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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


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

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 5899

reverse reactions; R is the universal gas constant. Rate constants ob- vibration of water which lies at 3426 cm1 is very much narrowed
tained at various reaction temperatures were fitted with Eqs. (6) compared to spectrum of MOR. The OH2 bending vibration is lo-
and (7) by nonlinear curve fitting using Matlab 7.0. 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
3. Results and discussion bending vibration is also seen to have reduced intensity. As phos-
phate vibrations also occur in the same region of Si–O–Si asym-
3.1. Characterization of the catalyst metric stretching, the peaks at 1090 and 1216 cm1, also
includes the vibrations of the former. OH vibration of phosphate
The results of NH3 TPD trace of MOR and PMOR are illustrated in generally occurs at 3660 cm1. But it is not clearly resolved in
Fig. 1. In the profile of MOR; there is an intense peak between 100 the higher energy region due to adsorption of water. Hence the
and 300 °C and followed by a broad peak between 350 and 580 °C. above changes indicate the phosphoric acid modification.
The low temperature peak is due to the desorption of NH3 from From the SEM image of MOR it is evident that the presence of
weak acid sites. The latter high temperature peak is attributed to aggregation of small sponge likes morphology. All of them appear
the strong acid site. Among the weak acid sites, distribution of acid nearly similar without any impure phase. Similar result was also
strength is evident. There are four maximums lying close to 150, reported in the literature (Korkuna et al., 2006). Aggregation of
175, 185, and 225 °C. In the region of strong acidity, a gradual var- sponge like morphology is also seen in the image of PMOR similar
iation in acid strength is observed. The volume of NH3 desorbed, to that of the MOR. Hence, as a result of phosphoric acid modifica-
corresponding to weak acid sites is 4.92 mL/g where as for strong tion, there might not be any structural degradation. Compared to
acid sites, and it is 3.5 mL/g. In the profile of PMOR, there is an in- MOR, the aggregates appear larger in size in the modified image.
tense broad peak between 100 and 350 °C. It includes large It is also supported by XRD results as discussed above. Hence phos-
amounts of weak acid sites and a portion of medium acid sites. phoric acid modification might have some role in the agglomera-
The broad peak due to strong acid sites in Fig. 1b (above 350 °C) tion of particles altogether. In other words, phosphoric acid in
are absent in Fig. 1a. Hence, as a result of phosphoric acid modifi- each particle, instead of lying exclusively inside the pore, might
cation, strong acid sites are converted into weak acid sites. The vol- also expose outwards to interact with other particles in order to
ume of NH3 desorbed is equal to 5.87 mL/g. It is clear that there is facilitate agglomeration.
an increase in the acidity of PMOR compared to MOR catalyst.
The XRD patterns of MOR resemble those reported in literature
3.2. Catalyst activity on esterification reaction
(Hutchings et al., 1997). Most of the patterns of parent MOR are re-
tained in the spectrum of PMOR illustrating avoidance of crystalli-
Results of esterification reaction in terms of percentage of free
zation loss as a result of phosphoric acid modification. There is a
fatty acid removal of neem oil and oleic acid using PMOR and
decrease in the intensity of the patterns but no complete disap-
MOR are given in Table 2. From the results it is apparent that ester-
pearance of peaks.
ification reaction is well favored by PMOR than MOR in both the
In FTIR spectrum of MOR there is an intense broad band, be-
substrates. The higher acid value reduction for PMOR compared
tween 2600 and 3700 cm1, is due to the OH bond stretching vibra-
with MOR is discussed as follows. The higher acid value reduction
tion of water. The corresponding bending vibration is seen in
is conformed by the high hydrophobic property of PMOR when
1646 cm1. The asymmetric Si–O–Si vibration gives an intense
compared to MOR. High hydrophobic property requires less
broad peak between 1000 and 1300 cm1. The peaks at 759 and
amount of water absorption, and it was tested by thermogravimet-
810 cm1 are due to symmetric vibration of Si–O–Si bonds. The
ric analysis of both PMOR and MOR. The thermogram is presented
bending bond modes of Si–O–Si give a sharp intense peak at
in Fig. 2. The percentage loss of water was found to be 12.25% for
459 cm1. The above results are comparable to reported spectrum
PMOR and 24% for MOR. Hence the PMOR is confirmed to be more
(Korkuna et al., 2006). In the PMOR spectrum, the OH stretching
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
Fig. 1. NH3 TPD profile of (a) phosphoric acid modified mordenite and Myristic Tetracosanoic C24H4802 14:0 2
(b) H-mordenite.
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,


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.),
Fig. 2. Thermogram of (a) phosphoric acid modified mordenite and the conversion also increased. Up to 1% there was a clear increase
(b) H-mordenite (c) phosphoric acid modified mordenite obtained after esterifica-
tion (c) H-mordenite obtained after esterification.
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-
pores of MOR. The weight loss below 270 °C is attributed to mainly vious work (Marchetti and Errazu, 2008; Zhang and Jiang, 2008).
methanol, but that of between 270 and 550 °C is attributed to the Temperature clearly influenced the reaction rate and yield (Ma
loss of adsorbed fatty acids (the original MOR showed a weight loss and Hanna, 1999). The temperature range taken for this study
of about 35.41%) PMOR shows a 40.32% loss of free fatty acids. The was 30–90 °C. From the results obtained it is evident that when
increase of about 5% for the PMOR, compared to the parent MOR, is the temperature increases the reaction rate also increases. But after
attributed to its enhanced hydrophobicity as a result of phosphoric a certain temperature the ester yield decreases and the optimum
acid modification. This observation is in accordance with our view temperature was fixed at 60 °C. The reason for decrease in esterifi-
of conferring enhanced hydrophobicity by phosphoric acid cation is described as follows. The boiling point of methanol is
modification. 64.7 °C, and the temperature higher than this may burn methanol,
In Table 3, recently reported literatures on esterification reac- even though there is a condenser.
tion using several heterogeneous acid catalysts with different
starting materials having different FFA concentration are given. It 3.4. Esterification kinetics
was found that the conversion was best (100%) with heteropoly
acid immobilized silica, but the time period taken was quite high. The fitting of the experimental data obtained at different meth-
The conversion obtained in our work is comparable to the values anol oil ratio and catalyst concentration was done by constructing
obtained with Metatitanic acid and Lipozyme CALB. In cases, time, 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
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