Two-step biodiesel production from Calophyllum inophyllum oil: Optimization

of modied b-zeolite catalyzed pre-treatment

Vasanthakumar SathyaSelvabala, Dinesh Kirupha Selvaraj, Jalagandeeswaran Kalimuthu,
Premkumar Manickam Periyaraman, Sivanesan Subramanian

Department of Chemical Engineering, A.C. College of Technology, Chennai 600025, India

a r t i c l e i n f o
Article history:
Received 26 May 2010
Received in revised form 13 August 2010
Accepted 16 August 2010
Available online 22 August 2010
Keywords:
RSM
b-Zeolite
Phosphoric acid modication
Calophyllum inophyllum
a b s t r a c t
In this study, a two-step process was developed to produce biodiesel from Calophyllum inophyllum oil.
Pre-treatment with phosphoric acid modied b-zeolite in acid catalyzed esterication process preceded
by transesterication which was done using conventional alkali catalyst potassium hydroxide (KOH). The
objective of this study is to investigate the relationship between the reaction temperatures, reaction time
and methanol to oil molar ratio in the pre-treatment step. Central Composite Design (CCD) and Response
Surface Methodology (RSM) were utilized to determine the best operating condition for the pre-treat-
ment step. Biodiesel produced by this process was tested for its fuel properties.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
Biodiesel, which is known as FAME (fatty acid methyl ester), is
derived from vegetable oils and animal fats. Since it is biodegrad-
able, renewable, nontoxic possesses inherent lubricity, and having
relatively high ash point attracts a special attention during the
recent years as an alternative to petroleum based diesel fuel
(Kitakawa et al., 2007). FAME is produced by acid or alkali catalytic
transesterication of oil. Biodiesel synthesized from various edible
vegetable oils like sunower oil, cotton seed oil and palm oil has
been tested successfully in the diesel engine. Since Indias invest-
ments are more on importing edible oils, the use of edible oils
for diesel engine fuel is not feasible (Soriano et al., 2008). Hence-
forth, non-edible vegetable oil extracted from certain species such
as Honge (Pongamia pinnata), Jatropha (Jatropha curcas), Mahua
(Madhuca indica) and Neem (Azadirachta indica) etc., could be used
as alternative fuel for diesel engine (Meher et al., 2006).
One such non-edible oil extracted from the seed of the tree
Calophyllum inophyllum is found to be a better source for the
biodiesel synthesis. Origin of the species is uncertain and rarely
found in tropics. It falls under the group of coastal species that
grows widely on sandy beaches but to some extent along the river
margins. The free fatty acid content of unrened ltered pinnai oil
was found to be 22% (Acid value of 44 mg KOH g
1
of oil).
(Venkanna and Reddy, 2009). In India the estimated amount of
non-edible oil seeds annual production potential is more than
20 mega tones, of which pinnai contributes 70,000 metric tones
(Sahoo et al., 2007).
Very few researchers have worked on this oil using conven-
tional catalyst. Sahoo and Das (2009) synthesized biodiesel using
conventional acid and base catalyst, further it was tested as a fuel
in diesel engines. Venkanna and Reddy (2009) carried out the syn-
thesis of biodiesel from pinnai using a three-stage method.
It was found that oils with high free fatty acid (FFA) level are not
a better source for the synthesis of biodiesel. Due to the high FFA
(>2% w/w), soap formation may occur when alkaline catalyst is
used (Kansedo et al., 2008). Therefore researchers proposed a com-
bined two-step process, in which pre-treatment prior to transeste-
rication utilizing acid catalyst was carried out to overcome this
problem. In the pre-treatment step, esterication reaction converts
most of the FFAs into its corresponding FAME, respectively. How-
ever, triglycerides are still remaining in the pre-treated oil and so
transesterication reaction was performed consequently to com-
plete the biodiesel production.
Some of the solid acid catalysts have been investigated for the
potential replacements of mineral acids in esterication and
transesterication reactions are tungstated zirconia (Lopez et al.,
2008), sulfated zirconia (Garcia et al., 2008), carbohydrate derived
solid acid catalyst (Lou et al., 2008), ion exchange resins (Marchetti
et al., 2007), mesoporous aluminosilicate Al-MCM41 (Carmo et al.,
2009). The preparation of solid catalysts is a complicated proce-
dure because of high expense and thermal stability; this in turn be-
comes an issue when resin type catalysts are used at higher
temperature. Zeolites and modied Zeolites attracted special
0960-8524/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.08.052

Corresponding author. Tel./fax: +91 44 22203525.

E-mail address: sivanesh@yahoo.com (S. Subramanian).
Bioresource Technology 102 (2011) 10661072
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
attention because of their effectiveness in removing the free fatty
acids present in non-edible oils (Chung et al., 2008). Moreover in
zeolites, acid strength can be adjusted to t the reaction require-
ment (Lotero et al., 2005).
In the present study, as a novel attempt we used heterogeneous
solid acid catalyst for the reduction of FFA present in pinnai oil. The
objective of this study is to optimize the parameters affecting the
esterication of free fatty acids present in pinnai oil. During opti-
mization, RSM (Response Surface Methodology) was also used be-
sides the classical technique. RSM is considered as an important
tool to develop a novel process which shows promising results in
industrial research, especially where large numbers of variables
inuences the system (Gopinath et al., 2010).
2. Methods
2.1. Materials
b-zeolite (Al/Si ratio = 19) was purchased from Sud-Chemie
India Ltd, Mumbai, India. Phosphoric acid, methanol, phenolphtha-
lein and ethanol were purchased from Qualigens Fine Chemicals
Ltd. Non-edible grade pinnai oil was obtained from local market.
Fatty acid prole and the results of chemical analysis of the oil
were given in Table 1. All the chemicals were used without further
purication.
Pinnai is strong pungent odoured greenish yellow colored oil
with specic gravity and refractive index 0.9250.940 and 1.469
1.4772, respectively. Pinnai oil has iodine value in the range of
8298 and saponication value in the range of 191202. Pinnai
oil is rich in Linoleic and Oleic acid. The composition of the oil
are C16:1; 12.01 wt.%, C18:0; 12.95 wt.%, C18:1; 34.01 wt.%,
C18:2; 38.26 wt.% and C24:0; 0.3 wt.%.
2.2. Catalyst preparation
Phosphoric acid modication was done as described by Sat-
hyaselvabala et al. (2010). About 2.25 g of b-zeolite (b) in 25 ml
of double distilled water was mixed with 0.75 g of phosphoric acid.
The mixture was kept under vigorous stirring at room temperature
(2025 C) for about 12 h which was then evaporated and dried in
an air oven at 120 C. The obtained white colored powder is phos-
phoric acid modied b-zeolite (Pb).
2.3. Catalyst characterization
The X-ray diffraction (XRD) patterns of the b and Pb were re-
corded on an X-ray diffractometer (Rigaku D/Max Ultima III) oper-
ating less than 40 kV and 40 mA with the scan rate of 2/min. FTIR
spectra of the Zeolites were recorded on a Nicolet (AVATAR 360)
instrument using KBr pellet technique. Shapes and sizes of the
Zeolites were examined by Scanning electron microscope (SEM,
Hitachi S-4900). Thermo grams were recorded using a Thermo
gravimetric analyzer (TGA Q 50 V 20.6 Build 31 instrument). The
acidity of the zeolites was analyzed by NH
3
TPD method. Adsorp-
tion of ammonia was carried out on each sample in a quartz tube
packed with 100 mg of the sample. The initial ushing was carried
out with pure Helium (at 25 cc/min ow) for about1 h and cooled
to 115 C. Ammonia adsorption was carried out by passing the
ammonia vapors over the catalyst bed. Later, adsorbed helium
was passed to remove the physisorbed ammonia.
2.4. Two-step biodiesel production
This work presents the development of two-step process for the
production of biodiesel from pinnai oil having high FFA. Initially,
the phosphoric acid modied b-zeolite (Pb) was used to catalyze
the esterication of free fatty acids present in the pinnai oil. After
the recovery of methanol, the insoluble Pb in oil can be separated
by centrifugation and studies on reusability had been carried out.
After the reduction of FFA to 62, transesterication reaction was
carried out, in which the pre-treated oil reacts with methanol using
conventional KOH catalyst.
Both the steps of biodiesel production were carried out in a
three necked round bottom ask equipped with a reux condenser
to avoid alcohol evaporation. Stirring was performed with the help
of a mechanical stirrer. The temperature of the ask was main-
tained at different levels using silicon oil bath, which was in con-
nection with the dimmer stat.
2.5. Acid catalyzed pre-treatment
Pinnai oil was poured into the ask and solid acid catalyst was
added followed by methanol. The progress of the reaction was
monitored by measuring the acidity value. Different methanol to
oil ratios were employed between 3,6,9,12,15 (0.10.5 wt.%);
Table 1
Experimental design and results of the CCD.
Run
order
Temperature
(C)
Catalyst amount
(wt.%)
Oil to methanol ratio
(wt.%)
Acid value (mg KOH/g of oil)
(Experimental)
Acid value (mg KOH/g of oil)
(Predicted)
1 60 1.0 0.3 1.90 2.6484
2 50 1.2 0.2 15.20 14.6606
3 70 0.8 0.2 11.70 11.3106
4 50 0.8 0.2 23.40 24.5606
5 60 1.0 0.3 1.90 2.6484
6 60 1.0 0.2 7.92 6.5775
7 70 1.2 0.4 7.40 6.8006
8 70 0.8 0.4 8.20 9.3006
9 50 1.0 0.3 13.60 12.5775
10 50 0.8 0.4 16.40 15.8506
11 60 0.8 0.3 8.50 7.1775
12 60 1.0 0.4 3.32 2.4175
13 60 1.2 0.3 1.90 0.9775
14 60 1.0 0.3 1.90 2.6484
15 60 1.0 0.3 1.90 2.6484
16 70 1.2 0.2 5.30 6.4106
17 70 1.0 0.3 6.40 5.1775
18 50 1.2 0.4 7.40 8.3506
19 60 1.0 0.3 1.90 2.6484
20 60 1.0 0.3 1.90 2.6484
V. SathyaSelvabala et al. / Bioresource Technology 102 (2011) 10661072 1067
catalyst amount was varied between 0.2 and 2(wt.%). Temperature
range of 3090 C was evaluated during pre-treatment. The nal
reaction mixture was centrifuged at 8000 rpm and the supernatant
methanol was removed. From the remaining residue, solid acid
catalyst was separated and the pre-treated oil was processed by
base catalyzed reaction. Process parameters were optimized using
Classical and Response Surface Methodology. The separated cata-
lyst was checked for its reusability.
2.6. Experimental design and optimization by Central Composite
Design (CCD)
Optimum condition for the esterication of free fatty acids was
determined by Response Surface Methodology (RSM) and the
important class of second order design called Central Composite
Design (CCD) was used for the analysis. CCD is an effective design
and an ideal method for sequential experimentation. Optimization
studies were carried out by studying the effect of three variables
such as, temperature, methanol to oil ratio and catalyst amount.
To describe the effect of process parameters, a 2
3
full factorial
CCD leading to 20 sets of experiments were performed. The inde-
pendent variables chosen in this study were coded according to
the equation given below.
x
i

X
i
X
o
DX
1
where x
i
is the dimensionless coded value of the i
th
independent
variable, X
o
is the value of X
i
at the center point and DX is the step
change value. The experimental design and results of the CCD were
shown in Table 1. The uncoded values are given in Table 2.
The behavior of the system is explained by the following
second-order polynomial model.
Y b
0
b
1
x
1
b
2
x
2
b
3
x
3
b
11
x
2
1
b
22
x
2
2
b
33
x
2
3
b
12
x
1
x
2
b
23
x
2
x
3
b
31
x
3
x
1
2
where Y is the predicted response (Acid value, mg KOH g
1
of oil);
x
1
, x
2
and x
3
are the code forms of the input variables such as, tem-
perature, methanol to oil ratio and catalyst amount, respectively; b
0
is a constant; b
1
, b
2
and b
3
are the linear coefcients; b
11
, b
22
and b
33
are the quadratic coefcients; b
12
is a cross-product coefcient. A
statistical program package was used for regression analysis of
the data obtained and to estimate the coefcients of the regression
equations. Analysis of variance (ANOVA) was used for graphical
analysis of the data in order to obtain the interaction of process
variables with the response. The quality t of polynomial model
equations was expressed by the coefcient of determination R
2
.
2.7. Base catalyzed transesterication
The pre-treated oil was poured into the reaction ask and
heated. The solution of KOH in methanol (1%) was thermo stated
at 60 C and mixed with the pre-treated oil. The molar ratio of
methanol to oil was set to 6 and the reaction mixture was stirred
constantly by a mechanical stirrer. The reaction was stopped after
1 h and was poured into a separating funnel. The lower layer, con-
taining glycerol and other impurities, was drained off. The upper
layer containing biodiesel was washed with hot distilled water
thrice, discarding the lower layer; the upper layer after the third
wash is the nal biodiesel product.
2.8. Product Analysis
Acid value of the reaction mixture was determined by the acid
base titration technique. The conversion of FFA was calculated
using the equation (Chung et al., 2008).
X
FFA

a
i
a
t
a
i
3
where a
i
is initial acidity and a
t
is acidity at time t. Production of
biodiesel was conrmed by High Performance Liquid Chromatogra-
phy (HPLC), equipped with refractive index detector. A sphere -5
C-18 column at temperature 40 C was used for the separation with
1 ml/min ow rate of methanol as a carrier solvent. The sample
injection was 20 lL and each constituent was quantied by com-
paring the peak areas with respective standards. Physical and
chemical properties of fatty acid methyl esters were analyzed by
ASTM standard procedures. The ash point was determined by a
PenskyMartens closed-cup tester (ISL, Model FP93 5G2), using
ASTM D 93. Cloud point and pour point determinations were made
using ASTM D 2500 and ASTM D 97. The kinematic viscosities were
determined at 1540 C, using a Viscometer (Anton Parr, Stabinger,
Model SVM3000). The procedure of ASTM D 7042 was followed. The
water contents were determined following ASTM D 95.
3. Results and discussion
3.1. Characterization of the catalyst
In FTIR spectrum of b, the asymmetric SiOSi vibration gives
an intense broad peak between 1000 and 1300 cm
1
(Landau
et al., 2003). The peaks at 759 and 810 cm
1
are due to symmetric
vibration of SiOSi bonds. The bending bond modes of SiOSi
give a sharp intense peak at 459 cm
1
(Newsam et al., 1988). In
the Pb spectrum the asymmetric SiOSi vibrations at 1090 and
1216 cm
1
are narrowed. The corresponding symmetric vibration
at 810 becomes less intense. In addition, the SiOSi bending
vibration is also seen to have reduced intensity. As phosphate
vibrations occur in the same region of SiOSi asymmetric stretch-
ing, the peaks at 1090 and 1216 cm
1
includes the vibrations of the
former. This agrees with the already reported literature
(Sathyaselvabala et al., 2010). Hence the above changes indicate
the phosphoric acid modication.
3.2. Catalytic Activity of modied b-zeolite on pre-treatment of pinnai
oil
The results of esterication of free fatty acids of pinnai oil over
parent b and Pb shows that Pb exhibits higher conversion than b.
Even though, our previous study explained the potential of phos-
phoric acid modied mordenite zeolite on esterication of fatty
acids in neemoil (Sathyaselvabala et al., 2010), this study gives fur-
ther explanation on the activity of the phosphoric acid modied b
zeolite. From the results of ammonia TPD, it is evident that Pb car-
ries weak and medium acid sites without strong acid site. In gen-
eral the presence of strong acid sites inuence more absorption
of water and so the catalyst must be hydrophilic in nature. If there
are many protic sites, the catalyst will be more hydrophilic since Pb
does not hold water molecules as strongly as b. Generally equilib-
rium is established in the esterication of FFA with mineral acid
catalyst but such equilibrium must not be applicable to Zeolite
catalysis as the active site is not available outside the Zeolite pore.
One of the products of esterication reaction, water can be easily
Table 2
The uncoded values of design analysis.
Variables Levels
1 0 +1
Temperature 50 60 70
Methanol oil ratio 0.8 1.0 1.2
Catalyst 0.5 1 1.5
1068 V. SathyaSelvabala et al. / Bioresource Technology 102 (2011) 10661072
expelled out of the above mentioned pore thus facilitating more
conversion. These may be external acid sites on the surface of
the catalyst but they cannot adsorb water as strongly as b. In this
context lower conversion over b can be better understood, as it car-
ries strong acid sites by which it can retain more number of acid
sites either inside the channel or outside the channel. Based on this
argument it could be said that less conversion over b is attributed
to the existence of equilibrium in mineral acid catalyses reaction.
The hydrophilic nature of Pb was conrmed by the IR spectrum
of used Pb and b. It is well evident that the intensity of OH stretch-
ing vibrations around 26003700 cm
1
and the corresponding
bending vibration around 1646 cm
1
is very weak for Pb, when
compared to that of b. It shows the water repelling property of
Pb helps in the esterication reaction. Thermo gravimetric analysis
of both Pb and b also proves the hydrophobic property. From the
thermograms shown in Fig 1, it is clear that for b, the percentage
of loss of water was found to be 11.25% and for Pb it was 12.52%.
From the thermograms of used Pb, it is clear that the weight loss
below 200 C is attributed to mainly methanol, but that of between
200 C and 400 C is attributed to the loss of adsorbed fatty acids.
This observation is in accordance with our view of conferring en-
hanced hydrophobicity by phosphoric acid modication.
In Table 3, recently reported literature on esterication reaction
using several heterogeneous acid catalysts with different starting
materials having different FFA concentration, are given. In our
present work with Pb, we achieved 93% yield. This result is compa-
rable with our previous work with phosphoric acid modied
mordenite zeolite. Park et al. (2010a,b) showed 93% conversion
of free fatty acids, but the catalyst amount and the reaction time
are high. Commercial oleic acid was esteried with an ion ex-
change resin, Amberlyst 15, achieved 90% conversion. But in this
case also the catalyst and the time taken for completion of the
reaction are quite high. From the discussion, it is evident that our
modied catalyst shows better conversion efciency of 93%. Ester-
ication ratio (conversion) of oil is the most important quality
parameter in diesel production and it should be over 96% (ASTM
standard) for an effective conversion and feasible production. It
might be anticipated that, the phase separation of the by product
would play a major role in achieving a conversion close to 100
(Sahoo et al., 2007).
3.3. Reusability Check
To evaluate the reusability of Pb, the esterication reaction was
repeated under the same optimum conditions. The catalyst was
removed from the reaction mixture by centrifugation. The process
was repeated thrice. In all the three processes conversion remain
the same; thus establishing the absence of catalyst deactivation.
In order to conrm further, the catalyst was removed and sub-
jected to XRD analysis. The XRD patterns of Pb zeolite before and
after usage reveal the avoidance of crystallization after using the
catalyst for esterication. Hence the catalyst stability and reusabil-
ity for FFA esterication is thus veried.
3.4. Pre-treatment process parameters optimization; Classical
Methodology
3.4.1. Effect of methanol content on pre-treatment
To study the effect of methanol content on the esterication of
FFA in pinnai oil, the content of the former was varied as
0.10.5 wt.%. The FFA conversion increased from 0.1% to 0.3%, but
decreased slightly there after. The decrease in conversion above
0.3% is due to the dilution of FFA by excess methanol. The excess
methanol could increase the diffusion of FFA into the zeolite pore
where the active sites are mainly located. As the reaction time
was 1 h, it could be the reason that increase in reaction time could
enhance conversion, as the reaction over Pb is exempted from the
concept of equilibrium of esterication with mineral acid catalyst.
In order to verify this, the reaction period was increased to 24 h;
nearly 90% conversion was obtained. This conrms our view.
3.4.2. Effect of catalyst amount on pre-treatment
In order to study the effect of catalyst loading on the esterica-
tion of free fatty acid with methanol, the weight of the former was
increased from 0.2 to 2.0 for the same level of methanol to oil ratio
(9). There is a non-linear variation in the conversion with increase
in the amount of catalyst. The conversion increases from 0.2% to
1%, and then remains constant between 1.0% and 1.4% and de-
creases above 1.4%. The decrease in conversion above this weight
is due to the decrease in the concentration of both FFA and meth-
anol around an active site. In order to verify this, the reaction
Fig. 1. Thermo gram of (a) b-zeolite (b) Phosphoric acid modied b-zeolite
(c) Phosphoric acid modied b-zeolite obtained after esterication.
Table 3
Recently reported literatures on esterication reaction using several heterogeneous acid catalysts with different starting materials having different FFA concentration.
Oil, free fatty acid amount(mg
KOH/g of oil)
Name of catalyst Catalyst
loading
Time
(h)
Oil methanol
ratio
Temperature Conversion Reference
Waste cooking oil, 1.72 Fe
2
(SO
4
)
3
0.4 g 3 7:1 60 C 81.3% Wan omar et al. (2009)
Crude palm oil, 33.4 Fe
2
(SO
4
)
3
2 wt.% 2 10:1 95 C 80% Buasri et al. (2009)
Waste frying oil, 13.7 Cation exchange resin NKC-9 20 wt.% 2 6:1 64 C 79.7% Feng et al. (2010)
Sunower oil, 7.4 WO
3
/ZrO
2
29% 2 9:1 75 C 93% Park et al. (2010a,b)
Oleic acid, 279 Amberlyst 15 20% 2 6:1 80 C >90% Park et al. (2010a,b)
Neem oil, 24.4 Phoshphoric acid modied
mordenite
1% 1 6:1 60 C 92.5% Sathyaselvabala et al.
(2010)
Pinnai oil, 44 Phosphoric acid modied
b-zeolite
1% 1 9:1 60 C 93% Present work
V. SathyaSelvabala et al. / Bioresource Technology 102 (2011) 10661072 1069
period was increased to 48 h. The conversion was increased to
91.6%. In order to evaluate any glycerides of esters during esteri-
cation of FFA over Pb, a separate reaction involving heating of pin-
nai oil without methanol over Pb was carried out. The reaction was
continued for 24 h. The resulting product is tested for FFA content
and an increment of 61% was notied. As the value was found to be
very much less, direct transesterication of pinnai oil over Pb,
might also be insignicant. Though TGA analysis shows 11% of
water, the same water content appears to be insignicant to effect
hydrolysis of pinnai oil. The reaction categorically rejects the appli-
cability of Pb for fast transesterication of pinnai with methanol.
Transesterication of pre-treated pinnai oil with methanol over
KOH is necessary for biodiesel production.
3.5. Pre-treatment process parameters optimization; Response Surface
Methodology
In contrast with the classical optimization process, which may
lack to account the effectiveness of different combination of
parameters, RSM provides elaborate vision over various combina-
tions of parameters. Experiments were conducted with various de-
signs through CCD to visualize the effects of independent factors
on responses and the results were evaluated. The full quadratic
models were established by using the method of least squares.
The predicted pre-treatment product yield is shown in the
equation
Y
pre
2:6484 3:700T 3:100C 2:080O 6:2291T
2
1:429C
2
1:8491O
2
1:2500TC 1:6750TO
0:600CO 4
where Y
pre
stands for the predicted pre-treatment product yield val-
ues; T is temperature; O is oil to methanol ratio and C is catalyst
amount.
ANOVA results of these quadratic models are presented in
Table 4, indicating that these quadratic models can be used to nav-
igate the design space. Fig. 2 compares the observed experimental
pre-treatment product yield with the predicted pre-treatment
yield. The model was found to have correlation value (R
2
) of
0.975, which means 97.5% of the total variation in the results
was attributed to the independent variables investigated. The
entire three parameters temperature, catalyst amount and oil
methanol ratio have positive effect in reducing the acid value when
they are increased.
From Table 4, it is very clear that interaction between variables
have signicant effect on the yield of biodiesel. It is evident from
the coefcient values obtained from the coded units. The increase
in parameter values will reduce the acid value in the following or-
der T > C > M. The inuence of the combination of parameters in
the reduction of acid value is in the following order
T&M > T&C > C&M, whereas the acid value reduced to a major ex-
tent under the inuence of temperature and oil methanol ratio
combination. Henceforth, instead of analyzing single variable (clas-
sical method) the interactions between the variables will be inves-
tigated which plays a major role in comprehensive optimization
study.
3.5.1. Response surface plots
Fig. 3 shows the effects of different variables such as reaction
temperature, molar ratio of methanol to oil and catalytic amount
on the yield of biodiesel in three dimensional surface response
plots respectively. From Fig 3b, it is obvious that at any designated
temperature from 50 to 70 C, the acid value decreases from 0.8%
to 1% catalyst amount and then increases from 1% to 1.2%. In con-
trast at constant catalyst amount, the acid value decreases in the
temperature range of 5060 C and then increases.
The effect of reaction temperature and methanol to oil ratio on
acid value is shown in Fig 3c. At the reaction temperature of 50 C,
the reduction in acid value is marginally affected by the methanol
to oil ratio. However the reaction temperature reaches 60 C and
shows better reduction in acid value. As the temperature increases
to 60 C, the reduction in acid value decreases. Fig 3a represents
the effects of interaction between catalyst amount and methanol
ratio on acid value reduction. When temperature increased in com-
binations with catalyst amount, the acid value decreased to some
extent and then increases. The rate of reduction in acid value is
higher when catalyst amount is increased from 0.8 to 1.0 (wt.%)
and then it decreases.
3.5.2. Global solution validation
Based on Eq. (4), the exact global solution for the free fatty acid
reduction from 44 to 2 mgKOH g
1
of oil, predicted by Minitab 14
were having the temperature of 60 C, oil methanol ratio of 0.33
(wt.%) and catalyst amount of 0.1%.The global solution thus ob-
tained was validated by running the experiment and the result ob-
tained was 1.9 mg KOH g
1
of oil which lies very close to that
obtained from predicted global solution (2.0 mg KOH g
1
of oil).
3.6. Base catalyzed transesterication
Besides the presence of FFA, moisture as well as the agitation
intensity, the base catalyzed transesterication are also affected
by the concentration of catalyst, the molar ratio of methanol to
oil and the reaction temperature. The most often used molar ratio
of methanol to oil and the KOH amount are 6% and 1% respectively.
A test case of alkaline catalyzed transesterication was carried out
using an esteried sample using Pb which has an acid value of
62 mg KOH/g of oil.
Table 4
ANOVA table for design analysis.
Source Degrees of
freedom
Seq SS Adj SS Adj MS F P
Regression 9 673.780 673.780 74.864 44.25 0.000
Linear 3 276.264 276.264 92.088 54.44 0.000
Square 3 359.691 359.691 119.897 70.87 0.000
Interaction 3 37.825 37.825 12.608 7.45 0.007
Residual
Error
10 16.917 16.917 1.692
Lack-of-Fit 5 16.917 16.917 3.383
Pure Error 5 0.000 0.000 0.000
Total 19 690.69 690.69
R
2
= 0.9755
0
5
10
15
20
25
30
0 5 10 15 20 25
Observed values
P
r
e
d
i
c
t
e
d

v
a
l
u
e
s
Fig. 2. Parity plot for the observed and predicted pre-treatment product yield.
1070 V. SathyaSelvabala et al. / Bioresource Technology 102 (2011) 10661072
3.7. Biodiesel characterization
The samples of biodiesel produced by this method were tested
for their fuel properties. The fuel properties of biodiesel are sum-
marized in Table 5. The table shows that the biodiesel had compa-
rable fuel properties with those of diesel and the values and
parameters were within the limits prescribed in latest ASTM stan-
dards for biodiesel.
4. Conclusions
This study on biodiesel production from pinnai oil by two-step
process satises the objective of reducing the FFA present in the oil,
followed by KOH catalyzed transesterication. Phosphoric acid
modied b-zeolite would be the better replacement for the con-
ventional liquid acid catalyst. The CCD and RSM were effective in
determining the relationship among reaction temperature, oil to
methanol ratio and catalyst amount. The experimental values ob-
tained in the optimum conditions established by RSM and CCD sat-
ises the predicted values. The biodiesel obtained was
characterized using standard methods.
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Distillation temperature 360
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