ARTICLE IN PRESS

BIOMASS AND BIOENERGY 32 (2008) 354 357

Available at www.sciencedirect.com

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Production of biodiesel from high free fatty acid Karanja

(Pongamia pinnata) oil

Malaya Naika, L.C. Meherb, S.N. Naikb, L.M. Dasa,

a
Centre for Energy Studies, Indian Institute of Technology, Delhi, Hauz Khas, New Delhi 110016, India
b
Centre for Rural and Development and Technology, Indian Institute of Technology, Delhi, Hauz Khas, New Delhi 110016, India

ar t ic l e i n f o abs tra ct

Article history: Non-edible oil contains several unsaponifiable and toxic components, which make them
Received 26 July 2006 unsuitable for human consumption. Karanja (Pongamia pinnata) is an underutilized plant
Received in revised form which is grown in many parts of India. Sometimes the oil is contaminated with high free
8 October 2007 fatty acids (FFAs) depending upon the moisture content in the seed during collection as
Accepted 15 October 2007 well as oil expression. The present study deals with production of biodiesel from high FFA
Available online 28 November 2007 Karanja oil because the conventional alkali-catalyzed route is not the feasible route. This
paper discusses the mechanism of a dual process adopted for the production of biodiesel
Keywords:
from Karanja oil containing FFA up to 20%. The first step is acid-catalyzed esterification by
Karanja oil
using 0.5% H2SO4, alcohol 6:1 molar ratio with respect to the high FFA Karanja oil to produce
Methanolysis
methyl ester by lowering the acid value, and the next step is alkali-catalyzed
Transesterification
transesterification. The yield of biodiesel from high FFA Karanja oil by dual step process
Biodiesel
has been observed to be 96.697%.
Methyl esters
& 2007 Elsevier Ltd. All rights reserved.

1. Introduction of soap with alkaline catalyst. In the present set of experi-

ments, the alternative route of using acid catalyst was
adopted for biodiesel production from Karanja oil [79].
In consideration of its production potential and emission
Typically Karanja oil, collected for the present investigation,
characteristics, biodiesel derived from locally available non-
was observed to contain 3.2% of free fatty acid (FFA). Oleic
edible oils is being considered as a substitute to diesel fuel in
acid was added in measured quantity to the Karanja oil with a
India. Production of biodiesel from non-edible oil seeds and
view to increase the level of FFA in the oil. It is relevant to
its utilization in diesel engine is being actively pursed in
emphasize here that oleic acid happens to be the major
Engine and Un-conventional Fuel Laboratory at Indian
constituent of Karanja oil. Oleic acid was added to Karanja oil
Institute of Technology Delhi [15].
in desired proportion so as to increase the high FFA content of
Karanja oil is one of the potential oils with yearly
the Karanja oil, 20%, 15% and 5%. Such steps were adopted to
production of 200 t (metric ton), out of which 6% is being
evaluate the effect of FFA level on the production of biodiesel.
presently utilized [6]. The main production area for the
Karanja oil is in the village level and villagers use this oil in
some of their daily activities. This paper highlights the efforts
made to develop biodiesel from Karanja oil, which is available 2. Materials and methods
in rural India. Our experiment in the lab closely agrees with
the reported literature that the presence of high FFA makes In context of the present series of tests, the high FFA
transesterification reaction difficult because of the formation Karanja oil was first converted to esters in a pretreatment

Corresponding author. Tel.: +91 11 2659 1260; fax: +91 11 2658 1121.
E-mail addresses: lmdas@ces.iitd.ernet.in, lmdas1@rediffmail.com (L.M. Das).
0961-9534/$ - see front matter & 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2007.10.006
 ARTICLE IN PRESS
BIOMASS AND BIOENERGY 32 (2008) 354 357 355

process with methanol using acid catalyst (H2SO4). A Bronsted

acid such as H2SO4 is used for methyl esterification of FFA [7].
The reaction was conducted at 65 1C with MeOH/oil at a
molar ratio of 6:1 and an acid catalyst concentration
of 0.5% w/w of oil. Esterification was continued till the
acid value was lowered and remained constant. Subse-
quently, the alcohol layer was removed from the pre-
treated oil before the second step alkaline-catalyzed transes-
terification.
The pretreated oil contains water and acid catalyst
that need to be removed before alkali-catalyzed transe-
sterification. The oil layer was separated from the mixture
and passed over anhydrous Na2SO4 before alkali-catalyzed
transesterification. At the first step, oil was preheated
to 65 1C and the mixture of methanol and KOH was
added to the oil. The reaction was carried out with MeOH/
oil at a molar ratio of 6:1 and catalyst concentration of
1% w/w of oil at 65 1C, which is the optimum condition for
Karanja oil [10].
3. Results and discussion
3.1. Effect of FFA on single-step alkali-catalyzed
transesterification reaction
The decrease in the yield of methyl esters with different levels
of FFA is shown in Fig. 1. It has been observed that the yield of
methyl esters decreases from 97% to 6% by increasing the FFA
content oil from 0.3% to 5.3%.
3.2. Dual step process
3.2.1. Pretreatment of high FFA Karanja oil with acid-
catalyzed esterification
The acid-catalyzed pretreatment of high FFA Karanja
oil results in the value during acid-catalyzed pretreat-
ment is shown in Fig. 2. As evident in the graph during
pretreatment of oil containing 20% FFA, the acid value
decreases from 41.9 to 3.970.3 mg KOH/gin 1 h. Similarly,

2.1. Analysis of biodiesel

Ester content of Karanja methyl esters was determined

100
using high-performance liquid chromatography, Perkin
Elmer Series 200 equipped with a refractive index detector
(Shodex RI 71). A Spheri-5 C-18 column (PerkinElmer Brown- 80
lee Column) (220  4.6 mm with 5 mm particle size) with
1 ml min 1 flow rate of methanol was used as a carrier
Ester (%)

60
solvent with the column kept at 40 1C. The sample
injection was 20 ml and comparing their respective standards
40
made peak identification. The fatty acid methyl esters
composition is given in Table 1. The fuel properties of Karanja
methyl esters were determined as per the ASTM (D6751) 20
standards.
0
0 1 2 3 4 5 6 7
2.2. Purification and characterization of biodiesel
FFA (%)

After the reaction was complete, biodiesel and glycerol Fig. 1 Effect of FFA on the yield of methyl ester during
were separated. Subsequently, the biodiesel was washed alkali-catalyzed transesterification.
with hot distilled water to remove the excess methanol,
catalyst and traces of glycerol. The washed ester layer
was dried at 70 1C under the required vacuum to remove
the moisture and methanol, and it was again passed
45
over anhydrous Na2SO4. The fuel properties of the 40
Karanja biodiesel were compared with the ASTM D6751
35
Acid Value (mgKOH/g)

specifications.
30 6.5 mgKOH/g
25 20 mgKOH/g
40 mgKOH/g
Table 1 Fatty acid composition of Karanja oil 20
9.9 mgKOH/g
15
Fatty acids (Wt %) 10
Palmitic acid 11.65 5
Srearic acid 7.50
Oleic acid 51.59 0
Lilonic acid 16.64 0 15 30 45 60 75 90 105 120
1 Time (Min)
Free fatty acid (mg KOH g ) 520

Fig. 2 Decrease in acid value with time in minutes.

 ARTICLE IN PRESS
356 BIOMASS AND BIOENERGY 32 (2008) 354 357

the acid value decreases up to 3.470.3 mg KOH/g for the oil
containing 510% FFA. This shows that the acid-catalyzed
esterification results in significant reduction of the FFA in
the oil.
3.2.2. Alkali-catalyzed transesterification reaction with the
pretreated acid-catalyzed Karanja oil
The tests conducted proved extremely useful as the pretreat-
ment of high FFA Karanja oil resulted in the reduction of acid
value to an extent, which is suitable for alkali-catalyzed
transesterification.
Then the conventional alkali-catalyzed transesterification
of pretreated oil was used in the reaction to compensate for
the acidity due to H2SO4 and the remaining part acted as
transesterification catalyst. Thus, transesterification was very
effectively carried out, which resulted in the desired products,
biodiesel and glycerol layer.
Fig. 3 closely indicates that Karanja oil with FFA upto 20% is
also capable of producing the appropriate quality of biodiesel.
Experimental results show that the yield of methyl ester
ranged between 96.6% and 97%, when produced from oil
having 20%, 15% and 5% FFA contents.
100
80
Yield of ester (%)
3.3. Fuel properties of Karanja biodiesel
After successful completion of the series of reaction results in
the production of KOME (Karanja Oil Methyl Ester), all the
phisico-chemical properties were experimentally evaluated
as per the ASTM specification, as shown in Table 2. As evident
in the table, the viscosity of Karanja-based biodiesel is found
to be 4.33 cSt, which is well within the limits of ASTM
specification of biodiesel. Its calorific value was found
to be lower than that of the diesel, because of the oxygen
content. The flashpoint of Karanja biodiesel is 174 1C, which is
higher than that of the conventional diesel. Hence, storing
biodiesel and biodiesel diesel blend are safe as compared to
storing diesel alone. The acid value of the biodiesel was found
to be 0.23 mg KOH g 1, which is within the limit of ASTM
specification. All other properties like total glycerin and free
glycerin are also in the range prescribed in the ASTM 6751
specifications.
4. Conclusion
The Indian non-edible oils are often contaminated with FFAs,
depending on the process of oilseed collection, expelling and
storage condition, and contamination of oil/oilseed with
moisture. The conventional alkali-catalyzed route of biodiesel
production does not work out effectively with high FFA
feedstock such as Karanja oil. However, the dual-step process

of transesterification using acid-catalyzed and followed by

60 base-catalyzed reaction proves effective in producing the
appropriate quality of biodiesel as per the ASTM specification.
40

20
Acknowledgement
0
The authors wish to express their gratitude to General Motors,
0 5 10 15 20
USA, for the financial support in carrying these tests in IIT
FFA (%)
Delhi as part of the GM-sponsored on going project entitled
Fig. 3 Effect of FFA on the yield of methyl ester on dual step an experimental evaluation of Karanja based biodiesel as a
process. supplementary diesel fuel.

Table 2 Fuel quality of Karanja biodiesel formed by dual step process

Properties Limits Test methods Biodiesel quality

Flash point, 1C 4130 ASTM D93 174

Water and sediments, % vol. max 0.050 ASTM D2709 0.005
Kin.viscosity at 40 1C (cSt) 1.96.0 ASTM D445 4.33
Sulfated ash, %mass ma 0.020 ASTM D874 0.001
Sulfur, % mass, max 0.0015/.05 ASTM D5453 15 ppm
Cetane number 47 ASTM D613 57.6
Acid value, mg/KOH 1 g 1 0.80 ASTM D974 0.23
Free glycerin, %mass 0.020 ASTM D6584 102 ppm
Total glycerin, %mass 0.240 ASTM D6584 1867 ppm
Phosphorous content, % mass, max 0.001 ASTM D4951 o10 ppm
Distillation temperature 360 max ASTM D1160 356
 ARTICLE IN PRESS
BIOMASS AND BIOENERGY
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