Biodiesel from minor vegetable oils like karanja oil

and nahor oil

B. K. De* and D. K. Bhattacharyya*
The present study investigated the scope of two minor vegetable oils,
i.e. karanja (Pongamia glabra) oil and nahor (Mesua ferrea L., Guttiferae) oil, as raw material for biodiesel fuel. The distilled fatty acid
methyl esters obtained from karanja oil and nahor oil have the following characteristics: cetane indices 56.2, 54.6; heat of combustion
(kcal/mol) 8.26, 8.39; flash points (C) 134, 142; cloud points (C) 8.3,
6.1, respectively. All these properties of the distilled methyl esters reveal that karanja oil and nahor oil can be suitably used as cheap raw material for the synthesis of biodiesel.

1 Introduction
Karanja (Pongamia glabra) oil and nahor (Mesua ferrea
L., Guttiferae) oil are two oils of Indian origin, which in spite
of having immense potential as raw material, are not exploited and widely used for edible and other purposes. This is due
to their content of toxic non-lipid furanoflavonoids and
coumarins [1].
However, inevitable use of fuels other than petroleum
based diesel fuel was predicted by Diesel some time ago in
1895. A century has passed in course of time, still vegetable
oils or their derived products have not emerged as major
diesel substitute primarily due to some inherent disadvantages of vegetable oils like high viscosity, low volatility etc.
[2]. Scientists then tried to utilize alkyl esters of vegetable
oils in modern diesel engines, which successfully overcame
the previous problems by lowering their viscosity by a factor
of eight and also by increasing the volatility.
Biodiesel i.e. the methyl or ethyl esters of fatty acids,
then did not come into market due to a single, but highly important reason: the costs. To overcome the economic reason
many fleets utilize biodiesel blends called B20 [2], which is
a mixture of 20% biodiesel and 80% petroleum diesel.
Vast amounts of research work are pursued on the production of methyl and ethyl esters from various virgin major oils
e.g. soybean, rapeseed, sunflower, tallow etc., and they have
been completely characterized as biodiesel fuel [28]. Research is also endeavoured to utilize off-quality seed oil
(canola), which is expected to reduce the raw-material (oil)
cost. This however needs some processing steps to remove
sulphur and phosphorus [2].
Another important source of vegetable oil may be found
looking at the fats and oil sources of less competition. Hydrogenated waste frying oil is one such source, though this is
not available world-wide in sufficient quantity, and hydrogenation often increases the pour point above ambient temperature.
However, there are countries like India where thousands
of minor oilseeds are available, which are not used primarily
for their toxicity. Toxicity prevents them from their edible
use and detoxification is therefore found to be the prime step
[9, 10] prior to their edible use. The present study therefore
aimed at utilization of two such non-traditional oils, i.e.
* Department of Chemical Technology, Oil Technology Division, University of Calcutta, India.

404

Fett/Lipid 101 (1999), Nr. 10, S. 404406

Biodiesel aus pflanzlichen Minorlen wie Karanjal und Nahorl.

In der vorliegenden Studie wurden die Verwendungsmglichkeiten von

zwei pflanzlichen Minorlen, nmlich Karanjal (Pongamia glabra)
und Nahorl (Mesua ferrea L., Gutiferae), als Rohstoffe fr Biodiesel
untersucht. Die destillierten Fettsuremethylester aus Karanjal und
Nahorl haben die folgenden Eigenschaften: Cetanindices von 56,2 und
54,6; Verbrennungsenergie 8,26 bzw. 8,39 kcal/mol; Entzndungspunkt
134 bzw. 142 C; Trbungspunkt 8,3 bzw. 6,1 C. All diese Eigenschaften belegen, da sich Karanjal und Nahorl fr die Nutzung als billige
Rohstoffe fr die Synthese von Biodiesel eignen.

karanja oils and nahor oil, which are still not being used as
edible oil, however, they have low costs compared to other
edible oils, for the production of biodiesel and for their characterization.

2 Materials and Methods

2.1 Materials

Crude karanja oil was obtained by the solvent (hexane:

boiling point 6570 C, S.D. Fine Chem., Boiser, Mumbai,
India) extraction of the finely pulverized karanja seed in
Soxhlet apparatus, followed by desolventization at 9095 C,
first at atmospheric pressure and finally under 30 mm Hg
pressure. Crude nahor oil was obtained similarly; the seed
was a gift from State Forest Research Institute, Vanvihar,
Itanagar, Arunachal Pradesh, India.
Methanol, sodium hydroxide, and sulphuric acid were
purchased from S.D. Fine Chem., Boiser, Mumbai, India.
2.2 Methods

Content of free fatty acids, saponification value, and

iodine value of karanja oil and nahor oil were determined
according to the standard methods and practices recommended by the American Oil Chemists Society [11].
Quantitative detection of toxic non-lipids:
Contents of toxic non-lipid furanoflavonoids and
coumarins in the crude oils were determined quantitatively
by partition thin layer chromatography (PTLC). For this, a
known quantity (0.100.15 g) of oil (karanja or nahor) was
spotted on a 20 20 cm glass plate coated with a 0.5 mm
thick layer of silica gel G. The plate was developed in a
90:10 (v/v), hexane:diethyl ether solvent system. The nonlipid band was identified under UV light by the development
of a bluish-white colour. The non-lipid part was extracted
with chloroform, and the quantity was determined gravimetrically.
Transesterification with methanol:
A known quantity (ca. 150 g) of oil (karanja or nahor) and
three times of it (by volume, ca. 450 ml) methanol were
taken in a round bottom flask (capacity 1 l). Catalyst (1%
concentrated H2SO4, 36N, by weight of free fatty acids present) was then added and refluxed over water bath for 5 h.
This acid-catalyzed transesterification process esterified the
free fatty acids nearly quantitatively as evident from thin-

WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999

0931-5985/99/1010-0404$17.50+.50/0

layer chromatography (TLC). Anhydrous sodium hydroxide

pellets were then added in such quantity that after neutralization 0.2% (on weight of oil) sodium hydroxide remains in the
methanol layer. 25 ml excess methanol were then added due
to evaporation loss, and the content of round bottom flask
was refluxed over water bath for another 6 h. After complete
esterification (as evident from TLC) bulk volume of unreacted methanol was distilled off and finally traces of methanol
along with the catalyst NaOH and Na2SO4 (formed previously during neutralization of acid with NaOH) were washed
with water. The methyl ester formed was dried under vacuum (30 mm Hg pressure, 90 C temperature).
Methyl ester thus obtained contained unsaponifiable matters along with toxic furanoflavonoids and coumarins in
karanja oil and nahor oil, respectively. Crude methyl ester
was then distilled at 170190 C under 4 mm Hg pressure to
obtain pure methyl ester usable as biodiesel.
Thin-layer chromatography:
Transesterification of vegetable oils with methanol to
form methyl ester, i.e. biodiesel, was monitored by TLC of
the product mixture. The product mixture was applied on a
20 20 cm glass plate coated with 0.2 mm thick layer of
silica gel G (100120 mesh). The plate was developed in a
solvent system n-hexane-diethyl ether: 90:10 (v/v). After
removal of the solvent the spots were visualized by strong
iodine absorption. Completion of acid-catalyzed and basecatalyzed transesterification reaction was indicated by the
disappearance of fatty acid and triacylglycerol spots, respectively, as identified by comparing with the standard spots.
To determine the suitability for use in diesel engines,
methyl esters were then characterized by determining their
diesel properties following the standard methods. The gross
heat of combustion (HG) of the fatty acid methyl esters
was determined according to the formula proposed by Krishnangkura [12]. Cetane number or the cetane indices were also estimated according to Krishnangkura [13]. Kinematic
viscosity [14], density [15], flash point and fire point [16],
cloud point [17], pour point [18], ash content [19], and sulphur content [20] were determined following the Standard
Methods for Analysis and Testing of Petroleum and Related
Products.

3 Results and Discussion

Some alternative renewable fuels such as biodiesel are
supposed to emerge as prime fuel when the stock of nonrenewable crude petroleum is diminishing world-wide.
Though the technology for production of biodiesel is well
established, the main hurdle for commercial exploitation of
methyl ester biodiesel are the costs. The use of low priced
non-edible minor oils for the production of biodiesel will
likely improve the economy of biodiesel production and its
use. The characteristics of methyl esters of karanja oil and
nahor oil to serve as fuel were therefore investigated in the
present study.
Tab. 1 shows the composition and characteristics of crude
karanja oil and nahor oil, i.e. the fatty raw material for the
synthesis of biodiesel. The oils are dark-coloured and contain 25 wt-% toxic non-lipids [1]. These non-lipids are primarily responsible for the development of dark colour and
toxicity. The fatty acid compositions, saponification value,
iodine value as well as the content of unsaponifiables and
toxic non-lipids indicate that the samples are authentic. After
transesterification with methanol the product was distilled
Fett/Lipid 101 (1999), Nr. 10, S. 404406

Tab. 1. Characteristics and composition of karanja oil and nahor oil

used for the production of methyl ester biodiesel.
Characteristics

Karanja oil
(Pongamia
glabra)

Nahor oil
(Mesua ferrea L.,
Guttiferae)

Colour (Lovibond, 1 inch cell)

35Y + 4.1R

28Y + 17.2R

Free fatty acid [wt-%]

8.3

9.2

Unsaponifiable matter [wt-%]

3.3

2.7

Non-lipid constituents [wt-%]

4.6

3.9

89.9

89.4

189.2

190.6

Palmitic (C16:0) acid

14.1

15.3

Stearic (C18:0) acid

10.9

12.0

Iodine value [g/100 g]

Saponification value [mg/g]
Fatty acid composition [wt-%]

Oleic (C18:1)acid

56.0

53.2

Linoleic (C18:2) acid

15.0

17.0

Arachidic (C20:0) acid

2.1

2.0

Behenic (C22:0) acid

1.9

0.5

90.4

91.5

Yield of distilled methyl ester [wt-%]

under vacuum (at 4 mm Hg pressure and high temperature)

for the purpose of purification. Distilled methyl esters were
found to be free from other impurities as evident from a
single spot in the TLC plate. The yields of distilled methyl
esters were found to be 90.4 and 91.5 wt-%, respectively, for
karanja oil and nahor oil. Small quantities of unreacted
triglyceride and unsaponifiables and the product mono- and
diglyceride would account for the lower yield of distilled
methyl esters.
The physical properties of methyl esters obtained from
karanja oil and nahor oil are shown in Tab. 2. The results
were also compared with the specifications of biodiesel standard DIN V 51606 (Germany) [4] to evaluate their quality.
Specific gravity of the two pure methyl esters was well within the specified limits of 0.875 to 0.900. To determine the
fluidity in the pipe lines and nozzles kinematic viscosity
(mm2/s at 4 C) of the two methyl esters was determined and
was found to be within the speculated range of 3.5 to 5.0 and
have values of 3.8 and 4.1, respectively, for karanja oil and
nahor oil.
The high temperature properties such as flash point and
fire point of the methyl esters were also determined. The
minimum flash point assigned for the biodiesel standard in
Germany is 100 C. The flash points of the methyl ester
biodiesel from karanja oil and nahor oil were 134 and
Tab. 2. Physical properties of methyl ester biodiesel from karanja oil
and nahor oil.
Properties of pure methyl ester

Karanja oil

Nahor oil

Specific gravity [at 15.5 C, kg/l]

0.882
Kinematic viscosity [mm2/s at 40 C]
3.8
Flash point [C]
134
Fire point [C]
141
Cloud point [C]
8.3
Pour point [C]
2.1
Cetane index
56.2
Gross heat of combustion [kcal/mol]
8.26
Sulphur content [wt-%]
0.02
Ash content [wt-%]
0.006

0.897
4.1
142
150
6.1
1.2
54.6
8.40
0.01
0.003

405

142 C, the values being fairly low enough. The low temperature properties of biodiesel, i.e. cloud point and pour point
(referred to in Tab. 2) of the two oils under investigation
were found to be a little high, that can be further improved by
low temperature crystallization.
The gross heat of combustion values (kcal/mol) of the two
methyl esters (8.26 and 8.40, respectively, for karanja and
nahor) are slightly high for using these two methyl esters in
an compression-ignition engine.
The cetane index is important to determine the ignition
quality of a diesel fuel. Cetane index values have therefore
characterized the biodiesel fuels sufficiently. The cetane indices of the biodiesels under investigation are acceptable and
have values of 56.2 and 54.6 for karanja and nahor oil fatty
acid methyl esters.
Sulphur and ash content (as shown in Tab. 2) in the product methyl esters are low enough so that these two oils can be
used as biodiesel.
Characteristics of the karanja and nahor oil fatty acid
methyl esters show that the toxic minor oils can be used in
making biodiesel, which will not only improve the biodiesel
economy, but also save large quantities of edible vegetable
oils. These toxic vegetable oils are found to be a very useful
biodiesel raw material in countries like India where numerous minor oils are available all over the country and even
throughout the year. Countries other than India, where such
minor oils are available may also use these oils in making
biodiesel.

References
[1] N. V. Bringi, Nontraditional Oil Seeds and Oils in India, Oxford &
IBH Publishing Co. Pvt. Ltd., New Delhi 1987.
[2] T. Krawczyk, Biodiesel, INFORM 7 (1996), 801815.
[3] R. Varese and M. Varese, Biodiesel, Ibid. 7 (1996), 816824.
[4] R. O. Dunn and M. O. Bagby, Low-Temperature Properties of
Triglyceride-Based Diesel Fuels: Transesterified Methyl Esters
and Petroleum Middle Distillate/Ester Blends, J. Am. Oil Chem.
Soc. 72 (1995), 895904.

[5] D. F. S. Natusch, D. W. Richardson, and R. J. Joyce, International

Symposium on Alcohol Fuels Technology Conference, May
2125, 1984, Ottawa, Canada, pp. 340 346.
[6] Y. Ali, M. A. Hanna, and S. L. Cuppett, Fuel Properties of Tallow
and Soybean Oil Esters, J. Am. Oil Chem. Soc. 72 (1995),
15571564.
[7] I. Lee, L. A. Johnson, and E. G. Hammond, Use of Branched-Chain
Esters to Reduce the Crystallization Temperature of Biodiesel,
Ibid. 72 (1995), 11551160.
[8] S. Ghosh and D. K Bhattacharyya, Utilization of Acid Oils in Making Valuable Fatty Products by Microbial Lipase Technology, Ibid.
72 (1995), 15411544.
[9] B. K. De and D. K. Bhattacharyya, Refining of Karanja Oil and
Nahor Oil by Batch Liquid-Liquid Extraction, J. Oil Technol.
Assn. of India 29 (1997), 9295.
[10] B. K. De, S. Rakshit, M. Sen, and D. K. Bhattacharyya, Nutritional
quality of detoxified karanja (Pongamia glabra) oil, Fett/Lipid
100 (1998), 4851.
[11] Official and Tentative Methods of the American Oil Chemists Society. Vol. 1, 3rd edition, Additions and Revisions 1975. Ca 5a40,
Cd 3-25, Cd 1-25.
[12] K. Krishnangkura, Estimation of Heat of Combustion of Triglycerides and Fatty Acid Methyl Esters, J. Am. Oil Chem. Soc. 68
(1991), 5658.
[13] K. Krishnangkura, Simple Method for Estimation of Cetane Index
of Vegetable Oil Methyl Esters, Ibid. 63 (1986), 552563.
[14] Standard Methods for Analysis and Testing of Petroleum and Related Products, the Institute of Petroleum, London 1989. Published
by John Wiley & Sons, Great Britain, Method No. IP 71/87
(ASTM D445-87).
[15] Ibid. Method No. IP 160/87 (ASTM D1298-85).
[16] Ibid. Method No. IP 35/63.
[17] Ibid. Method No. IP 219/83 (ASTM D2500-87).
[18] Ibid. Method No. IP 15/67 (ASTM D97-66).
[19] Ibid. Method No. IP 4/81 (ASTM D482-80).
[20] Ibid. Method No. IP 61/84 (ASTM D129-83).
Address of the authors: Prof. Dr. B. K. De and Prof. Dr. D. K.
Bhattacharyya (author to whom correspondence should be sent),
Department of Chemical Technology, University of Calcutta, Oil Technology Division, 92, A.P.C. Road, Calcutta-700 009, W. B., India.
[Received: March 3, 1999; accepted: June 9, 1999].

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