found that the FFA content of tobacco seed oil was reduced
from 17 wt% to less than 2 wt% using a molar ratio of 18:1 of meth-
anol to oil.
3.2.3. Effect of reaction temperature
In this study reaction temperature was varied from 40 to 80 C.
Fig. 4 presents the effect of reaction temperature on the FFA con-
tent in SPO, yield of treated SPO and conversion of FFA to FAME.
The results showed that the targeted FFA with high yield was ob-
served at the reaction temperature of 60 C. High temperatures
could affect the reaction by increasing the kinetic energy during
the process. Increased temperature gives energy to the molecules
to move faster; therefore, it is easier to break the carbon bond in
the glycerides with the help of alcohol and a catalyst during the
reaction process. As temperature increases the kinetic energy in
the reaction process also increases and thus shortens the reaction
time. The temperatures of 40 and 50 C are considered as low tem-
peratures and when a low reaction temperature was applied, the
0
4
8
12
16
20
24
0 2 4 6 8 10
Dosage of PTSA, wt%
F
F
A
%
0
20
40
60
80
100
120
Y
i
e
l
d
%

&

C
o
n
v
e
r
s
i
o
n
%
FFA%
Limits of FFA%
Yield% of treated SPO
Conv. of FFA to FAME
Fig. 2. Effect of dosages of PTSA on reduction of FFA content, yield of treated SPO
and conversion of FFA to FAME.
Table 3
Effect of dosages of PTSA on yield of treated SPO and catalyst consumption.
Dosage of catalyst (wt%) Yield (%) Catalyst consumption (mg/gm)
0 0 0
0.25 75.9 3.3
0.5 93.3 5.36
0.75 96 7.81
1 96.7 10.34
1.5 94 19.16
2 93 22.60
4 96 40.54
6 94.4 63.55
8 95 91.57
10 94.6 110.08
0
4
8
12
16
20
24
0 2 4 6 8 10 12 14 16 18 20 22
Molar Ratio
F
F
A
%
0
20
40
60
80
100
120
Y
i
e
l
d
%

&

C
o
n
v
e
r
s
i
o
n
%
FFA%
Limits of FFA%
Yield% of treated SPO
Conv.% of FFA to FAME
Fig. 3. Effect of molar ratio on reduction of FFA content, yield of treated SPO and
conversion of FFA to FAME.
A. Hayyan et al. / Bioresource Technology 101 (2010) 78047811 7807
reaction did not fully completed. Hence, the results at 40 and 50 C,
low yield of treated SPO, low conversion of FFA to FAME and high
FFA content were obtained. On the other hand, results at 70 and
80 C, a low yield of treated SPO was obtained because at higher
temperatures more methanol evaporated and the reaction lost
some of its methanol during reaction. At 60 C, a high yield of trea-
ted SPO (96%) was obtained, the FFA was reduced to 2%, and a
90.93% conversion of FFA to FAME was achieved.
The ndings obtained are supported by Leung and Guo (2006).
They found that temperatures higher than 50 C had a negative im-
pact on the product yield for neat oil, but had a positive effect for
waste oil with higher viscosities. Guan et al. (2009) found that the
yield of FAME reached 97.1% when the reaction was done at 80 C,
using 4 wt% of PTSA in the presence of dimethyl ether with 2-h
reaction time.
3.2.4. Effect of reaction time
In order to complete the esterication reaction, sufcient con-
tact time must be provided. Fig. 5 shows the effect of reaction time
on the reduction of FFA content, yield of treated SPO and conver-
sion of FFA to FAME. It was observed that the yield of treated
SPO increased with an increase in reaction time as well as the con-
version of FFA to FAME. After 30 min of reaction, the FFA content
was 5.4%, which is higher than the limits of FFA for transesterica-
tion reaction, whereas FFA content at 60 min up to 120 min was
less than 2% FFA. Therefore, in order to save the energy and to de-
crease the cost of the pretreatment process, 60 min of reaction
time is sufcient for the completion of esterication reaction,
which gave 96% yield of treated SPO, 90.93% conversion of FFA to
FAME and the FFA content decreased from 22.33% to 2%.
A study by Veljkovic et al. (2006) showed that esterication re-
duced the FFA level from about 35% to less than 2% in 25 and
50 min, with a molar ratio of 18:1 and 13:1, respectively. In the
present study, FFA content was reduced from 22.33% to less than
2% in 60120 min and 10:1 M ratio. Di Serio et al. (2008) reported
that using 6.4 10
5
mol of PTSA as an acid catalyst can decrease
the FFA content in soybean oil from 20.5% to 1.1% and the yield ob-
tained after reaction obtained was only 48%. The reaction condition
was 12:1 M ratio, 180 C temperature, and 60 min reaction time.
While the optimum reaction time was 60 min with the PTSA dos-
age of 0.75% at reaction time, 60 C in order to obtain a high yield
of 96% which is double the results of the study by Di Serio et al.
(2008).
3.2.5. Effect of stirrer speed
In order to achieve effective mass transfer between the reagents
and SPO during the esterication process, continuous mixing and
sufcient reaction time have great consequence for a complete
reaction. An understanding of mixing effects on the kinetics of
the reaction process is a valuable tool in the process scale-up and
design. After adding the methanol and catalyst to the oil, stirring
for 510 min promotes a higher rate of conversion (Demirbas,
2009).
Mixing intensity (stirrer rate) was investigated in the range
from 200 to 800 rpm. Fig. 6 shows the effect of stirrer speed on
the reduction of FFA content, yield of treated SPO and conversion
of FFA to FAME. The results revealed that the stirrer rates of 200
and 400 rpm were sufcient for the completion of esterication
reaction and to decrease FFA content from 22.33% to 2%. However,
the yield for 400 rpm was slightly higher than that for 200 rpm.
Mixing signicantly affects the reaction rate; insufcient mixing
could lead to a very slow reaction rate, thus lowering the conver-
sion value. Therefore, 400 rpm stirrer speed was selected as the
optimum stirrer speed in the pretreatment process of SPO. How-
ever, too high a stirrer speed would negatively impact to the reac-
tion as well. The results showed that increasing the stirrer speed to
600 rpm, not only consumes more energy but also results in a low-
er yield than that of 400 rpm. The conversion and FFA content after
esterication, however, were the same as with 400 rpm. The stirrer
rate of 800 rpm was not recommended because the FFA content in-
creased above 2%, and both yields of treated SPO and conversion of
FFA to FAME decreased. It is believed that high mixing creates a
very unstable condition in which some of methanol evaporates
and there is a lack of sufcient contact with the SPO during the
reaction. In addition, high rates of revolution consume a lot of en-
ergy, which would not be economic.
0
4
8
12
16
20
24
0 20 40 60 80 100
Temperature,

C
F
F
A
%
0
20
40
60
80
100
120
Y
i
e
l
d
%

&

c
o
n
v
e
r
s
i
o
n
%
FFA% Limits of FFA%
Yield% of treated SPO Conv.% of FFA to FAME
Fig. 4. Effect of reaction temperature on reduction of FFA content, yield of treated
SPO and conversion of FFA to FAME.
0
4
8
12
16
20
24
0 20 40 60 80 100 120 140
Reaction Time, min
F
F
A
%
0
20
40
60
80
100
120
Y
i
e
l
d
%

&

C
o
n
v
e
r
s
i
o
n
%
FFA%
Limits of FFA%
Yield% of treated SPO
conv.% of FFA to FAME
Fig. 5. Effect of reaction time on reduction of FFA content, yield of treated SPO
treated SPO and conversion of FFA to FAME.
0
4
8
12
16
20
24
0 200 400 600 800 1000
Stirrer Speed, rpm
F
F
A
%
0
20
40
60
80
100
120
Y
i
e
l
d
%

&

C
o
n
v
e
r
s
i
o
n
%
FFA%
Limits of FFA%
Yield% of treated SPO
Conv.% of FFA to FAME
Fig. 6. Effect of stirrer speed on reduction of FFA content, yield of treated SPO and
conversion of FFA to FAME.
7808 A. Hayyan et al. / Bioresource Technology 101 (2010) 78047811
Pretreatment process using a stirrer rate of 400 rpm was uti-
lized by Yuan et al. (2008) in the pretreatment of waste rapeseed
oil with high FFA to produce biodiesel. Lifka and Ondruschka
(2004) have studied the PTSA as an acid catalyst and different
methods of mixing using a magnetic stirrer, ultrasound and ultra-
turrax. The study found that ultrasonic mixing was lowest in en-
ergy costs.
3.3. Alkaline catalyzed transesterication process
The rst phase of the study was to reduce the FFA of SPO by an
acid catalyzed esterication process. Different dosages of PTSA
(0.252%) were applied with other process conditions to evaluate
the FFA conversion at less than 2% from its initial content of
22.33% which is favorable to a further transesterication process.
In the second phase, pre-treated SPO after esterication is consid-
ered as the pre-treated material for the transesterication process
where triglycerides are converted to FAME using an alkaline cata-
lyst. All pre-treated SPO materials with the dosages of PTSA (0.5%,
0.75%, 1%, 1.5% and 2%) were further transesteried into biodiesel
using an alkaline catalyst under these conditions: molar ratio of
methanol to SPO 10:1, reaction temperature 60 C, reaction time
60 min, stirrer speed 400 rpm and 1% wt/wt KOH.
The biodiesel yield, catalyst consumption and properties of
puried biodiesel as well as glycerol content after alkaline cata-
lyzed transesterication (based on pre-treated SPO with different
PTSA dosages) are shown in Table 4. The results showed that each
pre-treated SPO by PTSA dosage was evaluated in the production of
biodiesel with its yield and properties. It was observed that a sig-
nicant effect of the dosage of PTSA in the esterication reaction
was found towards the biodiesel yield from the transesterication
process, but there was no signicant effect of PTSA dosages in the
yield of glycerol (Table 4). The pre-treated SPO with the PTSA dos-
age of 0.25 was not included in the transesteried biodiesel as the
reaction was not completed due to saponication (FFA is more
than 6%) and hence no product (biodiesel) was formed. When
0.5% of PTSA was used, the experiment was successful but the yield
was low because the FFA of treated SPO esteried with 0.5% of
PTSA was 4%. These results support that there is an acceptable limit
of FFA in SPO after it is treated using PTSA as an acid catalyst. It
would conrm that transesterication reaction with an alkaline
catalyst is not effective when the FFA of oil is more than 2% and
the dosage of acid catalyst during the esterication process was
insufcient.
The high yield of biodiesel was obtained from the pre-treated
SPO with 0.751.0% wt/wt of PTSA, but the yield was slightly high-
er at 0.75% of PTSA treated SPO (from rst phase) than at that of 1%.
However, the yield of biodiesel obtained using 1.5% and 2% of PTSA
was lower compared to the results using 0.5% and 0.75%. The rea-
sons might be of an excessive dose of PTSA (acid) in the reaction
mixture, which reacts with the alkaline catalyst in the form of
hydroxide and to form salt. This may cause a lower yield with
insufcient alkaline catalyst during the transesterication process.
In terms of catalyst consumption (CC), 0.75% PTSA dosage was
more economic than 1% PTSA dosage, as it is shown that CC for
0.75% PTSA dosage was 9.78 mg of PTSA, as compared to
13.19 mg of PTSA for 1% PTSA, to produce 1 gm of biodiesel.
To evaluate the puried biodiesel produced from different pre-
treated SPO by different dosages of PTSA, the properties of biodie-
sel fuel as compared to EN 14214 specications are also shown in
Table 4. It can be seen that the ester content of puried biodiesel at
0.75% of PTSA was 95% mol/mol with mono, di, and triacylglycerine
after the transesterication reaction, which meets the standard
specication. All of these results reported that two-step reaction
processes were completed at 0.75% of acid catalyst (PTSA). The re-
sults showed that monoacylglycerine, diacylglycerine, total glyc-
erol and acid value decreased simultaneously with an increase in
dosage of PTSA, whereas free glycerol remained constant for all
samples in different PTSA dosages. Triacylglycerine was high in
pretreated SPO which was treated by 0.5% of PTSA and constant
with 1%, 1.5% and 2% of PTSA, whereas it was less than 0.01% with
dosage 0.75% of PTSA.
It can be concluded that ester content was high for the pre-trea-
ted SPO samples with 0.75%, 1%, 1.5% and 2% of PTSA, and FFA con-
tent was less than 0.5% for all samples except for the dosage of 0.5%
PTSA. FFA content of puried biodiesel from all acid catalyzed
esteried SPO meets the standard specication for biodiesel fuel
(B100) blend stock for distillate fuels ASTM D6751-02 and EN
14214. Finally, dosage of acid catalyst during esterication process
has signicant effects on esterication reaction, transesterication
reaction, yield of biodiesel and its quality.
3.3.1. Characteristics of biodiesel from SPO after transesterication
with purication process
The properties of biodiesel fuel vary with their origins. Fatty
acids compositions of raw materials determine some of the proper-
ties of the biodiesel produced. It was found that biodiesel from SPO
Table 4
Yield, catalyst consumption and properties of puried biodiesel as well as glycerol content after transesterication reaction.
Parameters Test method Unit Specications (max) PTSA treated puried biodiesel
0.5% 0.75% 1% 1.5% 2%
Yield of biodiesel Eq. (1) % 63.71 76.62 75.80 54 45
Yield of glycerol Eq. (1) % 10.66 13.16 11.43 17 14.66
CC Eq. (3) mg/gm 7.84 9.78 13.19 27.77 44.44
Ester content EN14103 %(mol mol
1
) 96.5 81 95 90 89 96
Monoacylglycerol EN14105 %(mol mol
1
) 0.8 0.49 0.48 0.39 0.18 0.08
Diacylglycerols EN14105 %(mol mol
1
) 0.2 0.11 0.03 0.01 0.01 <0.01
Triacylglycerols EN14105 %(mol mol
1
) 0.2 2.92 <0.01 0.01 0.01 0.01
Free glycerol EN14105 %(mol mol
1
) 0.02 0.01 0.01 0.01 0.01 0.01
Total glycerol EN14105 %(mol mol
1
) 0.25 0.43 0.13 0.1 0.07 0.03
Acid value EN14104 mg KOH g
1
0.5 0.27 0.12 0.11 0.09 0.085
FFA AOCS 1997 % <1 0.59 0.26 0.24 0.19 0.18
Table 5
Fatty acid composition of biodiesel from sludge palm oil.
Fatty acids Structure wt%
Lauric acid methyl ester C12:0 0.08 0.001
Myristic acid methyl ester C14:0 1.08 0.23
Palmitic acid methyl ester C16:0 46.2 2.38
Stearic acid methyl ester C18:0 4.45 0.14
Oleic acid methyl ester C18:1 37.99 1.07
Linoleic acid methyl ester C18:2 9.85 0.05
Alpha-linolenic acid methyl ester C18:3 0.02 0.0
Arachidic acid methyl ester C20:0 0.33 0.002
A. Hayyan et al. / Bioresource Technology 101 (2010) 78047811 7809
contained 47.17 wt% of saturated fatty acids. These saturated fatty
acids give biodiesel fuel advantages in terms of a higher cetane
number and better oxidation stability; in contrast, saturated fatty
acids shows disadvantages such as the fuel having a higher cloud
point and pour point. The higher cetane number in biodiesel from
SPO increases the ignition quality and efciency of combustion and
decreases engine deposits results in the less smoke, lower exhaust
emissions and lower engine wear. Due to higher saturated fatty
acids in biodiesel from SPO, the oxidation stability provides long
age of using biodiesel fuel and nally improves fuel economy.
However, higher saturated fatty acids in biodiesel from SPO having
the disadvantages with the higher cloud point and pour point if it
is used in cold weather. It is associated with some problems such
as not easily to start and transferring the fuel from tank to the
engine.
Fatty acids composition of biodiesel from SPO is presented in
Table 5. It was found that the fatty acids composition of SPO was
a little different with its ester due to esterication and transesteri-
cation reactions. Table 6 shows the biodiesel specications
according to EN 14214 and ASTM 6751 standards. The ndings
showed that the biodiesel produced under the optimum conditions
meets European standard and ASTM specications for biodiesel
fuel. After studying the specications of puried biodiesel from
SPO, it was determined that the ester content was 96% (mol/
mol), which is slightly lower than the 96.5% specied in EN stan-
dards. Kinematic viscosity at 40 C is 5.581 mm
2
/s), which was
slightly higher than the EN standard (5.0 mm
2
s
1
) and within
the ASTM standard (6.0 mm
2
/s). Other properties of puried bio-
diesel from SPO were met to the European and American standards
for biodiesel fuel. The cetane number of biodiesel from SPO was
high compared to petroleum diesel and biodiesel from different
sources of oils and fats due to a high percentage of saturated fatty
acids in biodiesel from SPO.
4. Conclusions
The results indicate that SPO would be an attractive alternative
feedstock for biodiesel production with the development of a pre-
treatment method using a PTSA catalyst. It was found that there
are signicant effects of PTSA dosage on the production of puried
biodiesel production. The optimum conditions for esterication
process were 0.75 wt% PTSA, 10:1 M ratio of methanol to SPO,
60 C of reaction temperature, 60 min reaction time and 400 rpm
stirrer speed. The highest yield of biodiesel obtained after transe-
sterication reaction was 76.62% with an ester content of
96% mol/mol. This study shows a positive route of large scale bio-
diesel production with the optimum esterication conditions
awaiting further research development.
Acknowledgements
The authors would like to thank the personnel of Processing &
Engineering of Sime Darby Research Sdn Bhd and Sime Darby Bio-
diesel Sdn Bhd for supplying sludge palm oil. The Department of
Biotechnology Engineering, International Islamic University
Malaysia (IIUM) is acknowledged for providing the facilities to
undertake this research.
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Water content 469 mg kg
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EN ISO 12937 500 mg kg
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max ASTM D 2709 0.050% (v/v) max
Methanol content 0.18 mol mol
1
EN 14110 0.20% (mol mol
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) max
K content 1 mg kg
1
max EN 14108 5.0 mg kg
1
max UOP 391 5.0 mg kg
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max
P content 7.8 mg kg
1
max EN 14107 10.0 mg kg
1
max ASTM D 4951 0.001% (w/w) max
Density (15 C) 877.9 kg m
3
EN ISO 3675 860900 kg m
3

Kinematic viscosity (40 C) 5.581 mm
2
s
1
EN ISO 3104 3.55.0 mm
2
s
1
ASTM D 445 1.96.0 mm
2
s
1
Flash point 183.6 C EN ISO 3679 120 C min ASTM D 93 130 C min
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Sulfated ash <0.005% (w/w) ISO 3987 0.02% (mol mol
1
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Total contamination 0.011 mg kg
1
EN 12662 24 mg kg
1
max
Acid value 0.065 mg KOH g
1
EN 14104 0.50 mg KOH g
1
max ASTM D 664 0.50 mg KOH g
1
max
Iodine value 51.3 g I2 100 g
1
EN 14111 120 g I2 100 g
1
max
Heating value 9572.464 (cal/g) ASTM D240
Cetane number 79 EN ISO 5165 51 min ASTM D 613 47 min
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