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Bioresource Technology 99 (2008) 6656–6660

Short Communication

Transesterified sesame (Sesamum indicum L.) seed oil as a biodiesel fuel


Abdurrahman Saydut a,*, M. Zahir Duz b, Canan Kaya b,
Aylin Beycar Kafadar b, Candan Hamamci b
a
Dicle University, Engineering and Architecture Faculty, Mining Engineering Department, TR-21280 Diyarbakir, Turkey
b
Dicle University, Science and Art Faculty, Chemistry Department, TR-21280 Diyarbakir, Turkey

Received 9 March 2007; received in revised form 21 November 2007; accepted 22 November 2007
Available online 21 February 2008

Abstract

The sesame (Sesamum indicum L.) oil was extracted from the seeds of the sesame that grows in Diyarbakir, SE Anatolia of Turkey.
Sesame seed oil was obtained in 58 wt/wt%, by traditional solvent extraction. The methylester of sesame (Sesamum indicum L.) seed oil
was prepared by transesterification of the crude oil. Transesterification shows improvement in fuel properties of sesame seed oil. This
study supports the production of biodiesel from sesame seed oil as a viable alternative to the diesel fuel.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Biodiesel; Sesame; Oil extraction; Transesterification; Renewable energy

1. Introduction tries like Germany, China, India and Turkey, ethnobotani-


cal uses against health problems including cancer, cold,
Sesame (Sesamum indicum L) is an oilseed herbaceous colic, etc. are common (Koca et al., 2007). The chemical
crop of the Pedaliaceae family. It is an economically impor- composition of sesame shows that the seed is an important
tant oil seed crop which is widely cultivated in many parts of source of oil (44–58%), protein (18–25%), carbohydrate
the world, primarily in tropical and subtropical areas of the (13.5%) and ash (5%) (Elleuch et al., 2007). The main constit-
world, including India, China, Sudan, Burma, Tunisia, uents of sesame seeds are oil and protein. Oil content ranges
Egypt, Thailand, Mexico, Guatemala, El Salvador, 57–63%, and protein from 23% to 25% (Tunde-Akintunde
Afghanistan, Pakistan, Bangladesh, Indonesia, Sri Lanka, and Akintunde, 2004). The fat of sesame is of importance
Saudi Arabia and Turkey, and has recently been adapted in the food industry due to its flavour and stability, and
to semi-arid regions (Elleuch et al., 2007; Koca et al., because it can be used to cook meals of high quality. Sesame
2007; Uzun et al., 2007; Wu, 2007). It is an ancient culti- oil contains sesamin and sesaminol lignans in its nonglycerol
vated plant and thought to have originated from Africa fraction, which are known to play an important role in the
and Turkey is known to be the second genetic resource. Ses- oxidative stability and antioxidative activity (Wu, 2007).
ame (3 321 458 t) are produced in 7 554 200 ha areas in the The addition of unsaponifiable matter extracted from
world. In Turkey, it is grown in 43 000 ha areas and pro- sesame seed increases the stability of sunflower oil. This
duces 23 000 t (Koca et al., 2007; Uzun et al., 2007). stability is more pronounced in the case of unsaponifiable
Sesame is widely used in food, nutraceutical, pharmaceu- matter extracted from roasted sesame seeds due to a
tical and industry in many countries because of its high oil, synergistic role. The most abundant fatty acids were oleic
protein and antioxidant contents. Hence, in several coun- (43%), linoleic (35%), palmitic (11%) and stearic (7%) acids,
which together comprised about 96% of the total fatty acids
*
Corresponding author. Tel.: +90 412 248 84 03; fax: +90 412 248 83
(Elleuch et al., 2007).
89. Biodiesel is produced from animal fat, plant oil or waste
E-mail address: saydut@dicle.edu.tr (A. Saydut). cooking oil, and that can be used as the basis for a clean

0960-8524/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2007.11.063
A. Saydut et al. / Bioresource Technology 99 (2008) 6656–6660 6657

substitute for fossil fuel without any modification to diesel molar ratio) and 1.5 g NaOH. The reaction was carried
engines, boilers or other combustion equipments (Canakci, out for 2 h under reflux at 60 °C while stirring. The reac-
2007; Gerpen, 2005; Ma and Hanna, 1999; Meher et al., tion was carried out using 100% excess methanol, i.e. molar
2006). Oil seeds have been one of the major biomass ratio of methanol to oil is 6:1 and catalyst concentration of
sources of fuel (Karaosmanoglu, 1999). It is renewable 0.5%. The reactor was equipped with reflux condenser to
and does not contribute to global warming due to its closed condense back the methanol escaping from the reaction
carbon cycle. A life cycle analysis of biodiesel showed that mixture. The reaction mixture was then allowed to stand
overall CO2 emissions were reduced by 78% compared with overnight and the methyl ester layer was separated from
petroleum-based diesel fuel. Its additional advantages the glycerol layer using separatory funnel. After comple-
include outstanding lubricity, excellent biodegradability, tion of reaction, crude glycerol was separated by gravity.
superior combustion efficiency and low toxicity, among The catalyst was removed by hot water washings. Phenol-
others (Gerpen, 2005; Holser and O’Kuru, 2006; Rama- phthalein indicator checked the complete removal of the
dhas et al., 2005). The plant oils usually contain free fatty catalyst. Traces of moisture and unreacted methanol were
acids, phospolipids, sterols, water, odorants and other removed by vacuum distillation. The distillation was con-
impurities. Because of these, the oil cannot be used as fuel tinued until the loss in weight of ester was constant thus
directly. To overcome these problems the oil requires slight confirming the complete removal of moisture and unre-
chemical modification (Canakci, 2007). There are three acted methanol. The crude methyl ester was further puri-
kinds of catalysts that can be used in transesterification fied by distilling-off the unreacted methanol under normal
reaction, a strong alkaline catalyst, a strong acid, and an atmospheric pressure, washing several times with water,
enzyme. The main advantages of using a strong alkali as centrifugation and drying with vacuum destigator.
a catalyst are shorter reaction time and less amount of cat- After completion of the transesterification, the reaction
alyst required in the manufacturing process of the transe- mixtures were allowed to cool down to room temperature
sterification reaction (Ma and Hanna, 1999; Meher et al., to produce two phases: crude ester phase and glycerol
2006). phase. This phase separation generally occurred quickly
In the present study, sesame (Sesamum indicum L.) seed and can be observed within the first 10 min of settling,
was investigated as an alternative feedstock for the produc- but the ester layer was opaque, indicating that the separa-
tion of a biodiesel fuel. Biodiesel was prepared from sesame tion was incomplete. Experimental results showed that
seed by transesterification of the crude oil with methanol in given enough time for complete settling, the opaque ester
the presence of NaOH as catalyst. Properties of sesame phase could turn crystalline and transparent. This complete
seed oil and biodiesel produced by transesterification were separation could take as long as 8–18 h. In fact, during the
within the limits of ASTM and EN standards. settling, the transesterification process was still going on.
Therefore, the longer the settling time, the more favorable
2. Experimental are the separation and the conversion. All chemicals used
were of analytical grade unless otherwise stated.
Sesame seeds used in the present study were provided
from Agricultural Faculty of Dicle University in Diyarba- 2.3. Analysis of sesame seed oil and biodiesel
kir, situated in SE Anatolia of Turkey in 2005. The seeds
were cleaned manually to remove all foreign matter such Kinematic viscosity at 40 °C was obtained using Koeh-
as dust, dirt, stones and chaff as well as immature, broken ler Kinematic Viscosity Bath Model K 23377 while in
seeds. In order to preserve its original quality, the sample warm water bath. Pour point and cloud point were deter-
was stored at an ambient temperature of 25 ± 3°C in sealed mined simultaneously using Tanaka Mini-Pour/Cloud
plastic bags prior to any conditioning. Point Tester Model MPC-101A/101 L. For flash point,
Tanaka Automatic Flash Point Tester Model APM-6T-A
2.1. Extraction of sesame seed oil was used. Heating value was determined using IKA Calo-
rimeter System C 2000 basic control calorimeter. C and S
Soxhlet extraction was employed to know the total oil were determined by Carlo Erba 1108 Model elemental ana-
content of the sesame seed. According to the Turkish Stan- lyzer and Eltra CS 500 Carbon, Sulfur Determinator. Mea-
dard, traditional Soxhlet extraction was carried out in stan- surements of the density at 15 °C by Metler–Toledo
dard apparatus by standard methods using 250 ml n-hexane densimeter. The iodine number, cetane number was calcu-
and 20.0 g sesame seeds the smallest particle size mixed with lated, while the acid value was obtained by titration (Meher
20.0 g sand. After extraction 5 h, the extracts were concen- et al., 2006).
trated and dried, and the solvent was then evaporated.
3. Results and discussion
2.2. Production procedure for biodiesel
Sesame oil contains a class of unusual compounds
Biodiesel derived from sesame seed oil was prepared by known as lignans, comprised of sesamin, sesamolin, and
reacting 300 g of oil, 60 g CH3OH (approximately 6:1 a small amount of sesamol (Wu, 2007). Sesame oil shows
6658 A. Saydut et al. / Bioresource Technology 99 (2008) 6656–6660

high stability to oxidation compared with other vegetable acceptable level to avoid negative impacts on fuel injector
oils. It can also be used to prevent lipid oxidation in soy- system performance. Therefore, the viscosity specifications
bean, rapeseed, and sesame oil (Bozkurt, 2007). Sesame proposed are nearly same as that of the diesel fuel. Higher
seed oil was obtained in 58 wt/wt%, by traditional solvent viscosity of oils had an adverse effect on the combustion in
extraction in our laboratory. The high viscosity, low vola- the existing diesel engines (Meher et al., 2006; Ramadhas
tility and poor cold flow properties of triglycerides, which et al., 2005). Even more than density, this is an important
result in severe engine deposits, injector coking and piston property regarding fuel atomization, as well as fuel distri-
ring sticking, have prevented them from being used directly bution. The viscosity of vegetable oils is about ten times
in diesel engines (Marinkovic and Tomasevic, 1998; higher than that of diesel, with consequent poor fuel atom-
Szentmihalyi et al., 2002). ization, incomplete combustion, carbon deposition on the
Sesame seed oil was investigated as an alternative feed- injectors and valve seats, and fuel build-up in the lubricant
stock for the production of a biodiesel fuel. Although the oils. This can, therefore, cause serious engine deterioration,
oil content of sesame seeds varies widely, (37–63%), the hence, it is absolutely necessary to subject the vegetable oils
average percentage of oleic and linoleic acid content in to treatments that diminish the viscosity. Biodiesel not only
the sesame germplasms and cultivars is very similar has proper viscosity, boiling point, and high cetane num-
(41.3% and 43.7%, respectively) (Baydar et al., 1999). A ber, but also is simple to use, biodegradable, nontoxic,
maximum conversion of 74% (oil to ester) was achieved and essentially free of sulfur and aromatics. The kinematic
using 100% excess methanol, i.e. molar ratio of methanol viscosity of the biodiesel sample produced in this work
to oil is 6:1 and catalyst (NaOH) concentration of 0.5% 4.2 mm2 s 1.
at 60 °C. Sesame oil is used as the raw oil to be mixed with Density is important mainly in airless combustion sys-
methyl alcohol in a molar ratio of 1:6, and the mixture then tems because it influences the efficiency of atomization of
undergoes transesterification reaction in order to produce the fuel. The results obtained showed that for the condition
biodiesel. studied, the biodiesel produced in this study had a density
The fuel characteristics of the alkyl esters synthesized 0.8672 g cm 3.
were evaluated according to ASTM standard methods Flash point of a fuel is the temperature at which it will
(Antolin et al., 2002; Holser and O’Kuru, 2006; Ramadhas ignite when exposed to a flame or spark. The flash point
et al., 2005). The quality of biodiesel is most important for of biodiesel is higher than the petrodiesel, which is safe
engine part of view and various standards have been spec- for transport purpose (Ma and Hanna, 1999). The flash
ified to check the quality. Fuel properties of methyl esters point of the biodiesel sample produced in this work has
of sesame seed oil compare well with ASTM D 6751-06 been found 170 °C. It is highly lower than flash point of
and EN 14214 biodiesel standards (Table 1). The major sesame oil (245 °C).
problem associated with the use of pure vegetable oils as Two important parameters for low temperature applica-
fuel in diesel engines is caused by high fuel viscosity in tions of a fuel are cloud point and pour point. The cloud
the compression ignition. High viscosity leads to poor point is the temperature at which wax first becomes visible
atomization of the fuel, incomplete combustion, cooking when the fuel is cooled. The pour point is the lowest tem-
of the fuel injectors, ring carbonization, and accumulation perature at which the oil specimen can still be moved.
of fuel in the lubricating fuel (Karaosmanoglu, 1999). The pour point is the temperature at which the amount
Among the general parameters for biodiesel, the viscosity of wax out of solution is sufficient to gel the fuel can flow.
controls the characteristics of the injection from the diesel Sesame seed oil ester has higher cloud point and pour point
injector (Karmee and Chadha, 2005). compared to No.2 petroleum diesel. Cloud point and pour
The viscosity of fatty acid methyl esters can go very high point of produced biodiesel are 6 °C and 14 °C, respec-
levels and hence it is important to control it within an tively (Demirbas, 2005).

Table 1
Fuel properties of sesame seed oil and its methylester
Sesame seed oil Biodiesel ASTM D6751-06 EN 14214 No. 2 petroleum diesel
%C 68.9628 62.1477 –
% S (ppm) 0 0 15 ppm 10 ppm % < 0.5
Kinematic viscosity (40 °C) 25.78 4.2 1.9–6.0 3.5–5.0 2.5–3.5
Heating value (MJ/kg) 39.5 40.4 42.7
Density (15 °C) 0.899 0.8672 0.86–0.90 0.82–0.86
Flash point (°C) 245.0 170.0 130.0 min >101 >55
Iodine number 82.45 80.32 120 max –
Neutralization number (mg KOH/g) 0.3 0.50 max 0.5 max –
Pour point (°C) 10.0 14.0 –33
Cloud point (°C) 1.0 6.0 –16
Cetane number 50.48 47 min 51 min 49–55
A. Saydut et al. / Bioresource Technology 99 (2008) 6656–6660 6659

Cetane number is indicative of its ignition characteris- oil content is of great importance in the breeding of sesame
tics. The cetane number measures how easily ignition (Baydar et al., 1999).
occurs and the smoothness of combustion. Higher the
cetane number better it is in its ignition properties. Cetane 4. Conclusions
number affects a number of engine performance parameters
like combustion, stability, drivability, white smoke, noise  Sesame (Sesamum indicum L.) is one of the oldest edible
and emissions of CO and HC (Ramadhas et al., 2006; oil crops and its seeds, used as a food source, contain up
Meher et al., 2006). Biodiesel has higher cetane number to 60% fat.
than conventional diesel fuel, which results in higher com-  Fuel properties of methylesters of sesame oil compare
bustion efficiency. The cetane number of biodiesel varies well with ASTM and EN biodiesel standards.
widely in the range of 48–67 depending upon various  Sesame oil has good potential as alternative diesel fuel,
parameters including oil processing technology and cli- but its use in direct-injection engines is limited by high
matic conditions where feedstock is collected. Cetane num- viscosity, low volatility and the polyunsaturated charac-
ber of the biodiesel sample produced in this work has been ter of the triglycerides. Sesame seed oil transesterifica-
found 50.48. tion is one approach to viable sesame seed oil-based
Neutralization number is specified to ensure proper age- fuel. This study used sesame oil as the raw oil to mix
ing properties of the fuel and/or a good manufacturing with methanol and sodium hydroxide (NaOH) to
process. It reflects the presence of free fatty acids or acids undergo a transesterification reaction.
used in manufacture of biodiesel and also the degradation  Sesame seed oil have about 7.5% less heating value than
of biodiesel due to thermal effects. that of diesel oil due to the oxygen content in their mol-
The iodine value is an important measure that allows ecules. Viscosity and density of methyl esters of sesame
determination of the unsaturation degree of the fuel. This seed oil are found to be very close to that of diesel. The
property greatly influences fuel oxidation and the type of calorific value of biodiesel is found to be slightly lower
aging products and deposits formed in diesel engines injec- than that of diesel (5.4%).
tors. Analyses of sample of the produced biodiesel revealed  The present experimental results support that methyl
iodine value 80.32. ester of sesame seed oil can be successfully used as diesel.
The results show that, transesterification improved the
important fuel properties of the oil like density, viscosity,
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