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Energy Conversion and Management 52 (2011) 20312039

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Energy Conversion and Management


journal homepage: www.elsevier.com/locate/enconman

Properties and quality verication of biodiesel produced from tobacco seed oil
N. Usta a,, B. Aydogan a, A.H. on b, E. Uguzdogan c, S.G. zkal b
a

Pamukkale University, Mechanical Engineering Department, 20070 Denizli, Turkey


Pamukkale University, Food Engineering Department, 20070 Denizli, Turkey
c
Pamukkale University, Chemical Engineering Department, 20070 Denizli, Turkey
b

a r t i c l e

i n f o

Article history:
Received 9 August 2009
Received in revised form 11 May 2010
Accepted 13 December 2010

Keywords:
Tobacco seed oil
Biodiesel
Quality
Oxidation stability
Iodine number
Cold lter plugging point

a b s t r a c t
Tobacco seed oil has been evaluated as a feedstock for biodiesel production. In this study, all properties of
the biodiesel that was produced from tobacco seed oil were examined and some solutions were derived
to bring all properties of the biodiesel within European Biodiesel Standard EN14214 to verify biodiesel
quality. Among the properties, only oxidation stability and iodine number of the biodiesel, which mainly
depend on fatty acid composition of the oil, were not within the limits of the standard. Six different
antioxidants that are tert-butylhydroquinone, butylated hydroxytoluene, propyl gallate, pyrogallol,
a-tocopherol and butylated hydroxyanisole were used to improve the oxidation stability. Among them,
pyrogallol was found to be the most effective antioxidant. The iodine number was improved with blending the biodiesel produced from tobacco seed oil with a biodiesel that contains more saturated fatty acids.
However, the blending caused increasing the cold lter plugging point. Therefore, four different cold ow
improvers, which are ethylenevinyl acetate copolymer, octadecene-1-maleic anhydride copolymer and
two commercial cold ow improvers, were used to decrease cold lter plugging point of the biodiesel and
the blends. Among the improvers, the best improver is said to be octadecene-1-maleic anhydride copolymer. In addition, effects of temperature on the density and the viscosity of the biodiesel were
investigated.
2010 Elsevier Ltd. All rights reserved.

1. Introduction
Vegetable oils can be used to produce biodiesel fuels that are
renewable alternative fuels for diesel engines. Among the vegetable oils, rapeseed, soybean and palm oils are the most-used vegetable oils for biodiesel production in the world. In addition, there
are many studies carried out in different countries to nd new
feedstocks such as mahua oil [1], castor oil [2], tall oil [3], tea seed
oil [4] and microalgae [5] for biodiesel production.
In this connection, tobacco seed oil (TSO) has been considered as
a new feedstock for biodiesel production. Giannelos et al. [6] examined some of physical and chemical properties of tobacco seed oil
and suggested that tobacco seed oil may be an appropriate substitute for diesel fuel. Usta [7] produced biodiesel fuel from tobacco
seed oil and examined ester content, density, viscosity, sulphur content, cetane number, water content, acid value, iodine value and
heating value of the biodiesel fuel. In addition, the effects of tobacco
seed oil methyl ester addition to diesel No. 2 on the performance and
emissions of a diesel engine were presented in the study. In addition,
Veljkovic et al. [8] produced methyl ester from crude tobacco seed
oil having high free fatty acids by using two steps: the acid-catalyzed
esterication followed by the base-catalyzed methanolysis. Density,
Corresponding author. Tel.: +90 2582963139; fax: +90 2582963262.
E-mail addresses: n_usta@pau.edu.tr, usta_n@yahoo.com (N. Usta).
0196-8904/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2010.12.021

kinematic viscosity, caloric value, iodine value, saponication


value and acid value of the methyl ester were examined. In another
study related to the biodiesel production from tobacco seeds, Parlak
et al. [9] examined some variables such as reaction temperature,
alcohol/oil molar ratio, type and amount of catalyst, reaction duration, the water content and free fatty acid, affecting the yield of
tobacco seed oil methyl ester for KOH and NaOH catalysts. Effects
of these variables on kinematic viscosity, ash point, and freezing
points were investigated.
Tobacco is a well-known plant due to its leaves used to produce
cigarette and cigar. However, cigarette and cigar are harmful products for human beings. Therefore, tobacco plant has a negative connotation on peoples mind. However, tobacco plant has so many
potentials beyond its cigarette and cigar production. Tobacco plant
has huge amount of small seeds other than the leaves. To the
authors best knowledge, unlike tobacco leaves, tobacco seeds generally are not collected from the elds and are not commercial
products. However, tobacco seed has a potential to become a commercial product.
Since the seeds are not collected as a product, there is no statistical information about the amount of tobacco seed in the literature.
However, it may be estimated from the tobacco plant cultivation
areas. The amount of seed that could be collected per hectare area
may change depending on the place, the type of tobacco plant
and weather conditions. As an example, the amount of seed per

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N. Usta et al. / Energy Conversion and Management 52 (2011) 20312039

hectare area is around 600 kg in DenizliTurkey and it was also


determined that the amount of seed may increase up to 1200 kg
per hectare area in some elds [7]. In addition, in Macedonia, the
amount of seed is around 2500 kg per hectare area; also, it was
informed that the new generated plants could give more than
this amount of seed [10]. In that case, tobacco plant may be grown
for the seeds other than leaves and it may be a useful plant for
human beings, not harmful. In this connection, there are some
ongoing studies to increase the amount of tobacco seed per hectare
area.
The seeds are collected after the leaves collection. Tobacco seed
contains signicant amount of oil (3549% by weight) [7,11].
Tobacco seed oil is extracted from tobacco seeds and does not contain nicotine [12]. Since tobacco seed oil is not edible oil, it can be
used in different applications such as biodiesel production [7]. In
addition, after the oil is extracted, the remaining part as a cake
can be used for animal food [13]. In this respect, it may be said that
tobacco plant is a promising crop and may be a useful plant for
human beings in near future.
A biodiesel fuel that will be used in diesel engines must meet
various specications included in biodiesel standards, mainly US
Biodiesel Standard ASTM 6751 [14] and European Biodiesel standard EN 14214 [15]. Properties of a biodiesel depend on the raw
vegetable oil and the production technique. While some of these
properties are related to biodiesel production technique, several
properties like oxidation stability, iodine number, cold lter plugging point (CFPP), cetane number, and viscosity directly depend
upon the fatty acid composition of the raw oil. Therefore, the fatty
acid composition of a vegetable oil is the most important parameter inuencing the properties of a vegetable oil and its methyl ester
[16]. The fatty acid composition of tobacco seed oil depends on the
type of tobacco plant, place and weather conditions. In general, the
main fatty acids of most of the tobacco seed oils extracted from tobacco seeds grown in Bulgaria [11], Macedonia [13], India, Turkey,
England [17], Pakistan [18] and Serbia [19], are linoleic, oleic,
palmitic and stearic acids.
The biodiesel production techniques from different kinds of oils
that are waste rapeseed oil [20], used frying oils, soapstocks, fats,
greases [21], jatropha oil, ricebran oil [22,23] were examined in
many studies. In general, it was reported that oils containing high
free fatty acids could not be effectively converted to biodiesel using
only an alkaline catalyst. It is required to reduce the free fatty acids
of the feedstock using an acid catalyzed pre-treatment to esterify
the free fatty acids before transesterifying the triglycerides with
an alkaline catalyst to complete the reaction [24,25]. Demirbas
[26] compared different transesterication methods for production
of biodiesel from vegetable oils and fats. In addition, Demirbas [27]
also examined biodiesel production via rapid transesterication.
In general, biodiesel fuels are blended with diesel fuel No. 2 and
the blends are used in diesel engines. The amount of biodiesel in
the blends may change depending on the properties of biodiesel,
regulations and application places. Most of the automotive companies allow maximum 5% (in volume basis) biodiesel usage in their
diesel engines. In Europe, the amount of biodiesel addition into
diesel fuel is around 5% (in volume basis) and this value is 20%
(in volume basis) in USA. Meanwhile, many studies have been carried out to characterize the performance and exhaust emissions of
diesel engines fuelled with biodiesel fuels produced from different
oils such as soybean oil, yellow grease [28], neem oil [29], soybean
oil [30], used cooking oil [31]. Agarwal [32] and Lapuerta et al. [33]
presented reviews including results of many studies.
This study is the extension of previous studies of rst author
[7,34]. To the authors best knowledge, an extensive study has
not been performed on the quality of biodiesel produced from
tobacco seed oil, yet. This was the basic motivation behind the
research in this paper. In this study, a comprehensive work was

performed to produce biodiesel fuel, which could meet the specications of European Biodiesel Standard EN 14214, from tobacco
seed oil. This is an important subject for biodiesel production from
any source. Meanwhile, it is thought that this study will give some
guidelines for future researchers who will try to produce biodiesel,
which meet the specications of EN 14214 standard, from new oil
sources.
2. Materials and methods
2.1. Tobacco seed oil
Since tobacco seed oil is not available in markets, it was
required to collect seeds from the elds in Buldan region of Denizli
in Turkey. The oil content of the seed was determined by using a
soxhlet apparatus on 10  0.001 g of ground tobacco seeds, by
using diethyl ether as a solvent for 8 h. The necessary amount of
tobacco seed oil was extracted by using a solvent extraction method that was performed in a special pilot reactor designed and manufactured for this study as shown in Fig. 1. Again, diethyl ether was
used as a solvent in the process. The oil extraction process is
explained below.
The collected seeds were dried to remove moisture in 2 h at
110  1 C in an oven and ground using a special grinding machine.
Then, the dried and ground seeds were put on a shelve in a main
tank of the reactor. The diethyl ether was poured onto the seeds
as solvent. The seed/diethyl ether ratio was 5 kg/12 L in the reactor.
The seeds were left in the diethyl ether for 3 h. Then, the oil and
diethyl ether mixture were allowed to ow in a second tank that
is heated via special heating plates. The diethyl ether was boiled
and the vapor was allowed to pass through a heat exchanger that
was cooled with a circulating water-cooling unit. The diethyl ether
condensed in the heat exchanger was collected in a third tank. The
oil was taken from the bottom of the second tank. The detailed
information about oil extraction unit and the process was given
in Usta et al. [35].
The fatty acid composition of the oil was determined by
gasliquid chromatography in Marmara Research Center of
The Scientic and Technological Research Council of Turkey
(MAM-TUBITAK).
2.2. Biodiesel production and determination of its properties
Free fatty acid content of tobacco seed oil was measured by the
method of AOCS Cd 3a-63 [36]. Since the free fatty acid content of
the extracted tobacco seed oil was below 0.5%, the oil was converted into methyl ester by means of transesterication process
that uses a base catalyst. Methyl alcohol and sodium hydroxide
were used as alcohol and catalyst in the transesterication process,
respectively. The optimum values for molar ratio of methyl alcohol
to glycerides and the amount of sodium hydroxide were determined as 6/1 and 7.5  0.2 g/kg the oil, respectively [35].
Transesterication process was carried out using a specially
designed stainless steel reactor (28 L) which have a heater and a
mixer as shown in Fig. 2. The biodiesel production process is
explained below. The tobacco seed oil was stirred by a mixer running at 900  5 rpm, meanwhile the oil was heated with the heater
to keep the oil temperature at 55  1 C. Sodium hydroxide was
dissolved in methyl alcohol to produce the sodium methoxide.
Then the prepared sodium methoxide was poured into the oil.
The mixture was stirred at 900  5 rpm for 2 h holding the temperature at 55  1 C. Then, the heater was turned off and stirring was
continued for 2 h without heating. The mixture was left in the reactor and was allowed to form two layers for at least 8 h. The bottom
layer was glycerol while the upper layer was the biodiesel. After
the settling was completed, the glycerin was taken out from the

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N. Usta et al. / Energy Conversion and Management 52 (2011) 20312039

8
9

1
5

11

12
7
16
10

10

13

10

15

14
16
10

10

Fig. 1. Oil extraction reactor (1. Main tank, 2. Second tank (diethyl ether + oil mixture), 3. Third tank (diethyl ether), 4. Shelve, 5. Seed, 6. Diethyl ether, 7. Heat exchanger, 8.
Manometer and pressure relief valve, 9. Heating plate, 10. Valve, 11. Cooling water inlet, 12. Cooling water outlet, 13. Control unit, 14. Diethyl ether and oil mixture, 15.
Diethyl ether, 16. Thermocouple).

4
3
2

6
7

8
Fig. 2. Biodiesel reactor (1. Main tank, 2. Heating plate 3. Valve liquid inlet, 4.
Electric motor, 5. Control unit, 6. Mixer, 7. Thermocouple, 8. Valve liquid outlet).

The Scientic and Technological Research Council of Turkey


(MAM-TUBITAK). The information about the accuracy of the measurements and the uncertainty of the computed results in determination of these properties were dened in each test method of the
standards given in EN 14214.
In addition, the viscosity measurements at different temperatures (045 C) were performed by using an A&D Sine-wave vibro
viscometer SV-10 which measures viscosity by detecting the driving electric current necessary to resonate the two sensor plates at a
constant frequency of 30 Hz and amplitude of less than 1 mm. The
sample was poured into a special sample cup that was replaced in a
special water jacket connected to a cold-water bath. The temperatures of samples were adjusted by changing temperature of the
water in the cold-water bath. The viscosity sensor plates and temperature sensor of the viscometer was inserted into the samples
and they were measured at the same time. The measurements
were recorded via special software running in a personal
computer. The viscosities were measured in 1% accuracy and the
temperatures were measured with an accuracy of 0.1 C.
Density measurements were carried out at different temperatures (080 C) using a pycnometer that has capacity of 100 mL
being calibrated with pure water. For weight measurement, an
analytical weighing balance with an accuracy of 1 mg was used.
The uncertainty in density values is less than 0.25%.
2.3. Additives

bottom. The biodiesel was washed with distilled water three times.
At the end of the process, the biodiesel was heated over 100 C to
remove any water left in the biodiesel. The nal biodiesel became
clear straw yellow.
All properties of tobacco seed oil methyl ester were determined
according to EN 14214 standards by Marmara Research Center of

Some additives were used to improve oxidation stability and


CFPP of TSOME. Six different antioxidants were used to improve
the oxidation stability. These are tert-butylhydroquinone (Sigma
Aldrich), butylated hydroxytoluene (Fluka), propyl gallate (Fluka),
Pyrogallol (Fluka), a-tocopherol (SigmaAldrich) and butylated
hydroxyanisole (SigmaAldrich).

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N. Usta et al. / Energy Conversion and Management 52 (2011) 20312039


Table 1
Fatty acid composition of the tobacco seed oil.
Fatty acid

Caprylic 8:0
Capric 10:0
Lauric 12:0
Myristic 14:0
Palmitic 16:0
Palmitoleic 16:1
Stearic 18:0
Oleic 18:1
Linoleic 18:2
Linolenic 18:3
Arachidic 20:0
Eicosenoic 20:1
Behenic 22:0
Erucic 22:1
Others

0.08
0.00
0.00
0.12
8.16
0.10
3.56
12.14
72.98
0.76
0.20
0.12
0.07
0.00
1.71

Four different additives were used to improve CFPP of TSOME.


These are ethylenevinyl acetate copolymer (SigmaAldrich),
octadecene-1-maleic anhydride copolymer (SigmaAldrich) and
two commercial cold ow improvers which are represented as
CCFI1 and CCFI2.

3. Results and discussions


The oil content of the collected seeds was determined as
approximately 38  2% (in weight basis) using diethyl ether as an
extraction solvent. Meanwhile the yield of biodiesel production
from tobacco seed oil was achieved as 88  1 wt.% by applying
the procedure mentioned in previous section. This may be

acceptable yield, because the oil was the virgin oil and contains
some matters other than triglycerides. The legends used in this
study are D100 for diesel fuel No. 2, TSOME for tobacco seed oil
methyl ester and TSOMExxD (100-xx) for the blend, which consists
of xx percentage (v/v) TSOME with (100-xx) percentage (v/v) D100.
Properties of a biodiesel fuel depend on the fatty acid composition of the raw oil and the biodiesel production process. This
means that the fatty acid composition of the raw oil is very important and may give some idea about the properties of the biodiesel
[16]. Therefore, at the beginning of the studies, fatty acid composition of tobacco seed oil used in this study was determined and it is
given in Table 1. The main fatty acids are linoleic, oleic, palmitic
and stearic acids. Similar fatty acid compositions were found in
the literature for tobacco seed oil [18].
The determined properties of TSOME are given in Table 2.
Among the properties, two properties were not within the limits
of EN 14214 standard. These are oxidation stability and iodine
value. The other properties were within the limits.
Oxidation stability is one of the major properties affecting the
use of biodiesel and mainly depends on the fatty acid composition
of the oil. Since tobacco seed oil mainly consists of unsaturated
fatty acids, the lower value for oxidation stability was an expected
problem. In addition, the biodiesel production techniques may
affect the oxidation stability. Therefore, the production should be
performed very carefully. The other important point is the storage
of the biodiesel. The biodiesel should be stored in suitable conditions. Different additives were used to improve the oxidation stabilities of biodiesel fuels [37,38]. However, there are some
important issues. The additive should be compatible with biodiesel
and should not affect negatively other fuel properties. In this study,
six different antioxidants that are tert-butylhydroquinone, butylated hydroxytoluene, propyl gallate, pyrogallol, a-tocopherol and

Table 2
Properties of TSOME.
Property

Unit

Analysis result

Min.

Max.

Ester content
Density at 15 C
Viscosity at 40 C
Flash point
Sulphur content
Carbon residue (on 10% distillation residue)
Cetane number
Sulfated ash content
Water content
Total contamination
Copper strip corrosion (3 h at 50 C)
Oxidation stability, 110 C
Acid value
Iodine value
Linolenic acid methyl ester
Polyunsaturated (P4 double bonds) methyl esters
Methanol content
Monoglyceride content
Diglyceride content
Triglyceride content
Free glycerol
Total glycerol
Group I metals (Na + K)
Na
K

% (m/m)
kg/m3
mm2/s
C
mg/kg
% (m/m)

98.6
888.5
4.23
165.4
8
0.029
51.6
0.0004
354.09
23.95
1A
0.8
0.3
136
0.759
<0.1
<0.01
0.54
0.13
0.17
0.002
0.23
<5
<2
<2

96.5
860
3.50
120

51.0

class 1
6.0

900
5.00

10.0
0.30

0.02
500
24

Group II metals (Ca + Mg)


Ca
Mg

mg/kg

<5
<2
<2

5.0

EN 14538

Phosphorus content
Cold lter plugging point

mg/kg
C

4
-5

10.0

EN 14107
EN116

% (m/m)
mg/kg
mg/kg
rating
hours
mg KOH/g
g iodine/100 g
% (m/m)
% (m/m)
% (m/m)
% (m/m)
% (m/m)
% (m/m)
% (m/m)
% (m/m)
mg/kg

EN 14214
Limits

Test method

0.50
120
12.0
1
0.20
0.80
0.20
0.20
0.02
0.25
5.0

EN 14103
EN ISO 12185
EN ISO 3104
EN ISO 3679
EN ISO 20846
EN ISO 10370
EN ISO 5165
ISO 3987
EN ISO12937
EN 12662
EN ISO 2160
EN 14112
EN 14104
EN 14111
EN 14103
EN 14103
EN 14110
EN 14105
EN 14105
EN 14105
EN 14105
EN 14105
EN 14108
EN 14109

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12
11
10

butylated hydroxytoluene

propyl gallate

tert-butylhydroquinone

pyrogallol

-Tocopherol

butylated hydroxyanisole

Oxidation Stability (h)

9
8
7
6
5
4
3
2
1
0
0

500

1000

1500

2000

Concentration (ppm)
Fig. 3. Effects of different antioxidants on oxidation stability of TSOME.

butylated hydroxyanisole were added to TSOME in concentrations


between 500 ppm and 2000 ppm and the oxidation stabilities were
measured. The change of oxidation stability with respect to the
concentrations of the antioxidants is shown in Fig. 3. Among the
antioxidants, pyrogallol was found to be the most effective
antioxidant, similar to Tang et al. [39] and Pahgova et al. [40].
The addition of pyrogallol at 500 ppm could increase the oxidation
stability from 0.8 h to over 6.5 h. It should be noticed that if the
oxidation of the original biodiesel was higher than 0.8 h, the smaller amount of pyrogallol could increase the oxidation stability over
6 h for different biodiesel fuels [35]. It was also determined that
pyrogallol does not affect the CFPP, viscosity, iodine number and
cetane number of TSOME negatively.
The iodine value of a biodiesel also directly depends on the fatty
acid composition [41]. It cannot be improved with additives.
Therefore, the only way is blending original biodiesel with a biodiesel that has a low iodine value. The biodiesels with low iodine
value contain more saturated fatty acids, which result in increasing
CFPP of the blend. Therefore, the percentage of the biodiesel with
low iodine value should be kept to a minimum in the blends to
meet the limit value 120 g iodine/100 g. Otherwise, the blending
results in low iodine value, but high CFPP. In this study, a blend
T70W30 which included 30% (in weight basis) biodiesel produced
from waste mixed cooking oil (WMCOME) and 70% (in weight basis) TSOME was prepared to decrease the iodine value just below
120 g iodine/100 g. The fatty acid composition of the waste mixed
cooking oil is shown in Table 3. As it is seen that the composition is
different from that of tobacco seed oil and more saturated. Its
iodine value was 60 g iodine/100 g. Since the waste mixed cooking
oil contained high free fatty acids, the biodiesel production technique from the waste mixed cooking oil was different. The details
of biodiesel production from waste mixed cooking oil were given in
Usta et al. [35]. The addition of WMCOME increased oxidation stability and the cetane number of the blend. However, the blending
resulted in an increase in CFPP. It should be pointed out that
although EN 14214 standard has a restriction on iodine number
of biodiesel; ASTM 6751 standard has no restriction on the iodine

number. This means that if ASTM 6751 standard is applied in any


country, there is no need to blend TSOME with any other biodiesel
to meet the standard.
Cold-ow quality of a fuel is determined by CFPP, cloud point
and pour point. However, CFPP is referred as a cold ow property
in EN14214 standard. Although the CFPP of TSOME which is
5 C, is acceptable for some weather conditions, the CFPP of the
blend T70W30 (70% TSOME and 30% WMCOME in weight basis) increased to 0 C. Therefore, four different cold ow improvers,
which are ethylenevinyl acetate copolymer, octadecene-1-maleic
anhydride copolymer and two commercial cold ow improvers
represented as CCFI1 and CCFI2, were added to TSOME, WMCOME
and the blend T70W30 in concentrations at 0.5% and 1% by weight
to decrease CFPP values. The effects of cold ow improvers on CFPP
of TSOME, WMCOME and the blend T70W30 are shown in Table 4.
Among the improvers, the best improver is said to be octadecene1-maleic anhydride copolymer. In addition, it was also determined
that octadecene-1-maleic anhydride copolymer also does not affect cetane number and the oxidation stability negatively. It is better to point out that the commercial improvers CCFI1 and CCFI2 are
advised especially for rapeseed oil methyl ester.
The other properties that are related to the biodiesel production
and purication techniques were within the limits. These properties are ester content, carbon residue, sulphated ash content, water
content, total contamination, acid value, methanol content, monoglyceride content, diglyceride content, triglyceride content, free
glycerol and total glycerol. If the process was incomplete and the
purication method was not suitable, there could be some
problems with these properties. This means that there was no
any problem with biodiesel production and purication technique
applied in this study.
The corrosiveness of a fuel is measured using the copper strip
corrosion test. The copper strip corrosion of TSOME is 1A. It means
that the corrosiveness of TSOME is fairly low. In addition, as it is
expected from fatty acid composition of tobacco seed oil, linolenic
acid methyl ester (0.759% by weight) and polyunsaturated (P4
double bonds) methyl esters (0.1% by weight) are within the limits.

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10 ppm. It is known that some oils may contain higher sulphur


content. The ash point temperature of TSOME is 165.4 C, which
is higher than the minimum value of the standard (120 C), and
there is no any problem from the safety point of view during transportation and storage of TSOME.
In other aspect, the cetane number of TSOME is 51.6, which is
higher than the lower limit of the standard. It is good value, because the cetane number is very important property of the fuel
affecting the ignition delay time that is the time between the start
of injection and start of combustion. As the cetane number
decreases, the ignition delay increases and the main combustion
phase decreases. Long ignition delay causes diesel knock.
Viscosity is another important property of biodiesel. Because it
affects the fuel delivery and the atomization of the fuel. Viscosity of
a biodiesel depends on the fatty acid composition of its oil source.
The viscosity increases with the chain length and decreases with
increasing the degree of unsaturation [42]. High viscosity causes
inadequate operation of the fuel injection system and poor atomization of the fuel. The kinematic viscosity of TSOME is
4.23 mm2/s at 40 C and is within the limits of the standard.
Furthermore, it was thought that it is better to investigate the

Table 3
Fatty acid composition of waste mixed cooking oil.
Fatty acid

Caprylic 8:0
Capric 10:0
Lauric 12:0
Myristic 14:0
Palmitic 16:0
Palmitoleic 16:1
Stearic 18:0
Oleic 18:1
Linoleic 18:2
Linolenic 18:3
Arachidic 20:0
Eicosenoic 20:1
Behenic 22:0
Erucic 22:1
Others

0.05
0.04
0.59
1.14
36.16
0.21
3.18
41.92
11.19
0.29
0.42
0.21
0.09
0.02
4.49

Also, the amounts of group I metals (Na + K), group II metals


(Ca + Mg) and phosphorus in TSOME are within the limits. In addition, the sulphur content of TSOME is 8 ppm and it is lower than

Table 4
Effects of different cold improvers on CFPP of TSOME, WMCOME and their Blend (T70W30-70% TSOME and 30% WMCOME).
Additives

Amount of Additive (% in weight basis)

CFPP (C)
WMCOME

T70W30

No additive
CCFI1

0.0
0.5
1.0

5
5
8

11
10
11

0
2
1

CCFI2

0.5
1.0

14
10

7
8

0
2

Ethylenevinyl acetate copolymer

0.5
1.0

7
6

7
8

3
0

Octadecene-1-maleic anhydride copolymer

0.5
1.0

12
9

6
6

5
2

Dynamic Viscosity (mPa s)

TSOME

20
19
18
17
16
15
14
13
12
11
10
9
8
7
6
5
4
3
2
1
0

TSOME
TSOME75D25
TSOME50D50
TSOME20D80

TSOME05D95
D100
0

10

15

20

25

Temperature

30

35

40

45

(oC)

Fig. 4. The dynamic viscosity measurements of TSOME, D100 and their blends in the temperature range from 0 C to 45 C.

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N. Usta et al. / Energy Conversion and Management 52 (2011) 20312039

25
D100
TSOME

TSOME with an additive (0.5% - octadecene-1-maleic anhydride copolymer)

Dynamic Viscosity (mPa s)

20

15

10

10

15

20

25

30

35

40

45

Temperature (oC)
Fig. 5. The change of dynamic viscosities of diesel fuel No. 2, TSOME and TSOME with an additive (octadecene-1-maleic anhydride copolymer, 0.5% in weight basis).

viscosity variation of TSOME and its blends with respect to the


temperature. Because the viscosity of liquids increases rapidly as
the temperature is decreased. The dynamic viscosity measurements of TSOME, D100 and their blends in the temperature range
from 0 C to 45 C are shown in Fig. 4. The lines show the experimental results. It should be pointed out that the measurements
were recorded automatically with a personal computer via special
software, there are huge numbers of measurements in the range,
and the markers cannot be shown on the gure. The viscosity of
TSOME rapidly increases below 6 C. However, D100 and the
blends do not show this kind of sharp increase. It was determined
that antioxidants do not affect the viscosity, however cold ow
improvers affect the change of viscosity. The change of viscosity
of TSOME, TSOME with additive octadecene-1-maleic anhydride
copolymer at 0.5% by weight and D100 are shown in Fig. 5.
Although octadecene-1-maleic anhydride copolymer increased
slightly the viscosity of TSOME, it prevented the increasing of
viscosity in the low temperatures. The regression equation for viscosities of D100, TSOME and TSOME with octadecene-1-maleic
anhydride copolymer was derived as

le

ABT C2
T


1

where A, B, and C are constants, T is the temperature in K, and l in


mPa s. The constants for the fuels are given in Table 5. The R2 value
was determined as 0.999 for this equation.

In general, densities of biodiesel fuels are higher than that of


D100. The chain length and saturation level of biodiesel fuels
increase the density. The density of a diesel engine fuel has some
effect on the break up of the fuel injected into the cylinder and
more fuel is injected by mass as the fuel density increases [21].
The density of TSOME is 888.5 kg/m3 at 15 C and within the limits
of standards. In addition, the densities of TSOME in the temperature range from 0 C to 80 C were measured and the change of
the density with respect to the temperature is given in Fig. 6.
The regression equation for the density of TSOME was derived
and is given in the following equation:

q 0:70484T 898:15485

where T is temperature in C, q is the density in kg/m3. The R2 value


was determined as 0.999 for this equation.
The obtained tobacco seed cake after extraction of oil was characterized by high yield of proteins (41% by weight) and crude
bers (15% by weight) and low percentage of mineral matters
(0.2% by weight) which makes it comparable to seed cakes of other
oil-bearing seeds, and could serve as feed supplement in premixes
for livestock and poultry [13].
4. Conclusions
The biodiesel production and fatty acid composition of the oil is
very important to obtain high quality biodiesel production. This
study explained the methods to produce biodiesel fuel, which

Table 5
The coefcients of Eq. (1) for Diesel Fuel No. 2, TSOME and TSOME with an additive (octadecene-1-maleic anhydride copolymer, 0.5% in weight basis) (045 C).
Material

D100
TSOME
TSOME
TSOME
TSOME

0.942688
0.691176
6162.894
108.708
0.409212

2366.578
1092.259
3441491.194
53593.021
1762.149

722364.449
530297.792
80623515.466
6306425.189
635774.807

(45.06.0 C)
(6.04.0 C)
(0.04.0 C).
with an additive (octadecene-1-maleic anhydride copolymer, 0.5% in weight basis)

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N. Usta et al. / Energy Conversion and Management 52 (2011) 20312039

910
900

Density (kg/m3)

890
880
870
860
850
840
830
0

10

20

30

40

50

60

70

80

90

Temperature (oC)
Fig. 6. The change of TSOME density with respect to temperature.

meets EN 14214 standard, from tobacco seed oil. There were no


any problems with the properties related to the biodiesel production technique. In addition, there were no problems with some
properties, like cetane number, density and viscosity, which
depend on the fatty acid composition of the raw oil. However,
the oxidation stability of the biodiesel was lower than the
minimum limit of the standard and the iodine number was higher
than the maximum limit of the standard. The oxidation stability
may be improved with the use of different antioxidants and pyrogallol was found to be most effective antioxidant. Iodine number
was improved with blending with an other biodiesel produced
from waste cooking oil that has more saturated fatty acids.
Although the blending decreased the iodine number of tobacco
seed oil methyl ester below the maximum limit of standard, cold
lter plugging point was increased. Therefore, it was required to
use cold ow improvers. Octadecene-1-maleic anhydride copolymer is an effective cold ow improver for TSOME and its blends
with WMCOME. It was determined that addition of pyrogallol at
500 ppm and octadecene-1-maleic anhydride copolymer at 0.5%
by weight does not affect the other properties negatively. Although
addition of octadecene-1-maleic anhydride copolymer increased
the viscosity slightly, it improves the viscosity of the biodiesel at
low temperatures.
Acknowledgement
The authors would like to thank The Scientic and Technological
Research Council of Turkey (TUBITAK) for supporting this study
under Project Contract No. 104M256.
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