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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
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
2032
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
2033
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).
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
2034
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
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
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
2035
12
11
10
butylated hydroxytoluene
propyl gallate
tert-butylhydroquinone
pyrogallol
-Tocopherol
butylated hydroxyanisole
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.
2036
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
Table 4
Effects of different cold improvers on CFPP of TSOME, WMCOME and their Blend (T70W30-70% TSOME and 30% WMCOME).
Additives
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
0.5
1.0
7
6
7
8
3
0
0.5
1.0
12
9
6
6
5
2
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.
2037
25
D100
TSOME
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).
le
ABT C2
T
1
q 0:70484T 898:15485
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)
2038
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.
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