CISAK 2013 C2/P/18

Alternative transesterification methods for biodiesel

production A review
Ayunda Nuradhisthana Utomo1
Chemical Engineering Department, Diponegoro University, Semarang, Indonesia
1
ayunda.utomo@gmail.com

Abstract. The serious increasing price of petroleum and the environmental effect was became the background for searching some
alternative diesel fuels (biodiesel) from renewable resources such as jatropha tree (Jatropha curcas), karanja (Pongamia pinnata),
tobacco seed (Nicotianatabacum L.), rice bran, mahua (Madhuca indica), neem (Azadirachta indica), rubber plant (Hevea
brasiliensis), castor, linseed, and microalgae. Biodiesel have many advantages such as made from renewable resources, readily mixes
with petroleum diesel fuel in any ratio, restores lubricity of low-sulfur diesel fuel by mixing as little as 1% biodiesel, can be burned
in modern diesel without modification, low toxicity, no sulfur dioxide (SO2) emissions, degrades more rapidly than diesel fuel, lower
emissions of contaminants: carbon monoxide, particulate matter, polycyclic aromatic hydrocarbons, aldehydes. Some disadvantages of
biodiesel like higher cloud point and pour point, higher nitrogen oxide (NOx) emission, lower engine speed and power, high viscosity,
injector coking, cold start problem, high copper strip corrosion, high price and higher engine wear. There are several
transesterification methods to produce biodiesel such as: conventional transesterification oil method, in situ process, ultrasound
assisted process, microwave, and enzymatic. Although biodiesel production from microwave and ultrasound assist will soon have a
bright future, a low cost production in industrial production still need to be explored and developed.
Keywords : Biodiesel, transesterification, in situ, ultrasonic, microwave, enzymatic.

1.

Introduction
The serious increasing price of petroleum and the
environmental effect was became the background for searching
some alternative diesel fuels from renewable resources called
biodiesel, such as jatropha tree (Jatropha curcas) [1,2], karanja
(Pongamia pinnata) [3,4], tobacco seed (Nicotianatabacum L.)
[5,6], rice bran [7,8], mahua(Madhuca indica) [9,10], neem
(Azadirachta indica) [11], rubber plant (Hevea brasiliensis)
[12,13], castor [14], linseed [15], and microalgae [16,17]. Many
studies have investigated the economic and environmental
impacts of the biofuels; such as biodiesel, bioethanol, biogas and
biohydrogen [1820]. In some applications, biodiesel can be a
direct replacement for diesel fuel in vehicle engines. Biodiesel
can be used in normal diesel engines without any modication
and has similar combustion characteristics to those of diesel [21].
When biodiesel blended with diesel fuel, the designation will
indicates the amount of BXX in the blend. For example B20 was
20% biodiesel and 80% diesel fuel and Europe used B5, it
contains 5% biodiesel in diesel fuel. Some standard was used to
determine the quality of the biodiesel like ASTM 6751
(American Society for Testing and Materials) and EN 14214
(European standard)[22].
Table 1
Potential biodiesel in several countries ascending order: [23]
No. Country
Biodiesel potential(ML) Production ($/L)
1
Malaysia
14,540
0.53
2
Indonesia
7595
0.49
3
Argetina
5255
0.62
4
USA
3212
0.70
5
Brazil
2567
0.62
6
Netherlands
2496
0.75
7
Germany
2024
0.79
8
Philippines
1234
0.53
9
Belgium
1213
0.78
10 Spain
1073
1.71

2. Advantages and Disadvantages of Biodiesel

2.1 Advantages
Biodiesel have been found to be a promising future fuel. The
advantages of biodiesel fuel are made from renewable resources,
readily mixed with petroleum diesel fuel in any ratio, restored
lubricity of low-sulfur diesel fuel by mixing as little as 1%
biodiesel, can be burned in modern diesel with no modification
[24], low toxicity, no sulfur dioxide (SO2) emissions, degrade
more rapidly than diesel fuel, lower emissions of contaminants:
carbon monoxide, particulate matter, polycyclic aromatic
hydrocarbons, aldehydes [25].
2.2 Disadvantages
There are some disadvantages of using biodiesel as a
replacement for diesel fuel that must be taken into consideration
such as higher cloud point and pour point, higher nitrogen oxide
(NOx) emission, lower engine speed and power, high viscosity,
injector coking, cold start problem, high copper strip corrosion,
high price and higher engine wear [26].
3.

Alternative transesterification methods for biodiesel

production
There are several transesterification methods to produce
biodiesel such as: conventional transesterification oil method
[27-29], in situ process [28-33], ultrasound assisted process [3439],
microwave
[40-44],
and
enzymatic
[45-49].
Transesterification is the reaction process to change the
triglyceride molecules present in animal fats or vegetable oils
react with an alcohol (Fig 1). The reaction are often catalyzed by
acid and base catalyst or enzyme. Different types of alcohols can
be used to produce biodiesel such as methanol, ethanol, propanol
and butanol. Nevertheless, methanol and ethanol are the most
widely that used in biodiesel process.

Figure 1. Transesterication reaction of triglicerides[50-53]

3.1 Conventional transesterification methods
Conventional transesterification method is reacting vegetable
oil (oil extraction) with alcohol and catalyst. For oil extraction,
the seed dried in an oven at 85oC for 1 h. The seed reduced of
particle size by using blender and then oil extracted by pressing
or extracting with solvent. Oil must be pretreated with
degumming or esterification (free fatty content >0.5%). Oil was
heated to reaction temperature and catalyst was added in reactor
[29]. Due to the efficiency of reaction time and to improve the
high quality oils, conventional transesterification was compared
with in situ transesterification [28,29].
3.2 In situ transesterification
In situ transesterification is an alternative method of
producing ester transport fuels. It differs from the conventional
reaction in that the oil-bearing material contacts with acidified or
alkalized alcohol directly instead of reacting with pre-extracted
oil and alcohol [29]. This method need a catalyst to activate the
reaction. Acid or alkali catalyst helps to breaks the cell wall of
the seeds and increases the ability of the solvent to access the oil.
Previous study reported that in-situ process had many advantages
such as reduce the production time [54], reduce the reagents,
solvents used, wastewater production, and significantly
maximized ester yield [55]. Johnson and Wen [56] studied that
the in situ transesterification process of Schizochytrium
limacinum, was resulted in 63.5% of the fatty acid methyl ester
(FAME) while Ehimen et al. [57] reported that high quality
biodiesel with almost 93% FAME content from Chlorella strains
was produced. The purity of the yield is defined as the percentage
of methyl esters in product obtained from the purification stage.
This percentage is mostly obtained from a gas chromatogram
result.
3.3 Ultrasound assisted process
Due to immiscible nature from the sample and different
density of the reactant (alcohol and vegetable oil), poor
interaction between them will leads to low reaction rates and
increase the reaction time [58, 59]. The use of ultrasonic energy
in biodiesel production process is an effective and attractive
procedure to solve problems that are faced by conventional
methods. Ultrasonic irradiation can enhance mass transfer rate
between the reactants which are immiscible liquids. The
advantages of these cavitation was have temperature near
boundary layer and formation of micro jets eliminates the need
for intense mechanical agitation to improve mass transfer
between the two reactant phases [37] also avoided increase
excessive temperature of the reaction mixture [38]. The
important operating parameters related to the chemistry of the
biodiesel synthesis include molar ratio of methanol to oil,
operating temperature, and catalyst concentration. Ultrasonic
offer considerable promise for intensification of biodiesel

production from sustainable raw materials [60]. Lee et al. [61]

reported that biodiesel yield from vegetable oils were increased
as irradiation power (from 150-450 W). However, methyl ester
content was decreased at irradiation power above 450 W. Hence,
the pulse type irradiation at 450 W ultrasonic power was the
optimum procedure. This result was in accordance with a study
from Ehimen et al. [57] which reported that the transesterification
process could be improved due to the use of ultrasound and cosolvent by 15-17% compared with the use of methanol and acidic
catalysts. Ultrasonication at 24 kHz for 40 min had the highest
yield of methyl esters and ethyl esters from sun flower seed
during transesterification using 2% NaOH as catalyst. Whereas
time (min) had effect on increased the yield percentage on transesterification process using mechanical stirring at 600rpm as the
additional treatment [28].
3.4 Microwave
Microwave is non-ionizing radiations with low energy
content that therefore cannot ionize the atom crossed. These
radiations can influence molecular movements (ion migration or
dipole reactions) but not change the molecular structure. The
microwave energy interact with the sample at molecular level,
thus heating become more efficient. For a short time there is a
localized overheating since the continuous interaction of the
molecules generates energy [43]. Sherbiny et al. [42] mentioned
that highest biodiesel yield was reached 97.4% by applying
microwave irradiation for two minutes compared to 1 h with the
conventional technique. It was accordance with Reefat et al. [62]
which the result indicated use microwave irradiation give very
fast time (2 min) compared with conventional technique (60
min). The yield is increasing from 96% to 100% under the same
reaction conditions. Microwave technique was found as a
promising technique to produce high quality biodiesel and can
reduce the production cost comparing with the conventional
techniques [63].
3.5 Enzymatic
The enzymatic transesterification can be a solution for
solvent-free systems. For biodiesel production, enzymes can be
used as the catalyst. However, to make enzymatic
transesterification competitive on industrial scale there are
several issues that have to be addressed: solvent engineering,
lipases immobilization, selection of acyl acceptor, and selection
of the reactor system [64]. Kumari et al. [65] reported that 94%
biodiesel yield from Jatropha oil was recovered as temperature
increased up to 55oC, using 50 of immobilized E. aerogenes
lipase with 1:4 oil to methanol molar ratio at 55C for 48 h.
Immobilized lipase in this study was stabile which indicates that
the process was efficient. In the other hand, Sotoft et al. [45]
reported that Enzymes were more expensive and slower reacting
than traditional chemical catalyst, but give a much easier and
simpler biodiesel purification.
Conclusion
Lack of fossil fuel reserve makes research regarding to the
development of biodiesel as a renewable energy become one of
the most popular topic. It can directly use as an additional
material in diesel engines without any modication. There are
several transesterification methods to produce biodiesel such as:

conventional transesterification oil method, in situ process,

ultrasound assisted process, microwave, and enzymatic.
Although biodiesel production from microwave and ultrasound
assist will soon have a bright future, a low cost production in
industrial production still need to be explored and developed.
Acknowledgments
The authors gratefully acknowledge the financial support through
Beasiswa Unggulan Program from Ministry of Education and
Culture of Republic of Indonesia.
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