Bioresource Technology 101 (2010) 5897–5902

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Removal of free fatty acid in Azadirachta indica (Neem) seed oil using
phosphoric acid modified mordenite for biodiesel production
Vasanthakumar SathyaSelvabala a, Thiruvengadaravi Kadathur Varathachary b, Dinesh Kirupha Selvaraj a,
Vijayalakshmi Ponnusamy a, Sivanesan Subramanian a,*
a
Department of Chemical Engineering, A.C. College of Technology, Chennai 600 025, India
b
Department of Chemistry, Velammal Engineering College, Chennai 600 066, India

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

Article history: In this study free fatty acids present in Azadirachta indica (Neem) oil were esterified with our synthesized
Received 23 December 2009 phosphoric acid modified catalyst. During the esterification, the acid value was reduced from 24.4 to
Received in revised form 19 February 2010 1.8 mg KOH/g oil. Synthesized catalyst was characterized by NH3 TPD, XRD, SEM, FTIR and TGA analysis.
Accepted 22 February 2010
During phosphoric acid modification hydrophobic character and weak acid sites of the mordenite were
Available online 25 March 2010
increased, which lead to better esterification when compared to H-mordenite. A kinetic study demon-
strates that the esterification reaction followed pseudo-first order kinetics. Thermodynamic studies were
Keywords:
also done based on the Arrhenius model.
Neem oil
Free fatty acid
Ó 2010 Elsevier Ltd. All rights reserved.
Esterification
Mordenite
Kinetics

1. Introduction Simarouba (Simarouba indica), which could be utilized for biodiesel

The world is facing a severe fossil fuel crisis due to increased
transportation and deficient energy production processes (Gui
et al., 2008). We can only cope up with a few more decades with
our current oil reserves (Sharma and Sing, 2007). Biodiesel is a
familiar alternative fuel; its advantage resides on its ease of usage
and integration with present engine models, requiring no major
changes in engine design. The replacement of petroleum-derived
diesel fuel with biodiesel reduces green house gas emissions up
to 45% (MacLeod et al., 2008). In addition, emissions of carbon
monoxide, particulates and hydrocarbons are significantly re-
duced, improving air quality in urban areas (Wang et al., 2000).
Currently, biodiesel is produced by the transesterification of tri-
glycerides of refined/edible type oils using methanol and an alka-
line catalyst (Ma and Hanna, 1999; Pinto et al., 2005; Lotero
et al., 2005).
According to a study done by Knothe (2002), the transesterifica-
tion of edible oils such as soybean oil, rapeseed oil, and palm oil
can be produced as biodiesel to fuel compression ignition engines.
In India, the usage of edible oils for the production of biofuel is not
feasible; however, there are several non-edible oils from different
species such as Pungam (Pongamia pinnata), Jatropha (Jatropha
curcas), Neem (Azadirachta indica), Mahua (Madhuca indica) and
* Corresponding author. Tel./fax: +91 44 22203525.
E-mail address: sivanesh@yahoo.com (S. Subramanian).
production processes (Meher et al., 2006).
Neem (A. indica) is a native South East Asian seed that contains
30% oil. Neem oil has been found to contain high amounts of free
fatty acids due to its difficult processing in its transesterification
with conventional basic catalysts. Earlier combustion of neem oil
methyl ester in a direct diesel engine was studied by Suryawanshi
(2008). Rao et al. (2008) examined the performance and emission
of different blends of neem oil methyl ester. Nabi et al. (2008) pro-
duced biodiesel from neem oil and studied the use of biodiesel
blends in a diesel engine. All these researchers used conventional
homogeneous catalysts to produce biodiesel from neem oil.
Biodiesel conversion is complicated if the oil contains large
amounts of free fatty acids (FFA) (>1% w/w) resulting in the forma-
tion of soap with alkaline catalyst. Soap prevents the proper sepa-
ration of biodiesel from glycerin (Demirbas, 2003; Zhang et al.,
2010). Since homogenous acid catalysts do not show measurable
susceptibility to FFAs they have the potential to replace base cata-
lysts. Certain characteristic features such as high temperature, high
molar ratio of oil and alcohol, separation of catalyst, serious envi-
ronmental and corrosion related problems makes them of less
use. Solid acid catalysts have the strong potential to replace
homogenous catalyst because of their salient features such as
interconnected system of large pores, a moderate to strong acid
sites and hydrophobic surface would be an ideal catalyst. (Lotero
et al., 2005). Apart from that it also eliminates corrosion and
environmental problems (Zhang et al., 2009). Several studies were

0960-8524/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.02.092
5898 V. SathyaSelvabala et al. / Bioresource Technology 101 (2010) 5897–5902

performed for the reduction of FFA in other oils by using acid cat- range of 30–90 °C with varying catalyst loading (0.5–2%) and
alysts (Zheng et al., 2006; Ramadhas et al., 2005; Marchetti et al., methanol to oil ratio was varied from 3 to 9. The final reaction mix-
2007; Ozbay et al., 2008). Zeolites and modified zeolite catalysts ture was centrifuged at 8000 rpm for 10 min and the supernatant –
can be used for effective reduction of free fatty acids. Chung that is, the excess methanol, was removed. From the remaining
et al. (2008) carried out the reduction of FFA using four different residue, solid acid catalyst was separated and further processed
Zeolites with varying Si–Al ratio. Carmo et al. (2009) used meso- by base catalyzed reaction. To compare the activity of the catalyst,
porous aluminosilicate Al-MCM-41 for esterification of palmitic Oleic acid (fatty acid, which is the major component in neem oil)
acid. was also processed using both MOR and MOR at optimum
The main goal of this study is to reduce the acid value of neem conditions.
oil using phosphoric acid modified mordenite (PMOR) with Si–Al
ratio 19 and makes it ready for further processing of biodiesel pro- 2.5. Product analysis
duction. Special attention was paid to synthesize the catalyst and
its activity towards esterification of catalyst. For comparison, the Acid value of the reaction mixture was determined by the acid
esterification of oleic acid using the PMOR was also carried out. base titration technique. The conversion of FFA was calculated
using the equation (Chung et al., 2008)
2. Methods ai  at
X FFA ¼ ð1Þ
ai
2.1. Materials
where ai is initial acidity and at is acidity at time t.
H-Mordenite (MOR) (Al/Si ratio = 19) was obtained from Sud-
Chemie India Ltd., Mumbai, India. Phosphoric acid, oleic acid, 2.6. Esterification kinetics
methanol, phenolphthalein and ethanol were purchased from
Qualigens Fine Chemicals Ltd. Commercial non-edible grade neem To analyze the esterification reaction of free fatty acid present
oil (average molecular weight = 815) was obtained from local in oil, the kinetic model suggested by Berrios et al. (2007) was fit-
market. The fatty acid profile is given in Table 1. All the chemicals ted with the experimental data obtained. The model was made by
were used as received without further purification. assuming that the esterification reaction was reversible and heter-
ogeneous and that the chemical reaction took place only in the oil
phase. The excess reactant – that is methanol, was high enough to
2.2. Catalyst preparation
remain constant throughout the process. It was also assumed that
non-catalyzed reaction was impossible; the rates of catalyzed
About 2.25 g of MOR in 25 ml of double distilled water was
esterification reactions were controlled by the chemical reaction
mixed with 0.75 g of phosphoric acid. The mixture was kept under
between oil and methanol. With these assumptions made, the ki-
vigorous stirring at room temperature for 12 h then evaporated
netic equation of esterification reaction can be written as
and dried in an air oven at 120 °C. The obtained white colored pow-   
der was PMOR. A0 þ E  b  12
2K 2  a  t ¼ ln   ð2Þ
½A0  E  b þ 12 
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi
2.3. Catalyst characterization u 2!
u K
a¼t þ K  A0 ð3Þ
The acidity of MOR and PMOR were analyzed by NH3 TPD meth- 4
od. Adsorption of ammonia was carried out on each sample in a a
quartz tube packed with 100 mg of the sample. The initial flushing b¼ ð4Þ
K
was carried out with pure helium (at 25 cc/min flow) for 1 h and K1
cooled to 115 °C. Ammonia adsorption was carried out by passing K¼ ð5Þ
K2
the ammonia vapors over the catalyst bed. Later, adsorption he-
lium was passed to remove the physisorbed ammonia. The X-ray A0 – initial acid value in mg KOH/g of oil; A – acid value at time t in
diffraction (XRD) patterns of the Zeolites were recorded on an X- mg KOH/g of oil; E – acidity removed in mg KOH/g of oil; K1 and K2
ray diffractometer (Rigaku D/Max Ultima III) operating less than are the rate constants for forward and backward reactions
40 kV and 40 mA with the scan rate of 2°/min. Cu Ka X-ray was respectively.
nickel filtered. Infra red spectra of the Zeolites were recorded on The values of K1 and K2 were calculated by fitting Eq. (2) with
a Nicolet (AVATAR 360) instrument using KBr pellet technique. experimental data obtained.
Shapes and sizes of the Zeolites were examined by Scanning elec-
tron microscope (SEM, Hitachi S-4900). Thermograms were re- 2.7. Thermodynamic studies
corded using a Thermogravimetric analyzer (TGA Q 50V 20.6
Build 31 instrument). The thermodynamic parameters reflect the feasibility and spon-
taneous nature of the process. The influence of temperature on
2.4. Acid catalyzed esterification specific reaction rate was modeled using Arrhenius equation. This
equation relates the kinetic constants K1 and K2 with temperature
The reaction was carried out in a three necked round bottom at which the reaction was carried out. The modeling equations are
flask equipped with a reflux condenser to avoid alcohol evapora- as follows:
 
tion. Stirring was performed with the help of a mechanical stirrer. Ea1
The temperature of the flask was maintained at different levels K 1 ¼ A1  exp ð6Þ
RT
using silicon oil bath, which was in connection with the dimmer  
Ea2
stat. Of 35 ml neem oil was poured into the flask and solid acid cat- K 2 ¼ A2  exp ð7Þ
RT
alyst was added followed by methanol. The progress of the reaction
was monitored by measuring the acidity value. Reaction parame- where A1 and A2 are the frequency factors of forward and reverse
ters were optimized using the classical method in the temperature reaction; Ea1 and Ea2 are the activation energies of forward and
 V. SathyaSelvabala et al. / Bioresource Technology 101 (2010) 5897–5902
reverse reactions; R is the universal gas constant. Rate constants ob-
tained at various reaction temperatures were fitted with Eqs. (6)
and (7) by nonlinear curve fitting using Matlab 7.0.
3. Results and discussion
3.1. Characterization of the catalyst
The results of NH3 TPD trace of MOR and PMOR are illustrated in
Fig. 1. In the profile of MOR; there is an intense peak between 100
and 300 °C and followed by a broad peak between 350 and 580 °C.
The low temperature peak is due to the desorption of NH3 from
weak acid sites. The latter high temperature peak is attributed to
the strong acid site. Among the weak acid sites, distribution of acid
strength is evident. There are four maximums lying close to 150,
175, 185, and 225 °C. In the region of strong acidity, a gradual var-
iation in acid strength is observed. The volume of NH3 desorbed,
corresponding to weak acid sites is 4.92 mL/g where as for strong
acid sites, and it is 3.5 mL/g. In the profile of PMOR, there is an in-
tense broad peak between 100 and 350 °C. It includes large
amounts of weak acid sites and a portion of medium acid sites.
The broad peak due to strong acid sites in Fig. 1b (above 350 °C)
are absent in Fig. 1a. Hence, as a result of phosphoric acid modifi-
cation, strong acid sites are converted into weak acid sites. The vol-
ume of NH3 desorbed is equal to 5.87 mL/g. It is clear that there is
an increase in the acidity of PMOR compared to MOR catalyst.
The XRD patterns of MOR resemble those reported in literature
(Hutchings et al., 1997). Most of the patterns of parent MOR are re-
tained in the spectrum of PMOR illustrating avoidance of crystalli-
zation loss as a result of phosphoric acid modification. There is a
decrease in the intensity of the patterns but no complete disap-
pearance of peaks.
In FTIR spectrum of MOR there is an intense broad band, be-
tween 2600 and 3700 cm1, is due to the OH bond stretching vibra-
tion of water. The corresponding bending vibration is seen in
1646 cm1. The asymmetric Si–O–Si vibration gives an intense
broad peak between 1000 and 1300 cm1. The peaks at 759 and
810 cm1 are due to symmetric vibration of Si–O–Si bonds. The
bending bond modes of Si–O–Si give a sharp intense peak at
459 cm1. The above results are comparable to reported spectrum
(Korkuna et al., 2006). In the PMOR spectrum, the OH stretching
Fig. 1. NH3 TPD profile of (a) phosphoric acid modified mordenite and
(b) H-mordenite.
5899
vibration of water which lies at 3426 cm1 is very much narrowed
compared to spectrum of MOR. The OH2 bending vibration is lo-
cated in 1637 cm1. The asymmetric Si–O–Si vibrations at 1090
and 1216 cm1 are also narrowed. The corresponding symmetric
vibration at 810 becomes less intense. In addition the Si–O–Si
bending vibration is also seen to have reduced intensity. As phos-
phate vibrations also occur in the same region of Si–O–Si asym-
metric stretching, the peaks at 1090 and 1216 cm1, also
includes the vibrations of the former. OH vibration of phosphate
generally occurs at 3660 cm1. But it is not clearly resolved in
the higher energy region due to adsorption of water. Hence the
above changes indicate the phosphoric acid modification.
From the SEM image of MOR it is evident that the presence of
aggregation of small sponge likes morphology. All of them appear
nearly similar without any impure phase. Similar result was also
reported in the literature (Korkuna et al., 2006). Aggregation of
sponge like morphology is also seen in the image of PMOR similar
to that of the MOR. Hence, as a result of phosphoric acid modifica-
tion, there might not be any structural degradation. Compared to
MOR, the aggregates appear larger in size in the modified image.
It is also supported by XRD results as discussed above. Hence phos-
phoric acid modification might have some role in the agglomera-
tion of particles altogether. In other words, phosphoric acid in
each particle, instead of lying exclusively inside the pore, might
also expose outwards to interact with other particles in order to
facilitate agglomeration.
3.2. Catalyst activity on esterification reaction
Results of esterification reaction in terms of percentage of free
fatty acid removal of neem oil and oleic acid using PMOR and
MOR are given in Table 2. From the results it is apparent that ester-
ification reaction is well favored by PMOR than MOR in both the
substrates. The higher acid value reduction for PMOR compared
with MOR is discussed as follows. The higher acid value reduction
is conformed by the high hydrophobic property of PMOR when
compared to MOR. High hydrophobic property requires less
amount of water absorption, and it was tested by thermogravimet-
ric analysis of both PMOR and MOR. The thermogram is presented
in Fig. 2. The percentage loss of water was found to be 12.25% for
PMOR and 24% for MOR. Hence the PMOR is confirmed to be more
hydrophobic than MOR. Tuning of hydrophobicity of the catalyst is
important in the esterification process as it could facilitate the
adsorption of hydrophobic acid and expulsion of released water
from the catalyst surface after esterification. Park et al. (2010) re-
ported that the water molecules present in the reaction mixture
inhibits the conversion of FFA to methyl esters by poisoning of acid
sites. Hence the enhanced hydrophobicity of the catalyst is an
important prerequisite for effective conversion.
In order to once again establish the enhanced hydrophobicity of
PMOR compared to MOR, an esterification study was carried out at
60 °C. After esterification reaction the catalysts were surface dried
using drying sheet and subjected to thermogravimetric analysis.
From thermograms it is clear that adsorption is mainly concerned
with free fatty acid and methanol, as it is too bulky to enter the
Table 1
Fatty acid profile of neem oil.
Fatty acid Systemic name Formula Structure wt.%
Palmitic Hexadecanoic C16H32O2 16:0 13
Stearic Octadecanoic C18H36O2 18:0 24
Oleic cis-9-Octadecenoic C18H34O2 18:1 62
Linoleic cis-9,cis-12-Octadecenoic C18H3202 18:2 10
Arachidic Eicosanoic C20H40O2 20:0 3.2
Myristic Tetracosanoic C24H4802 14:0 2
5900 V. SathyaSelvabala et al. / Bioresource Technology 101 (2010) 5897–5902

Table 2 catalyst loading, and the methanol oil ratio was found to be high.
Percentage reduction of free fatty acid using modified and unmodified mordenite. Esterification carried out with tungsted zirconia showed 93% con-
Substrate % Reduction of fatty acid version (Table 3), but overall reaction time was 2 h which was
Unmodified mordenite (%) Modified mordenite (%) higher than the reaction catalyzed by PMOR. Comparing PMOR
and MOR, PMOR shows better conversion efficiency with respect
Neem oil 79 92.6
Oleic acid 82 93
to neem oil (Table 2). Generally phosphoric acid modification in-
creases the density of the MOR catalyst because of the bulkier nat-
ure of phosphoric acid. This intern improves the activity of the
parent catalyst. The increased catalyst activity due to the increase
in density was also reported in literature (Lou et al., 2008). The
conversion efficiency for neem oil with MOR is comparable with
the result obtained by Chung et al. (2008) for used oil. From these,
it is evident that PMOR shows good conversion efficiency in ester-
ification of free fatty acid.

3.3. Reaction parameters optimization

Process parameters such as methanol oil ratio, catalyst loading,

Fig. 2. Thermogram of (a) phosphoric acid modified mordenite and
(b) H-mordenite (c) phosphoric acid modified mordenite obtained after esterifica-
tion (c) H-mordenite obtained after esterification.
pores of MOR. The weight loss below 270 °C is attributed to mainly
methanol, but that of between 270 and 550 °C is attributed to the
loss of adsorbed fatty acids (the original MOR showed a weight loss
of about 35.41%) PMOR shows a 40.32% loss of free fatty acids. The
increase of about 5% for the PMOR, compared to the parent MOR, is
attributed to its enhanced hydrophobicity as a result of phosphoric
acid modification. This observation is in accordance with our view
of conferring enhanced hydrophobicity by phosphoric acid
modification.
In Table 3, recently reported literatures on esterification reac-
tion using several heterogeneous acid catalysts with different
starting materials having different FFA concentration are given. It
was found that the conversion was best (100%) with heteropoly
acid immobilized silica, but the time period taken was quite high.
The conversion obtained in our work is comparable to the values
obtained with Metatitanic acid and Lipozyme CALB. In cases, time,
and temperature were found out using the classical method of
optimization. The molar ratio of methanol to oil was studied be-
cause it is one of the most important factors affecting the ester
yield. The studied methanol to oil ratio was 3–9. Up to the ratio
of 6 there was a steady reduction in FFA concentration and further
increase in methanol oil ratio did not make any marked difference
in the yield of ester. So this ratio was adopted as the experimental
limit in order to avoid unnecessary operational expenses. This is in
agreement with the results obtained by Ramadhas et al. (2005).
When the catalyst loading increased from 0.5% to 1.5% (wt./wt.),
the conversion also increased. Up to 1% there was a clear increase
after which it was negligible. Considering the above results 1% was
taken optimum for esterification. Required catalyst loading ob-
served from our experiment was lower when compared to the pre-
vious work (Marchetti and Errazu, 2008; Zhang and Jiang, 2008).
Temperature clearly influenced the reaction rate and yield (Ma
and Hanna, 1999). The temperature range taken for this study
was 30–90 °C. From the results obtained it is evident that when
the temperature increases the reaction rate also increases. But after
a certain temperature the ester yield decreases and the optimum
temperature was fixed at 60 °C. The reason for decrease in esterifi-
cation is described as follows. The boiling point of methanol is
64.7 °C, and the temperature higher than this may burn methanol,
even though there is a condenser.
3.4. Esterification kinetics
The fitting of the experimental data obtained at different meth-
anol oil ratio and catalyst concentration was done by constructing
several plots. Kinetic constants K1 and K2 were obtained and from

Table 3
Comparative analysis of conversion efficiencies for heterogeneous acid catalysts with different starting materials.

Initial free fatty acid Name of catalyst Catalyst Time Oil methanol Temperature Conversion Reference
amount loading ratio (°C) (%)
0.94 mg KOH/g Acidic resin A-15 2 wt.% 40 min 20% vol 50–60 45.7 Ozbay et al. (2008)
21.36 mg KOH/g Dowex monosphere 550 A 2.26 wt.% 120 min 6.128:1 45 – Marchetti et al. (2007)
195 mg KOH/g Lipozyme CALB 2.24 wt.% 3 days 16.13:1 55 96 Marchetti and Errazu
(2008)
279 mg KOH/g H3PW12O40 50 mg 3h 9:1 80 84.9 Xu et al. (2008)
13.7 mg KOH/g Cation exchange resins NKC-9001  7 20% 4h 6:1 66 90 Feng et al. (2010)
and D61
3.5 mg KOH/g WO3/ZrO2 29% 2h 1:9 75 93 Park et al. (2010)
190 mg KOH/g Al-MCM-41 0.6% 2h 60:1 130 79 Carmo et al. (2009)
190 mg KOH/g Heteropoly acids immobilized on 0.2 g 30 h 30 ml 60 100 Caetano et al. (2008)
silica
14 mg KOH/g Metatitanic acid 4 wt.% 2h 20:1 90 97 Lu et al. (2008)
1.25 mg KOH/g Mordenite 1g 3h 30:1 60 80.9 Chung et al. (2008)
24.4 mg KOH/g Phosphoric acid modified mordenite 1% 60 min 6:1 60 92.5 Present work
 V. SathyaSelvabala et al. / Bioresource Technology 101 (2010) 5897–5902 5901

Table 4 ciency was determined based on the conversion of FFA. Process

Kinetic constant values. optimization was carried out using classical method. The optimum
S. No. Catalyst Methanol K1 K2 R2 parameters were found out to be: methanol oil ratio 6; catalyst
loading (wt.%) oil ratio (min1) (g/mg min) loading 1% and temperature 60 °C. Kinetic and thermodynamic
1 0.5 6 0.0208 2.133  104 0.910 studies were done as per pseudo-first order and Arrhenius model
2 1 6 0.0296 3.037  104 0.996 respectively.
3 1.5 6 0.0297 3.043  104 0.980
4 1 3 0.0223 2.283  104 0.909
5 1 6 0.03 3.072  104 0.996 References
6 1 9 0.0306 3.133  104 0.986
Alenezi, R., Leeke, G.A., Winterbottom, J.M., Santos, R.C.D., Khan, A.R., 2010.
Esterification kinetics of free fatty acids with supercritical methanol for
biodiesel production. Energy Conversion and Management 51, 1055–1059.
Berrios, M., Siles, J., Martin, M.A., Martin, A., 2007. A kinetic study of the
Table 5 esterification of free fatty acids (FFA) in sunflower oil. Fuel 86, 2383–2388.
A comparative analysis of FFA reduction kinetics. Caetano, C.S., Fonseca, I.M., Ramos, A.M., Vital, J., Castanherio, J.E., 2008.
Esterification of free fatty acids with methanol using heteropolyacids
S. No Catalyst Rate constant References
immobilized on silica. Catalysis Communication 9, 1996–1999.
K (min1)
Cardoso, A.L., Neves, S.C.G., Da silva, M.J., 2008. Esterification of oleic acid for
1 H2SO4 0.025 Berrios et al. (2007) biodiesel production catalyzed by SnCl2: a kinetic investication. Energies 1, 79–
2 H2SO4 0.00359 Cardoso et al. (2008) 92.
3 SnCl2 0.00278 Cardoso et al. (2008) Carmo, A.C., de Souza, L.K.C., de Costa, C.E.F., Longo, E., Zamian, J.R., da Rocha Filho,
4 Supercritical methanol 0.230 Alenezi et al. (2010) G.N., 2009. Production of biodiesel by esterification of palmitic acid over
mesoporous aluminosilicate Al-MCM-41. Fuel 88 (3), 461–468.
5 PMOR 0.0296 Present work
Chung, K.H., Chang, D.R., Park, B.G., 2008. Removal of free fatty acid in waste frying
oil by esterification with methanol on zeolite catalysts. Bioresource Technology
99, 7438–7443.
Demirbas, A., 2003. Biodiesel fuels from vegetable oils via catalytic and non
the values it is evident that the rate of forward reaction (esterifica- catalytic supercritical alcohol transesterifications and other methods: a survey.
tion) is high when compared to backward reaction (ester hydroly- Energy Conversion and Management 44, 2093–2109.
Feng, Y., He, B., Cao, Y., Li, J., Liu, M., Yan, F., Liang, X., 2010. Biodiesel production
sis). Kinetic constants are given in Table 4. It is evident that K1
using cation-exchange resin as heterogeneous catalyst. Bioresource Technology
increases with increase in methanol oil ratio and catalyst loading. 101, 1518–1521.
This shows esterification reaction follows pseudo-first order kinet- Gui, M.M., Lee, K.T., Bhatia, S., 2008. Feasibility of edible oil vs. non-edible oil vs.
ics. Palani and Pandurangan (2006) showed the good fit to first or- waste edible oil as biodiesel feedstock. Energy 33, 1646–1653.
Hutchings, G.J., Burrows, A., Rhodes, C., Kiley, C.J., McClung, R., 1997. Dealumination
der kinetics over mesoporous Al-MCM-41 molecular sieves. of mordenite catalysts using a low concentration of steam. Journal of the
From the results obtained in the comparative analysis of FFA Chemical Society, Faraday Transaction Articles 93 (19), 3593–3598.
reduction kinetics as shown in Table 5, it is clearly evident that Knothe, G., 2002. Curr. Perspect. Biodiesel Inform. 13, 900–903.
Korkuna, O., Leboda, R., Skubiszewska-Zieba, J., Vrublevska, T., Gunko, V.M.,
the rate constants obtained were high in reactions carried out with Ryczkowski, J., 2006. Structural and physicochemical properties of natural
super critical methanol and PMOR. Even though the result was rea- zeolites: clinoptilolite and mordenite. Microporous and Mesoporous Materials
sonably well in case of supercritical methanol, it is not cost effec- 87, 243–254.
Lotero, E., Liu, Y., Lopez, D.E., Suwannakaran, K., Bruce, D.A., Goodwin, J.G., 2005.
tive. Henceforth, PMOR may be an alternate to the conventional Journal of Industrial and Engineering Chemistry Research 2005 (44), 5353–5363.
acid catalyst. When conventional acid catalyst was used, the rate Lou, W.Y., Zong, M.H., Duan, Z.Q., 2008. Efficient production of biodiesel from high
constant value was comparable with the rate constant value ob- free fatty acid-containing waste oils using various carbohydrate-derived solid
acid catalysts. Bioresource Technology 99, 8752–8758.
tained in the present study. But, by considering the fact that con-
Lu, H., Liu, Y., Zhou, H., Yang, Y., Chen, M., Ling, B., 2008. Production of biodiesel
ventional acid catalysts are difficult to separate from the reaction from Jatropha curcus L. oil. Computers and Chemical Engineering 33 (5), 1091–
mixture, PMOR catalyst is more preferable. 1096.
Ma, F., Hanna, M.A., 1999. Biodiesel production: a review. Bioresource Technology
70, 1–15.
3.5. Thermodynamic studies MacLeod, C.S., Harvey, A.P., Lee, A.F., Wilson, Karen., 2008. Evaluation of the activity
and stability of alkali-doped metal oxide catalysts for application to an
intensified method of biodiesel production. Chemical Engineering Journal 135,
Activation energy values and frequency factors were obtained 63–70.
for forward and reverse reactions during esterification of FFA in Marchetti, J.M., Errazu, A.F., 2008. Comparison of different heterogeneous catalysts
neem oil, as per Arrhenius model. From the results it is evident that and different alcohols for the esterification reaction of oleic acid. Fuel 87 (15–
16), 3477–3480.
the frequency factor of forward reaction was much higher com- Marchetti, J.M., Miguel, V.U., Errazu, A.F., 2007. Heterogeneous esterification of oil
pared to reverse reaction. The frequency factor is a measure of col- with high amount of free fatty acids. Fuel 86, 906–910.
lisions between reactants. If it is much lower for reverse reaction it Meher, L.C., Vidya, S., Dharmagadda, S., Naik, S.N., 2006. Optimization of alkali-
catalyzed transesterification of Pongamia pinnata oil for production of biodiesel.
is preferable because there is a low possibility of reverse reaction. Bioresource Technology 97, 1392–1397.
The activation energy values are also slightly higher for reverse Nabi, M.N., Hustad, J.E., Kannan, D., 2008. First generation biodiesel production from
reaction than forward reaction. The model equations obtained are non-edible vegetable oil and its effect on diesel emissions. In: International
Conference on Thermal Engineering.

31318:84 Ozbay, N., Oktar, N., Alper Tapan, N., 2008. Esterification of free fatty acids in waste
K 1 ¼ 2643:87 exp ð8Þ cooking oils (WCO): role of ion–exchange resins. Fuel 87, 1789–1798.
RT Palani, A., Pandurangan, A., 2006. Esterification of terephalic acid with methanol

33131:3 over mesoporous Al-MCM-41 molecular seives. Journal of Molecular Catalysis

K 2 ¼ 49:4 exp : ð9Þ
RT
4. Conclusions
In this study we showed that PMOR is an efficient alternate to
homogenous acid catalyst for esterification of FFA in neem oil.
The esterification process analyzed in this study showed that the
amount of FFA reduced from 24.4 to 1.8 mg KOH/g oil. Catalyst effi-
A: Chemical 245, 101–105.
Park, J.Y., Kim, D.K., Lee, J.S., 2010a. Esterification of free fatty acids using water-
tolerable Amberlyst as a heterogeneous catalyst. Bioresource Technology 101,
S62–S65.
Park, Y.M., Lee, J.Y., Chung, S.H., Park, I.S., Lee, S.Y., Kim, D.K., Lee, J.S., Lee, K.Y.,
2010b. Esterification of used vegetable oils using the heterogeneous WO3/ZrO2
catalyst for production of biodiesel. Bioresource Technology 101, S59–S61.
Pinto, A.C., Guarieiro, L.L.N., Rezende, M.J.C., Ribeiro, N.M., Torres, E.A., Lopes, W.A.,
Pereira, P.A.P., de Andrade, J.B., 2005. Biodiesel: an overview. Journal of Brazilar
Chemical Society 16, 1313–1330.
Ramadhas, A.S., Jayaraj, S., Muraleedharan, C., 2005. Biodiesel production from high
FFA rubber seed oil. Fuel 84, 335–340.
5902 V. SathyaSelvabala et al. / Bioresource Technology 101 (2010) 5897–5902
Rao, T.V., Rao, G.P., Reddy, K.H.C., 2008. Experiment investigation of pongamia,
jatropha and neem methyl esters as biodiesel on C.I. engine. Jordan Journal of
Mechanical and Industrial Engineering 2 (2), 117–122.
Sharma, Y.C., Sing, B., 2007. Development of biodiesel: curent scenario. Renewable
and Sustainable Energy Reviews 13 (6–7), 1646–1654.
Suryawanshi, J.G., 2008. Combustion of neem oil methyl ester in a direct injection
diesel engine. In: World Renewable Energy Congress.
Wang, W., Lyons, D., Clark, N., Gautam, M., 2000. Emissions from nine heavy trucks
fuelled by diesel and biodiesel blends without engine modification.
Environmental Science and Technology 34, 933–939.
Xu, L., Yang, X., Yu, X., Guo, Y., Maynurkader, 2008. Preparation of mesoporous
polyoxometalate–tantalum pentoxide composite catalyst for efficient
esterification of fatty acid. Catalysis Communications 9, 1607–1611.
Zhang, J., Jiang, L., 2008. Acid catalyzed esterification of Zanthoxylum bungeanum oil
with high free fatty acids for biodiesel production. Bioresource Technology 99
(18), 8995–8998.
Zhang, L., Xian, M., He, Y., Li, L., Yang, J., Yu, S., Xu, X., 2009. A Bronsted acidic
ionic liquid as an efficient and environmentally benign catalyst for biodiesel
synthesis free fatty acids and alcohols. Bioresource Technology 100, 4368–
4373.
Zhang, S., Zu, Y.G., Fu, Y.J., Luo, M., Zhang, D.Y., Efferth, T., 2010. Rapid
microwave-assisted transesterification of yellow horn oil to biodiesel
using a heteropolyacid solid acid catalyst. Bioresource Technology 101,
931–936.
Zheng, S., Kates, M., Dude, M.A., McLean, D.D., 2006. Acid catalysed production of
biodiesel from waste frying oil. Biomass and Bioenergy 30, 267–272.