Renewable Energy 34 (2009) 762–765

Contents lists available at ScienceDirect

Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Biodiesel production process optimization and characterization to assess the

suitability of the product for varied environmental conditions
T. Eevera*, K. Rajendran, S. Saradha
Department of Biotechnology, Periyar Maniammai University, Periyar Nagar, Vallam, Thanjavur, Tamilnadu 613 403, 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, both edible (coconut oil, palm oil, groundnut oil, and rice bran oil) and non-edible oils
Received 10 September 2007 (pongamia, neem and cotton seed oil) were used to optimize the biodiesel production process variables
Accepted 17 April 2008 like catalyst concentration, amount of methanol required for reaction, reaction time and reaction tem-
Available online 17 June 2008
perature. The fuel properties like specific gravity, moisture content, refractive index, acid value, iodine
number, saponification value and peroxide value were estimated. Based on the cetane number and iodine
Keywords: value, the methyl esters obtained from palm and coconut oils were not suitable to use as biodiesel in cold
Transesterification
weather conditions, but for hot climate condition biodiesel obtained from the remaining oil sources is
Biodiesel
Edible and non-edible oils
suitable.
Saponification value Ó 2008 Elsevier Ltd. All rights reserved.
Iodine value
Cetane number

1. Introduction process optimization and fuel property characterization to assess

The increased use of diesel fuel resulted in depletion of its fossil
reserves. This triggers for many initiatives to search for alternate
fuel, which can supplement or replace such fossil fuel. In recent
years, research has been directed to explore plant-based fuels and
plant oils and fats as fuels have bright future [1]. The most common
that is being developed and used at present is biodiesel, which is
fatty acid methyl esters of seed oils and fats and have already been
found suitable for use as fuel in diesel engine. Biodiesel is found to
be environmentally safe, non-toxic and biodegradable [2].
The raw material being exploited commercially by the de-
veloped countries constitutes the edible fatty oils derived from
rapeseed, soybean, palm, sunflower, coconut, linseed, etc. [3]. Use
of such edible oil to produce biodiesel in India is not feasible in view
of a big gap in demand and supply of such oils in the country. In-
creased pressure to augment production of edible oil has also put
limitation on the use of these oils for production of biodiesel. Under
such conditions, those crops that produce non-edible oil in
appreciable quantities can be grown in large scale in non-cropped
marginal lands and wastelands only considered for biodiesel
production [4].
Long list of trees, shrubs and herbs is available plenty in India,
which can be exploited for fuel production. In this study we have
utilized both edible and non-edible oils for the biodiesel production
* Corresponding author.
E-mail address: teevera2000@yahoo.com (T. Eevera).
the suitability of the different methyl esters to the varied envi-
ronmental conditions.
2. Materials and methods
Edible (coconut oil, palm oil, groundnut oil, rice bran oil, and
gingelly oil) and non-edible (pongamia, cotton seed oil and neem
oil) oils were used in this experiment.
All the oils were first filtered by cloth mainly to remove the dirt
and other inert materials from the oil and then placed in a conical
flask equipped with magnetic stirrer, thermometer and condenser.
Under agitation the raw oil was heated up to nearer to the boiling
point to remove the water contaminant present in the oil. After that
oil is allowed to cool down under room temperature, and the
treated oil alone was taken for biodiesel production purpose. Again,
under agitation, the above treated oil was heated up to a desired
temperature on a hot plate. A fixed amount of freshly prepared
sodium hydroxide–methanol solution was added into the oils,
taking this moment as the starting time of the reaction. When the
reaction reached the preset reaction time, heating and stirring were
stopped. The products of reaction were allowed to settle overnight.
During settling two distinct liquid phases were formed: crude ester
phase at the top and glycerol phase at the bottom. The crude ester
phase separated from the bottom glycerol phase was then washed
by cold or warm de-ionized water several times until the washed
water became clear. The excess methanol and water in ester phase
were then removed by evaporation under atmospheric condition.

0960-1481/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.renene.2008.04.006
 T. Eevera et al. / Renewable Energy 34 (2009) 762–765 763

After that weight of the ester was taken for product yield 1
calculation.
The reaction was investigated step by step. The optimal value of
each parameter involved in the process was determined while
the rest of the parameters were kept constant. After each optimal
value was attained, this value was adopted for the optimization of
the next parameter.

Methyl esters yield (Wt.%)

Physical and chemical properties of methyl esters were esti- 0.9
mated [5,6] under laboratory conditions. The cetane number (CN)
and higher heating values (HHVs) were calculated [4,6] from the
following equation by using the estimated saponification value (SV)
and iodine value (IV).

CN ¼ 46:3 þ 5458=SV  0:225IV (1)

0.8
HHV ¼ 49:43  ½0:041ðSVÞ þ 0:015ðIVÞ (2)

Pongamia Palm
3. Result and discussion
Neem Cotton seed
Groundnut Rice bran
3.1. Effect of catalyst concentration
Gingelly Coconut

The effect of sodium hydroxide concentration on the trans- 0.7

esterification of the edible and non-edible oils was investigated 0.5 1 1.5 2 2.5
with its concentration varying from 0.5 to 2.5 wt.% (based on the Catalyst concentration (Wt.%)
weight of raw oil). The operation conditions during the whole re-
Fig. 1. Effect of catalyst concentration on methyl esters’ yield.
action process were fixed at the optimal level: reaction temperature
of 55  C, reaction time of 90 min. and 180 and 210 ml of methanol
3.3. Effects of methanol amount
for edible and non-edible oils, respectively.
Experimental results showed changes in ester yield content
The effect of alcohol amount on yield of the transesterification
with varied catalyst concentration. As the sodium hydroxide
experiments was conducted with different amounts of methanol
concentration increased, the conversion of triglyceride as well as
to oil in the range of 120–240 ml. The optimized catalyst con-
the ester content also increased. Insufficient amount of sodium
centration and reaction time as obtained in the above sections
hydroxide resulted in incomplete conversion of triglycerides into
were adopted. Maximum ester content was obtained at a metha-
the esters as indicated from its lower ester content. The ester
nol amount of 180 ml for edible oil and 210 ml for non-edible oils.
content reached an optimal value when the sodium hydroxide
With further increase in the methanol to oil amount above
concentration reached 1.5 wt.%, and further increase in catalyst
210 ml, a very little effect on the biodiesel yield was observed
concentration in all the cases, ester production amount decreased
as shown in Fig. 1. Large amount of soap was observed in excess
amount of sodium hydroxide added experiments. This is because 1
addition of excess alkaline catalyst caused more triglycerides’
participation in the saponification reaction with sodium hydrox-
ide, resulting in the production of more amount of soap and
reduction of the ester yield [7].

3.2. Effect of reaction time

Methyl ester yield (Wt.%)

0.9
The reaction time of the transesterification reaction conducted
at 55  C was optimized with the highest achievable mixing degree,
an excess amount of alcohol (220 ml per liter of oil) and optimal
sodium hydroxide concentration of 1.5 wt.% for all the oils.
The changes in product composition with reaction time during
the transesterification of the oils and the distribution of various
components in the reaction system can be clearly seen. When the
reaction time reached 90 min, no triglyceride was left in the product 0.8
mixture, indicating complete conversion. In this experiment, glycerol
started to separate within 15 min. The ester content increased with
reaction time from 15 min onwards and reached a maximum at Pongamia Palm
a reaction time of 90 min at 55  C, and then remained relatively Neem Cotton seed
constant with increasing further the reaction time (Fig. 2). The results Groundnut Rice bran
indicated that an extension of the reaction time from 90 to 150 min Gingelly Coconut
had no significant effect on the conversion of triglycerides but leads 0.7
to a reduction in the product yield. This is because longer reaction 30 60 90 120 150
enhanced the hydrolysis of esters (reverse reaction of trans-
Reaction time (min.)
esterification), resulted in loss of esters as well as causing more fatty
acids to form soap. Fig. 2. Effect of reaction time on methyl esters’ yield.
764 T. Eevera et al. / Renewable Energy 34 (2009) 762–765

(Fig. 3). Moreover, it was observed that for high alcohol amount 1
added the set up required longer time for the subsequent sepa-
ration stage since separation of the ester layer from the water
layer becomes more difficult with the addition of a large amount
of methanol. This is due to the fact that methanol, with one polar
hydroxyl group, can work as an emulsifier that enhances emul-
sion. Therefore, increasing the alcohol amount to oil is another
important parameter affecting the biodiesel yield and biodiesel

Methyl esters yield (Wt.%)

0.9 Pongamia Palm
purity, apart from catalyst concentration and reaction time. This
Neem Cotton seed
result is in line with the report of many investigations based on
Groundnut Rice bran
neat vegetable oils [7–9]. However the non-edible like pongamia
Gingelly Coconut
and neem require 210 ml of methanol to give maximum ester
yield, possibly due to higher viscosity of non-edible oil than ed-
ible oils. In this case more amount of methanol is required to
increase the solubility of the oil in the methanol. This leads to
maximize the ester yield at high methanol concentration level. 0.8
However, when compared to edible oil ester content yield was
minimal in non-edible oil but glycerol yield was found to be more
in non-edible oil when compared to edible oil.

3.4. Effect of reaction temperature

To study the effect of reaction temperature on methyl esters’ 0.7

formation, the transesterification reaction was carried out under 40 45 50 55 60
the optimal conditions obtained in the previous section (i.e. 180 and Reaction temperature (degree C)
210 ml of methanol for edible and non-edible oils, respectively, and
1.5 wt.% sodium hydroxide). The experiments were conducted at Fig. 4. Effect of reaction temperature on methyl esters’ yield.
temperature ranging from 40 to 60  C at 5  C interval. The effect of
reaction time was shown in Fig. 4.
3.5. Methyl ester chemical and physical property
Experimental results showed that the transesterification re-
action could proceed within the temperature range studied but the
Fuel properties like specific gravity, moisture content, refractive
reaction time to complete the reaction varied significantly with
index, acid value (AV), iodine value (IV), saponification value (SV)
reaction temperature. It can be seen that a high product yield could
and peroxide value (PV) were estimated. The cetane number (CN)
be achieved at 50  C. With the temperature increase above 55  C,
and higher heating values (HHVs) of methyl ester were calculated
the product yield started to decrease. The reason for this is that
based on the estimated SV and IV (Tables 1 and 2).
higher temperature accelerates the side saponification reaction of
The estimated SV and IV range from 188 to 259 and 9 to 113,
triglycerides.
respectively. The CN value among the oils varied from 49.91 to
65.34; the HHV ranges in between 38.68 and 40.33 among the
different methyl esters.
1 CN is the ability of fuel to ignite quickly after being injected.
Better ignition quality of the fuel is always associated with higher
CN value. This is one of the important parameter, which is con-
sidered during the selection of methyl esters for use as biodiesel.
For this different countries/organization have specified different
minimum values. Biodiesel standards of USA (ASTM D 6751),
Germany (DIN V51606) and European Organization (EN 14214)
Methyl ester yield (Wt.%)

0.9
have set this value as 47, 49, and 51, respectively [10]. In our ex-
periment all the different methyl esters have CN value of higher
than 51 except methyl esters obtained from gingelly (49.91) and
groundnut (50.51) oils.
Another important criterion for selection of methyl esters is its
degree of unsaturation, which is measured as IV. To an extent, the
0.8

Table 1
Pongamia Palm Physical property of methyl esters

Neem Cotton seed S. No. Biodiesel Specific Viscosity Moisture content Refractive
Groundnut Rice bran gravity (106 Ns/m2) (wt.%) index
Gingelly Coconut 1 Pongamia 0.942 34.66 0.16 1.4447
2 Neem 0.942 26.286 0.35 1.4456
0.7 3 Palm 0.870 17.81 0.19 1.4418
120 150 180 210 240 4 Cotton seed 0.874 13.27 0.52 1.4428
Alcohol amount (ml) 5 Rice bran 0.878 18.95 0.72 1.4487
6 Gingelly 0.873 13.3 0.24 1.4466
Fig. 3. Effect of methanol concentration on methyl esters’ yield. 7 Groundnut 0.878 16.62 0.45 1.4495
8 Coconut 0.868 12 0.82 1.4271
 T. Eevera et al. / Renewable Energy 34 (2009) 762–765 765

Table 2
Chemical property of methyl esters

S. No. Biodiesel AV SV IV PV Moisture content (wt.%) HHV (kJ/g) CN

1 Pongamia 0.5 194 84 15.78 0.16 40.216 55.53
2 Neem 0.6 189 99 16.08 0.35 40.196 52.9
3 Palm 0.2 201 57 11.31 0.19 40.334 60.62
4 Cotton seed 0.3 199 76 12.52 0.52 40.131 56.63
5 Rice bran 0.4 188 100 15.02 0.45 40.222 52.83
6 Gingelly 0.1 188 113 14.66 0.72 40.027 49.905
7 Groundnut 0.2 187 111 19.21 0.24 39.048 50.51
8 Coconut 0.1 259 9 1.52 0.82 38.676 65.34

presence of unsaturated fatty acid component in methyl esters is
required as it restricts the methyl esters from solidification. How-
ever, with higher degree of unsaturation, methyl esters are not
suitable for biodiesel as the unsaturated molecules react with
atmospheric oxygen and are converted to peroxide, cross-linking at
the unsaturation site can occur and the material may get poly-
merized into a plastic like body. At high temperature, commonly
found in an internal combustion engine, the process can get ac-
celerated and the engine can quickly become gummed up with the
polymerized methyl esters. To avoid this kind of situation, biodiesel
standards have set a minimum limit of IV in their specifications. All
the eight species, which qualify the specification of CN, also meet
the specification of IV. All of them have IV less than 115, the lowest
maximum limit among the three biodiesel standards set by
European Organization (EN 14214 [10b]).
Generally, methyl esters with higher CN are favored for use as
biodiesel. However, with increase of CN, IV decreases which means
degree of unsaturation decreases. This situation will lead to the
solidification of methyl esters at higher temperature. To avoid this
situation, the upper limit of CN (65) has been specified in US bio-
diesel standards (ASTM D 6751-99 & ASTM PS 121-99) [10c,10d].
Among the eight methyl esters, which already met the specification
of CN and IV of biodiesel standards, two of them like palm and
coconut esters have low IV (<57.0) and exceed the upper limit of
CN. So these two methyl esters are not suitable to use as a biodiesel
in the cold weather conditions. The oils from remaining, as men-
tioned in the respective sources, are liquids under laboratory con-
ditions, can be used both in cold and hot climates.
increases beyond the optimum level it induces a negative im-
pact on the ester yield due to acceleration of the saponification
of triglycerides.
 Sufficient reaction time should be allowed to ensure complete
conversion of triglycerides into esters. However, excess
reaction time did not promote the conversion but favors the
reverse reaction of transesterification which resulted in a re-
duction in the ester yield.
 The optimal reaction conditions for production of methyl
esters from edible oil sources are established as follows: the
reaction time of 90 min at 50  C, 180 ml of methanol for
1000 ml of oil and 1.5 wt.% of NaOH catalyst. For non-edible
oil based methyl esters’ production except the amount of
methanol (210 ml/1000 ml of oil) requirement, the remaining
optimal parameters are similar to edible oil based methyl
esters’ production.
 Based on CN and IV, the palm and coconut oil based methyl
esters are not suitable to use as a biodiesel in cold weather
conditions. In hot climate conditions, however, all the methyl
esters produced in this experiment including coconut and palm
oil based esters are suitable to use as a fuel.
Acknowledgment
The authors thank Dr. K. Veeramani, Chancellor and Dr. N.
Ramachandran, Vice-Chancellor, Periyar Maniammai University for
encouragement and research funding.

4. Conclusion References

The study on the biodiesel production process optimization of
edible and non-edible oils showed that the quantity of catalyst,
amount of methanol, reaction temperature and reaction time are
the main factors affecting the production of methyl esters. The
optimal values of these parameters for achieving maximum con-
version of oil to esters depended on the chemical and physical
properties of these oils. The following conclusions are drawn from
the study:
 Addition of excess catalyst causes more triglycerides’ partici-
pation in the saponification reaction leading to a marked
reduction in the ester yield.
 Biodiesel production process is incomplete when the methanol
amount is less than the optimal value. Operating beyond the
optimal value, the ester yield would not be increased but will
result in additional cost for methanol recovery.
 Higher reaction temperature decreases the viscosities of the
[10] (a) Biodiesel standard, DIN V51606, Germany 1994. (b) Biodiesel standard, EN
oils and resulted in increased rate of transesterification and
shortening of the reaction time. When the temperature
[1] Martini N, Shell JS, editors. Plant oils as fuels – present state of science and
future development. Berlin: Springer; 1998. p. 276.
[2] Harrington KJ. Chemical and physical properties of vegetable oil esters and
their effect on diesel fuel performance. Biomass 1986;9:1–17.
[3] Korbitz W. Biodiesel production in Europe and North America, an encouraging
prospect. Renewable Energy 1999;16:1078–83.
[4] Mohibbe Azam M, Waris Amtul, Nahar NM. Prospects and potential of fatty
acid methyl esters of some non-traditional seed oils for use as biodiesel in
India. Biomass and Bioenergy 2005;29:293–302.
[5] Hodl P. Handbook of analytical methods for fatty acid methyl esters used as
biodiesel fuel substitutes. Vienna: Research Institute for Chemistry and
Technology; 1994.
[6] Demirbas Ayhan. Fuel properties and calculation of higher heating values of
vegetable oils. Fuel 1998;77:1117–20.
[7] Leung DYC, Guo Y. Transesterification of neat and used frying oil: optimization
for biodiesel production. Fuel Processing Technology 2006;87:883–90.
[8] Zhang Y, Dube MA, Mclean DD, Kates M. Biodiesel production from waste
cooking oil: 2. Economic assessment and sensitivity analysis. Bioresource
Technology 2003;90:229–40.
[9] Freedman B, Pryde EH, Mounts TL. Variables affecting the yield of fatty esters
from transesterified vegetable oils. Journal of the American Oil Chemists’
Society 1984;61:1638–43.
14214, European Standards Organization 2003. (c) Biodiesel standard, ASTM D
6751, USA 1999. (d) Biodiesel standard, ASTM PS 121, USA 1999.