Renewable Energy 34 (2009) 10591063

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Continuous esterication for biodiesel production from palm fatty acid

distillate using economical process
S. Chongkhong*, C. Tongurai, P. Chetpattananondh
Department of Chemical Engineering, Faculty of Engineering, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand

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

Article history: An overow system for continuous esterication of palm fatty acid distillate (PFAD) using an economical
Received 4 January 2007 process was developed using a continuous stirred tank reactor (CSTR). Continuous production compared
Accepted 12 July 2008 to batch production at the same condition had higher product purity. The optimum condition for the
Available online 10 September 2008
esterication process was a 8.8:1:0.05 molar ratio of methanol to PFAD to sulfuric acid catalyst, 60 min of
residence time at 75  C under its own pressure. The free fatty acid (FFA) content in the PFAD was reduced
Keywords:
from 93 to less than 1.5%wt by optimum esterication. The esteried product had to be neutralized with
Biodiesel
10.24%wt of 3 M sodium hydroxide in water solution at a reaction temperature of 80  C for 20 min to
Palm fatty acid distillate (PFAD)
Continuous esterication reduce the residual FFA and glycerides. The components and properties of fatty acid methyl ester (FAME)
Economical process could meet the standard requirements for biodiesel fuel. Eventually the production costs were calculated
to disclose its commercialization.
2008 Elsevier Ltd. All rights reserved.

1. Introduction
Biodiesel is renewable clean bio-energy as it can be produced
from vegetable oils and has no sulfur content. The quality of bio-
diesel is similar to diesel fuel; thus it becomes a promising alter-
native to diesel fuel [1].
At present, the main drawback for the commercialization of
biodiesel is its higher cost than petroleum-based diesel. The high
cost of biodiesel is due to its being produced mostly from expensive
high-quality virgin oil with a low content of free fatty acid (FFA)
[2,3]. A way of reducing biodiesel cost is to use less expensive
feedstock containing high FFA, recycled or waste oils and by
products of the rening vegetable oils. With feedstock having high
FFA, biodiesel production is processed in two steps. The rst step is
to reduce the FFA content of the oil by esterication. The second
step is transesterication, which converts the triglyceride portion
of the oils to mono-alkyl ester and glycerol [47].
Esterication is an acid-catalyzed chemical reaction involving
FFA and alcohol which yields fatty acid alkyl ester and water (H2O).
Methanol is the most commonly used alcohol because of its low
cost and high reactivity as compared to longer-chain alcohols [2,8].
Biodiesel production in the presence of enzyme catalysts can ach-
ieve satisfactory ester yield under mild conditions. However, the
process is costly and needs longer reaction times and higher cata-
lyst concentrations. For example, the enzymatic production of
* Corresponding author. Tel.: 66 74287055; fax: 66 74212896.
E-mail address: daodang33@yahoo.com (S. Chongkhong).
biodiesel from cotton seed oil observed 97% yield after 24 h at 50  C
with a reaction mixture containing 32.5% t-butanol, 13.5% meth-
anol, 54% oil and 0.017 g enzyme/gram of oil using a one step xed
bed continuous reactor [9]. The favorable acid catalyst is sulfuric
acid (H2SO4) because of its low cost [10,11].
Conventional continuous production of biodiesel usually oper-
ates under high pressure and temperature. The supercritical
process requires not only high pressure and temperature but also
a high amount of alcohol. The optimum condition of continuous
biodiesel production using supercritical methanol with a tube
reactor is a 40:1 molar ratio of alcohol to vegetable oil, 25 min of
residence time, 35 MPa and 310  C [12].
Biodiesel is conventionally produced from feedstock having FFA
content less than 20 wt% [212]. In this work, palm fatty acid
distillate (PFAD), a by product from the production of consumable
palm oil, with an FFA content of 93 wt% was used as a feedstock for
biodiesel production. The study is focused on the economical
process: using low cost PFAD and mild operating conditions with
continuous overow production. The material balance of the
process and biodiesel quality testing are included.
2. Materials and methods
2.1. Chemical
PFAD was obtained from Chumporn Palm Oil Industry Public
Company Limited, Thailand. It is a light yellow solid at room
temperature. The fatty acid prole of PFAD is given in Table 1. The
FFA level of 93 wt% is much greater than the 1% limit for sufcient

0960-1481/$ see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.renene.2008.07.008
1060 S. Chongkhong et al. / Renewable Energy 34 (2009) 10591063

Table 1 Table 2
Fatty acid proles of PFAD Independent variables and levels of L9(34) for Taguchi method

Fatty acid Formula Structure %wt Experimental run no. Independent variable values
Saturated fatty acids T ( C) T (min) R (mole/mole) S (%wt)
Myristic C14H28O2 14:0 1.0
1 65 60 5.7:1 0.92
Palmitic C16H32O2 16:0 45.6
2 65 90 7.2:1 1.83
Stearic C18H36O2 18:0 3.8
3 65 120 8.8:1 2.75
Arachidic C20H40O2 20:0 0.3
4 70 60 7.2:1 1.83
Monounsaturated fatty acids 5 70 90 8.8:1 0.92
Palmitoleic C16H30O2 16:1 0.2 6 70 120 5.7:1 2.75
Oleic C18H34O2 18:1 33.3 7 75 60 8.8:1 1.83
Ecosenoic C20H38O2 20:1 0.2 8 75 90 5.7:1 2.75
Tetracosenoic C24H46O2 24:1 0.6 9 75 120 7.2:1 0.92

Polyunsaturated fatty acids

Linoleic C18H32O2 18:2 7.7 experiments. The batch experiments were conducted as described
Linolenic C18H30O2 18:3 0.3
below.

alkaline-catalyzed transesterication process. Consequently, ester-
ication was operated. All chemicals including methanol (99.5%),
sulfuric acid (98%), and sodium hydroxide (99%) are of commercial
grade.
2.2. Experimental design
Continuous production using an overow process was simply
carried out under mild conditions, low reaction temperatures (65,
70 and 75  C) that made the system pressure slightly higher than
the atmospheric pressure. This process requires an uncomplicated
apparatus which is easily constructed and low cost. The
experiments were designed by the Taguchi method [13]. With
a three-level-four-factor array, L9(34), nine experiments were
investigated as shown in Table 2. Molar ratio of methanol to PFAD
(R), reaction temperature (T), reaction time (t) and catalyst amount
(S) were selected as independent variables.
2.3. Batch experiments
To save time and expenses the optimum condition for the batch
experiment was used as the initial condition for continuous
2.3.1. Esterication
Batch esterication was carried out in a laboratory scale. A hot
plate with a magnetic stirrer was used for heating the mixture in
the screw-capped bottle. The bottle was kept in an oil bath to
maintain the temperature. The mixture was stirred at the same
speed (300 rpm) for all test runs. After the esterication reaction,
the product mixture was poured into a separating funnel and then
allowed to settle into two phases. The bottom FAME-layer was
separated and puried by the water washing process before being
analyzed for its composition by thin layer chromatography (TLC).
Three trial runs were carried out and the results presented are
average values.
2.3.2. Purication
The FAME product obtained from the optimum esterication
process still had about 1.4 wt% residual FFA, which needed
further purication. A neutralization process was used instead of
the distillation process. Neutralization was carried out using 3 M
of sodium hydroxide in water (NaOHH2O) solution. Then, 2%wt
salt (NaCl) was dissolved in the solution to remove soap forma-
tion and mixed with FAME. The mixture was heated to a reaction
temperature of 80  C and stirred at a speed of 350 rpm for 15
20 min. After that, the neutralized product was poured into the

Fig. 1. A schematic diagram of a continuous unit for biodiesel production from PFAD using an economical process.
 S. Chongkhong et al. / Renewable Energy 34 (2009) 10591063 1061

Table 3
Batch process yields of FAME from PFAD in comparison with continuous process
yields

Process Esterication Purication

% Yield % FAME % Yield % FAME

Batch 99 93.9 94.4 99.6
Continuous 97 97.3 94 99.7

tank before entering a 30 L separator. The esteried products

Fig. 2. FAME content obtained from a Taguchis experimental condition (Table 2) for
deciding the initial condition used in the continuous process.
were allowed to settle into two phases. The top phase, consisting
of un-reacted methanol together with water formed during the
reaction, was then overowed at the top of the 30 L separator.
The methanol phase was puried by distillation and then recy-
cled. The FAME phase underowed at the bottom pipe line of the
separator. The FAME phase was passed into the evaporator to
recover traces of methanol and further treated in the purication
unit.

separating funnel and then allowed to settle into two phases. The
soap phase that formed in the neutralization reaction was
removed. The FAME phase was washed with water at 6080  C,
allowed to settle and heated to evaporate residual water.
2.4. Continuous experiments
The continuous experiments contain two processes: (1) an
esterication process, which is carried out in a continuous stirred
tank reactor (CSTR) and (2) a purication process, where FAME was
puried to meet the standard requirements for biodiesel fuel. A
schematic diagram of the continuous experiments is shown in Fig. 1.
2.4.1. Esterication
On the basis of the results from Section 2.3.1, the reaction
operating parameters were set to a 8.8:1 molar ratio of methanol to
PFAD, a 0.05:1 molar ratio of H2SO4 to PFAD, a reaction temperature
of 75  C under its own pressure (about 133 kPa) for residence time
of 60 min.
Fresh methanol (2.3 kg/h), recycled methanol (6.5 kg/h) and
H2SO4 (0.16 kg/h) were mixed rst and pumped into a 22.4 L
CSTR. PFAD was fed into the CSTR after being heated to 75  C.
The mixture was mixed at a constant stirring rate of 400 rpm.
After that, the product mixture overowed to the cooling water
2.4.2. Purication
To meet biodiesel specications, the FAME phase having
a residual FFA of about 1.4%wt was neutralized with 10.24%wt of
3 M NaOHH2O solution (10.24 g of the solution/100 g of FAME
phase) on the basis of the results from Section 2.3.2. The NaOH
H2O solution (0.8 kg/h) and the FAME phase (8.3 kg/h) were
preheated to 80  C before entering a 4.2 L CSTR. The mixture was
mixed at a 500 rpm stirring rate with a reaction temperature of
80  C for 20 min. After that, the neutralized products settled into
two phases in a 12.6 L separator. The FAME product overowed at
the top of the separator and the soap phase was removed at the
bottom. The FAME product was passed into a 20 L water washing
tank with a water feed rate of 10 L/h and then overowed into
a 20 L separator for water separation. Finally, the biodiesel
product was heated by an evaporator to remove the residual
water in the product.
2.5. Sample analysis
Thin layer chromatography equipped with a ame ionization
detector (TLC/FID) using an Itronscan MK-6s with Chromarods
type S-III quartz rod (Mitsubishi Kagaku Iatron) was used to
analyze the components of biodiesel. The sample was diluted in
hexane and 1 mL of the sample solution was spotted onto the

Table 4
Operating costs for the annual production of 72,000 kg of biodiesel from PFAD in this
study

Description Cost Annual Annual cost Unit cost

(baht) use (baht/year) (baht/kg)
Raw materials
PFAD 11/kg 76,464 kg 841,100
Methanol 19/kg 20,115 kg 382,199
Sulfuric acid 8/kg 1404 kg 11,232
Sodium hydroxide 19/kg 756 kg 14,364
Subtotal raw materials 1,248,895 17.34

Utilities
Electricity 1/kga 72,000
Charcoal 3.4/kg 2898 kg 9853
Process water 0.012/L 86,400 L 1037
Subtotal utilities 82,890 1.15

Labor
Operating 200/day 72,000 1.00

Gross production cost 1,403,612 19.50

Fig. 3. FAME and glycerides content in the neutralized product using the 3 M NaOH a
Kilograms of biodiesel; 31,425 baht per USD (April 23, 2008).
H2O solution at 80  C under atmospheric pressure for 15 min.
1062 S. Chongkhong et al. / Renewable Energy 34 (2009) 10591063

Table 5
Properties of PFAD biodiesel in comparison with others

Properties Unit PFAD Rubber seed Mahua Soy soapstock Diesel Biodiesel standards
biodiesela oil biodiesel biodiesel biodiesel ASTM D6751-02
Density at 15  C kg/m3 879 874 880 885 850 870900
Viscosity at 40  C mm2/s 4.87 5.81 3.98 4.302 2.60 1.96.0

Flash point C 180 130 208 169 68 130

Pour point C 14 8 6 NA 20 15 to 10
Water content % 0.03 NA 0.04 <0.01 0.02 0.03
Ash content % 0.007 NA 0.01 0.02 0.01 0.02
Carbon residue % 0.07 NA 0.20 0.01 0.17
Acid value mg KOH/g 0.33 0.118 0.41 0.05 0.35 0.80
a
PFAD biodiesel from neutralization with 10.24%wt of 3 M NaOHH2O solution at 80  C for 20 min.

rods. The rods were immersed in a mixture of hexane:diethyl
ether:formic acid (50:20:0.3 v/v) until the mixture reached 8 cm,
and then in a mixture of benzene:hexane (1:1 v/v) until the
mixture reached 10 cm. After that, the rods were dried at 105  C
for 5 min and scanned with the TLC/FID. Scanning was carried out
under a hydrogen ow rate of 160 mL/min and an air ow rate of
2.0 L/min to produce a chromatogram. Peak areas of FAME,
triglycerides (TG), diglycerides (DG), monoglycerides (MG) and
residual FFA were calculated with a chromatography data system
ChromStar and depicted as weight percentages (%wt) on a GL-free
basis.
3. Results and discussion
3.1. Batch experiments
3.1.1. Esterication
The esterication reaction hardly occurred without a catalyst.
Nevertheless, a good reaction rate required only an appropriate
amount of the catalyst. Excess addition of the catalyst caused a dark
color of the product and more neutralizing solution was needed.
From our experiments, the yield of FAME obtained by using 0.92,
1.83 and 2.75%wt of H2SO4 was not signicantly different. The
interaction between the reaction temperature and reaction time
was studied by experimental run no. 3 and 5. With the reaction
temperature of 65  C, a longer reaction time of 120 min was
required to obtain the same FAME content with the reaction
temperature of 70  C and reaction time of 90 min (Fig. 2). The
interaction between the reaction time and molar ratio of methanol
to PFAD was represented by experimental run no. 7 and 9. With
a higher ratio of 8.8:1 a shorter reaction time of 60 min was enough
to gain the same FAME content by using a lower ratio of 7.2:1 and
reaction time of 120 min. In addition, experimental run no. 3, 5, 7
and 9 obtained quite the same maximum yield of FAME. These
mean that with a higher reaction temperature the esterication
reaction was completed in a shorter time. Similarly, with a higher
amount of methanol a shorter reaction time was required.
However, the optimum operating condition was decided to be
experimental run no. 7 by using an 8.8:1 ratio for 60 min at 75  C
with 1.83 wt% H2SO4 because it possibly required the lowest energy
consumption.
3.1.2. Purication
Neutralization and saponication reactions took place as the
FAME phase was neutralized with the NaOHH2O solution. When
the solution increased, the glycerides (TG DG MG) content
decreased and the purity of FAME increased. Neutralization with
2.05%wt of the 3 M NaOHH2O solution could get rid of all the
residual FFA. To meet biodiesel specications, 10.24%wt of 3 M
NaOHH2O solution was required to reduce glycerides and 100%
FAME was obtained when using 13.32%wt of the 3 M NaOHH2O
solution (Fig. 3).
3.2. Continuous process
3.2.1. Esterication and purication
The optimum conditions for batch esterication and neutrali-
zation were used as the operating conditions for the continuous
process. The ester yields and purities for the batch and continuous
processes are shown in Table 3. The batch esterication yield was
2% higher than the continuous yield. On the other hand, the purity
of batch esterication was 3.4% lower than that of continuous
esterication. For the purication process the yields and purities
obtained from the batch and continuous processes were not so
different.
3.2.2. Production costs analysis
Production cost (Table 4) was calculated based on the process
ow diagram shown in Fig. 1. The gross production cost for making
biodiesel from PFAD is estimated to be 19.5 baht/kg. The cost of raw
materials constitutes the greatest component, while the cost of
PFAD is 60% of the overall production cost. However, the PFAD price
is cheaper than the used oil, crude palm oil and rened palm oil (2,
6 and 20 baht/kg cheaper, respectively). In addition, the process of
making biodiesel in this work is inexpensive as it is operated under
mild conditions (low temperature and pressure) and the capital
cost of the apparatus is low. Thus, the use of low cost PFAD feed-
stock can improve the economic viability of biodiesel.
3.3. Properties of PFAD biodiesel
A summary of the properties of PFAD biodiesel is presented in
Table 5 along with rubber seed oil, mahua and soy soapstock bio-
diesel [4,7,14] and diesel. The results show that the two step
process, esterication and neutralization, enabled the PFAD bio-
diesel properties with respect to density, viscosity, ash point,
water content, ash content and acid value to meet biodiesel stan-
dards (Table 1). Especially the ash content of PFAD biodiesel is the
lowest compared to biodiesel from other feedstocks and diesel,
which means that PFAD biodiesel is cleaner fuel in terms of lower
particulate matter and gas emission risk. But, the pour point of
PFAD biodiesel is a bit higher than the standard because the main
component of PFAD is 53.7% saturated FFA. However, the pour point
can be easily lowered by blending PFAD biodiesel with diesel.
Therefore, this PFAD biodiesel is a high potential alternative to
petroleum diesel for use in unmodied diesel engines. In addition,
it is widely known that the color of FAME obtained from the acid-
catalyzed esterication process is usually black. With our puri-
cation process the color of the PFAD biodiesel was the preferred
clear brown.
4. Conclusion
An economical process for the continuous production of bio-
diesel from low cost PFAD was established. The feature of the
 S. Chongkhong et al. / Renewable Energy 34 (2009) 10591063
process is a simplied operation with mild conditions that assists
the economic viability of biodiesel. The esterication and puri-
cation processes provided high-quality biodiesel with a clear
brown color and most properties met the requirement of the
American standard.
Acknowledgment
The authors gratefully acknowledge the nancial support from
the Graduate School of Prince of Songkla University.
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