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Abstract
The aim of this study was to estimate mathematical relationships between higher heating value (HHV) and viscosity, density or flash
point measurements of various biodiesel fuels. The HHV is an important property defining the energy content and thereby efficiency of
fuels, such as vegetable oils and biodiesels. The biodiesels were characterized for their physical and main fuel properties including vis-
cosity, density, flash point and higher heating value. The viscosities of biodiesels (2.8–5.1 mm2/s or cSt at 311 K) were much less than
those of pure oils (23–53 mm2/s at 311 K), and their HHVs of approximately 41 MJ/kg were 10% less than those of petrodiesel fules
(46 MJ/kg). Compared to No. 2 diesel fuel, all of the vegetable oil methyl esters were slightly viscous. The density and flash point values
of vegetable oil methyl esters are highly lower than those of vegetable oils. The HHVs of vegetable oils and their biodiesels were measured
and correlated using linear least square regression analysis. There is high regression between viscosity and higher heating value for veg-
etable oil and biodiesel samples. An increase in density from 848 to 885 g/L for biodiesels increases the viscosity from 2.8 to 5.1 cSt and
the increases are highly regular. There is high regression between density and viscosity values vegetable oil methyl esters. The relation-
ships between viscosity and flash point for vegetable oil methyl esters are considerably regular.
Ó 2007 Elsevier Ltd. All rights reserved.
0016-2361/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2007.08.007
1744 A. Demirbas / Fuel 87 (2008) 1743–1748
the transesterification process compared to methanol cup and a thermostat was used to measure the viscosity
because it is derived from agricultural products and is of all samples. The kinematic viscosity measurements were
renewable and biologically less objectionable in the envi- carried out as mm2/s or cSt at 311 K temperature. The tem-
ronment, however methanol because of its low cost and peratures were checked with a digital thermometer within
its physical and chemical advantages. The transesterifica- the thermostat and the viscosimeter. At the beginning of
tion reaction can be catalyzed by alkalis [9,17–19], acids each measurement a volume of 50 ml of the sample was
[20], or enzymes [21–24]. filled into the measuring cup.
A novel process of biodiesel fuel production has been Density measurements were carried out using a pycnom-
developed by a non-catalytic supercritical fluids (methanol eter at a temperature of 311.15 ± 0.05 K; the pycnometer
and ethanol) method. The transesterfication of triglycerides of capacity about 25 mL being calibrated with water [32].
by supercritical methanol, ethanol, propanol and butanol, Flash point measurements were carried out using a Koeh-
has proved to be the most promising process [25,26]. ler mark apparatus.
The standard measure of the energy content of a fuel is Relative standard deviation (RSD) for all measurements
its heating value (HV), sometimes called the calorific value was 0.9–1.2% for three separate determinations.
or heat of combustion. The heating value is obtained by the
complete combustion of a unit quantity of solid fuel in an
oxygen-bomb colorimeter under carefully defined condi- 3. Results and discussion
tions. The gross heat of combustion or higher heating value
(GHC or HHV) is obtained by oxygen-bomb colorimeter The viscosity, density, flash point, and higher heating
method as the latent heat of moisture in the combustion value (HHV) measurements of twenty two vegetable oils
products is recovered. The higher heating value is one of and their methyl esters are given in Table 1. The viscosity,
the most important properties of a fuel. density, flash point, and higher heating value (HHV) mea-
Higher heating values of biomass-derived fuels have surements of fourteen methyl esters of various vegetable
been estimated using their proximate and ultimate analysis oils are tabulated in Table 2.
data [27–29]. It has also been shown that an estimate of the Viscosity is a measure of the internal friction or resis-
heating values of vegetable oils can be calculated using tance of an oil to flow. As the temperature of oil is
saponification and iodine data of the oils [30,31]. The increased, its viscosity decreases and it is therefore able
higher heating value of a fuel increases with increasing car- to flow more readily. Viscosity is the most important prop-
bon number in fuel molecules and also increases as the erty of biodiesel since it affects the operation of fuel injec-
ratio of carbon and hydrogen to oxygen and nitrogen tion equipment, particularly at low temperatures when the
increases [28]. increase in viscosity affects the fluidity of the fuel. High vis-
Fuel properties of vegetable oils were characterized by cosity leads to poorer atomization of the fuel spray and less
determining its viscosity, density, cetane number, cloud
and pour points, distillation range, flash point, ash content, Table 1
sulfur content, carbon residue, acid value, copper corrosion Viscosity, density flash point and higher heating value (HHV) measure-
and HHV [11]. ments of twenty two vegetable oils
The objective of this study was to estimate mathematical Vegetable oil Viscosity Density Flash point HHV
relationships between higher heating value (HHV) and vis- (cSt) (g/L) (K) (MJ/kg)
cosity, density or flash point measurements of various bio- Ailanthus 30.2 916 513 39.44
diesel fuels from various vegetable oils by transesterification Bay laurel 23.2 921 499 39.30
method. Beech 34.6 915 515 39.59
Beechnut 38.0 912 533 39.82
Corn 35.4 914 532 39.66
2. Experimental Cottonseed 33.5 915 524 40.38
Crambe 53.0 902 557 39.83
The vegetable oils were obtained from commercial Hazelnut 24.0 920 503 39.33
sources and used without further purification. The samples Linseed 27.2 921 520 39.50
Mustard oil 33.8 913 518 39.57
were converted to methyl esters by alkali catalytic and non-
Olive 29.8 918 504 39.50
catalytic supercritical methanol transesterification methods. Palm 24.1 923 501 39.74
The HHVs of the vegetable oils and their methyl esters Peanut 39.6 908 543 39.85
were measured in a bomb calorimeter according to ASTM Poppy seed 42.4 907 538 39.73
D2015 standard method [30]. An oxygen-bomb was pres- Rapeseed 37.3 912 531 39.52
Safflower seed 31.3 914 531 39.79
surized to 3 MPa with an oxygen container. The bomb
H.O.Safflower 41.2 906 548 39.51
was fired automatically after the jacket and bucket temper- Sesame 35.5 913 533 39.63
atures equilibrated to within acceptable accuracy of each Soybean 32.6 914 528 39.44
other. Spruce 35.6 914 513 39.57
Each sample was used for viscosity and density measure- Sunflower seed 33.9 916 535 39.59
Walnut 36.8 912 524
ments. A Redwood No. 1 viscosimeter with a measuring
A. Demirbas / Fuel 87 (2008) 1743–1748 1745
40.2
40
Table 3
Viscosity, density and cetane number measurements of seven methyl ester
39.8
biodiesels
Source Viscosity cSt at Density g/L at Cetane References 39.6
313.2 K 288.7 K number
Sunflower 4.6 880 49 [33] 39.4
Soybean 4.1 884 46 [34]
Palm 5.7 880 62 [33] 39.2
20 25 30 35 40 45 50 55
Peanut 4.9 876 54 [35]
Cottonseed 3.8 874 46 [36] Viscosity, cSt
Babassu 3.6 – 63 [35]
Fig. 1. Correlation between viscosity and higher heating value for
Tallow 4.1 877 58 [37]
vegetables oils.
1746 A. Demirbas / Fuel 87 (2008) 1743–1748
42.1 890
Higher heating value, MJ/kg
41.8 880
Density, g/L
41.5 870
41.2 860
40.9 850
40.6 840
2.8 3.3 3.8 4.3 4.8 5.3 2.8 3.3 3.8 4.3 4.8 5.3
Viscosity, cSt Viscosity, cSt
Fig. 2. Correlation between viscosity and higher heating value for Fig. 4. Correlation between viscosity and density for biodiesels.
biodiesels.
470
vegetables oils and biodiesels decrease with density. The
equations between viscosity and density are 460
for vegetable oils:
450
VS ¼ –0:7328DN þ 938:57 ð3Þ
Flash point, K
42
925
920
Higher heating value, MJ/kg
41.7
915
Density, g/L
41.4
910
905 41.1
900
40.8
895 840 850 860 870 880 890
20 25 30 35 40 45 50 55 Density, g/L
Viscosity, cSt
Fig. 6. Correlation between density and higher heating value for
Fig. 3. Correlation between viscosity and density for vegetables oils. biodiesels.
A. Demirbas / Fuel 87 (2008) 1743–1748 1747
40.8 4. Conclusion
410 420 430 440 450 460
Flash point, K
Equations have been developed to calculate higher heat-
Fig. 7. Correlation between flash point and higher heating value for ing values (HHVs) of various vegetable oils and their bio-
biodiesels. diesels from their viscosity, density or flash point
measurements.
Fig. 7 shows the correlation between flash point and The vegetable oils are all extremely viscous with viscos-
higher heating value for biodiesels. The equation between ities ranging from 9 to 17 times greater than petroleum die-
flash point and higher heating value for biodiesels is sel. Biodiesel, an alternative diesel fuel, is made from
renewable biological sources such as vegetable oils and ani-
HHV ¼ 0:021FP þ 32:12 ð7Þ mal fats by transesterification reaction using methanol or
ethanol. The purpose of the transesterification process is
with coefficient of regression (r) value of 0.9530. There is to lower the viscosity of the oil.
considerably high regression between flash point and high- The properties of biodiesel are close to diesel fuels. Fuel
er heating value for biodiesel samples. The higher heating properties of vegetable oils and biodiesels are characterized
values increase with increasing flash point for the by determining its viscosity, density, cetane number, cloud
biodiesels. and pour points, distillation range, flash point, ash content,
Viscosity is one of the most important parameters sulfur content, carbon residue, acid value, copper corrosion
required in the design of combustion process. From the and HHV according to ISO norms.
physicochemical point of view, viscosity means the resis- The heating values of the vegetable oils and their methyl
tance of one part of the fluid to move relative to another esters (biodiesels) can be calculated by using the viscosity,
one. Therefore, viscosity must be closely correlated with density and flash point obtained from simple physical mea-
the structural parameters of the fluid particles. The viscos- surements. The experimental determination of heating
ity slightly decreases with increased degree of unsaturation value and an element (C, H, O) content requires special
and rapidly increases with polymerisation. The viscosity instrumentation, whereas physicochemical data can be
almost linearly decreases as the iodine value increases. obtained relatively easily by using common laboratory
On the other hand, no correlation was found for the depen- equipment.
dence of viscosity on saponification value, which character- There is high regression between HHV and viscosity val-
ises the chain length of fatty acids [39]. ues of vegetable oils and their methyl esters. An increase in
The length of the fatty acid chain was shown to have a density from 848 to 885 g/L for vegetable oil methyl esters
marked influence on the viscosity. The viscosity of the sys- or biodiesels increases the viscosity from 2.83 to 5.12 mm2/s
tems is also influenced by the degree of unsaturation. One and the increases are highly regular.
double bond was shown to increase viscosity, whereas two
or three double bonds caused a decrease in the viscosity of References
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ID Title Pages
207915 Relationships derived from physical properties of vegetable oil and biodiesel fuels 6
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