ELSEVIER

PII: SOO16-2361(a7)00289-5
Short Communication
Fuel Vol. 77, No. 9/10, 1117-1120, 1998 pp.
0 1998 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
0016.2361/98 $19.00+0.00
Fuel properties and calculation of higher heating
values of vegetable oils
Ayhan Demirbag
Department of Science Education, Educational Faculty, Black Sea Technical University,
61335 Akgaabat-Trabzon, Turkey
(Received 15 J uly 1997; revised 24 November 1997)
The physical, chemical and fuel properties of vegetable oils were investigated in this work. Combustion heats,
determined as higher heating values (HHVs), of vegetable oil samples obtained from different Turkish sources
were determined experimentally and calculated from chemical analyses. The HI-IV (kJ g-l) of the oils as a
function of saponification value (SV) and iodine value (IV) was calculated with the equation: HHV = 49.43 -
[O.O41(SV) + O.O15(IV)], for which the correlation coefficent was 0.9999. The HHVs calculated from this
equation showed a mean difference of 0.0067%. 0 1998 Elsevier Science Ltd. All rights reserved
(Keywords: vegetable oils; fuel properties; higher heating value; calculation)
Fuel properties for the combustion
analysis of vegetable oils can be grouped
conveniently into physical, chemical and
thermal properties. Physical properties
include viscosity, density, cloud point,
pour point, flash point, boiling range,
freezing point and refractive index. Che-
mical properties comprise chemical struc-
ture, acid value, saponification value,
iodine value, peroxide value, hydroxyl
value, acetyl value, overall heating value,
ash and sulfur contents, sulfur and copper
corrosions, water and sediment residium,
oxidation resistance, ignitability and ther-
mal degradation products. Thermal proper-
ties are distillation temperature, thermal
degradation point, carbon residue, specific
heating content, thermal conductivity, etc.
In an earlier study, formulae were
developed for calculation of the higher
heating values (I-II-IV) of biomass fuels
from their proximate analysis data. Numer-
ous formulae for calculating the HHVs of
coal from proximate analysis data have also
been proposedz-4.
In a previous study5, the fuel properties
of vegetable oils that can be grown as
domestic field crops were reviewed. The oil
samples were also characterized chemi-
cally, and certain fuel properties were
correlated to chemical composition. The
following mathematical relationship has
been developed for their HHV in MJ kg-:
HHV = 33.74 + 0.3356WACL
- 0.07946WADB
(1)
where WACL is the weighted average
number of carbon atoms in the fatty acid
chains and WADB is the square of the
weighted average number of double bonds
in the fatty acids. The correlation coeffi-
cient was given as 0.90 for eqn (1).
Vegetable oils have different chemical
structures to petroleum-based fuels. Up to
three fatty acids are linked to a glycerol
molecule with ester linkages. The fatty
acids vary in their carbon chain length and
in the number of double bonds. Vegetable
oil fuels are not petroleum-competitive
fuels because they are more expensive
than petroleum fuels. However, with
recent increases in petroleum prices and
uncertainties concerning petroleum avail-
ability, there is renewed interest in using
vegetable oils in diesel engines.
The objectives of this study were to
investigate and compare some fuel proper-
ties of vegetable oils, and to relate the
combustion heats to their chemistry.
EXPERIMENTAL
Some of the vegetable oil samples used in
this study were obtained from different
Turkish vegetal sources. The HHV of the
samples was measured in a bomb calori-
meter according to ASTM D2015 standard
method.
Standard procedures were applied to
determine the technological properties of
the vegetable oils. The oils samples were
saponified for 3.5 h at 65C with 0.5 N
methanolic potassium hydroxide to liberate
the fatty acids present as their esters6. The
unsaponifiables present in the mixture were
extracted three or four times with equal
volumes of petroleum ether.
Saponified solutions were diluted with
an equal volume of water, acidified to
pH 3-4 by the addition of 1.5 N hydro-
chloric acid, and the fatty acids present in
solution were extracted with diethyl ether.
After evaporation of the diethyl ether, the
acids were weighed and methylated with
diazomethane according to the method of
Schelenk and Gellermans.
Methyl esters of me fatty acids were
analysed on a 12 m long, 0.2 mm i.d.,
capillary Carbowax PEG 20 glass column
with a film thickness of 0.25 pm. The
carrier gas was helium. Chromatograms
and spectra were recorded with the follow-
ing instruments: a Hewlett-Packard 5790
gas chromatograph and a VG 70-250-SE
mass spectrometer with double focusing.
Ionization was carried out at 70 eV. The
mass spectrometer was fitted to the gas
chromatograph by means of a capillary
glass jet separator.
The characteristic properties of the oils
were determined by AOCS Tentative
Methods Cd 3a-63 and Cd 8-539. The
fatty acid compositions of some vegetable
oils are shown in Table 12-6.
The ASTM has developed a standard,
ASTM D975, for classifying hydrocarbon
diesel fuels. The standard ASTM test for
measuring each corresponding fuel prop-
erty and the ASTM limits for No. 2 diesel
fuel are given in Table 2.
Fuel 1998 Volume 77 Number g/IO 1117
Fuel properties and HHVs of vegetable oils: A. Demirbas
Table 1 Fatty acid compositions of vegetable oils, % by weight
Vegetable oil Fatty acid
16:0 16:l 180 18:l 18:2
Ailanthus 31.0 0 0 8.1 51.1
Bay laurel 25.9 0.3 3.1 10.8 11.3
Beech 11.6 3.5 4.2 10.4 33.3
Beechnut 8.8 0 3.2 30.4 48.9
Castor 1.1 0 3.1 4.9 1.3
Corn 11.8 0 2.0 24.8 61.3
Cottonseed 28.7 0 0.9 13.0 57.4 Crambe 2.1 0 0.7 18.9 9.0
Hazelnut ker- 4.9 0.2 2.6 83.6 8.5
nel
Linseed 5.1 0.3 2.5 18.9 18.1
Peanut 11.4 0 2.4 48.3 32.0
Poppyseed 12.6 0.1 4.0 22.3 60.2
Rapeseed 3.5 0 0.9 64.1 22.3
Safflowerseed 7.3 0 1.9 13.6 77.2
H.O. Safflo- 5.5 0 1.8 79.4 12.9
werseed
Sesame 13.1 0 3.9 52.8 30.2
Soybean 13.9 0.3 2.1 23.2 56.2
Spruced 5.2 0 1.0 14.7 30.4
Sunflowerseed 6.4 0.1 2.9 17.7 72.9
Walnut kemal 7.2 0.2 1.9 18.5 56.0
18:3 20:o Others
7.3 0 2.0
17.6 0 31.0
16.4 6.0 14.6
0 0 6.7
0 0 89.6
0 0.3 0
0 0 0 6.9 2.1 60.4
0.2 0 0
55.1 0 0
0.9 1.3 3.7
0.5 0 0.3
8.2 0 0
0 0 0
0 0.2 0.4
0 0 0
4.3 0 0
5.7 23.2 20.0
0 0 0
16.2 0 0
Reference no.
12
13
7
14
5
Determined
DeteFd
Determined
DeteFd
Determined
5
15
5
15
16
6
Determined
Determined
Bay laurel oil contains 26.5% of 12:0 and 4.5% of 14:0 fatty acids
bRicinoleic is the only 18:l fatty acid which contains a hydroxyl group. Its content in castor oil is 89.6%
Crambe oil contains 58.5% of 22:1,0.8% of 22:0, and 1.1% of 24:0 fatty acids
dSpruce oil only contains 18:3(5c, 9c, 12~) pinolenic acid (5.7%)
Table 2 ASTM tests and limits for diesel fuels
Test ASTM test no. ASTM limits
Distillation range (C) D86 282-338
Flash point (C) D93 52 mitt
Viscosity (mm* s-) D445 1.9-4.1
Water and sediment (% by volume) D1796 0.05% max.
Carbon residue (% by weight) D524 0.35% max.
Ash by weight (%) D482 0.01% max.
Sulfur by weight (%) D129 0.5% max.
Cetane no. D613 40 min.
Table 3 Fuel properties of vegetable oils
Vegetable oil ASTM test no. for each fuel property
D86 D93 D445 D524 D482 D129 D613
Ailantbus 150-350 238 30.2 0.22 0.02 0.01 35.1
Bay laurel 14.5-345 226 23.2 0.20 0.03 0.02 33.6
Beech 155-360 242 34.6 0.24 0.04 0.006 36.2
Beechnut 155-365 260 38.0 0.23 0.03 0.008 38.2
Castor - 260 29.7 0.21 0.01 0.01 42.3
Corn 155-365 276 35.1 0.22 0.01 0.01 37.5
Cottonseed 170-355 235 33.7 0.25 0.02 0.01 33.7
Crambe - 274 53.2 0.23 0.04 0.01 52.9
Hazelnut kernel 160-350 230 24.0 0.21 0.01 0.02 35.8
Linseed 165-365 240 28.0 0.24 0.01 0.01 27.6
Peanut - 270 40.0 0.22 0.02 0.01 34.6
Poppyseed 170-370 265 42.4 0.25 0.02 0.01 36.7
Rapeseed - 245 37.3 0.31 0.006 0.01 37.5
Safflowerseed 165-370 260 31.6 0.26 0.007 0.01 42.0
H.O. Safflower - 292 40.8 0.24 0.01 0.02 48.8
Sesame - 262 36.0 0.25 0.002 0.01 40.4
Soybean - 255 33.1 0.24 0.006 0.01 38.1
Spruce 150-350 238 35.6 0.26 0.01 0.01 34.2
Sunflowerseed 155-355 272 34.4 0.28 0.01 0.01 36.7
Walnut kemal 160-355 232 36.8 0.24 0.02 0.02 33.6
RESULTS AND DISCUSSION
The relationship between higher heating
value and structural properties of the oil
samples was investigated. For HI-IV, eqn
(1) shows an increase with increasing chain
length and a decrease with increase in the
number of double bonds. The increase in
heat content results from a high increase in
the number of carbons and hydrogens, as
well as an increase in the ratio of these
elements relative to oxygen. A decrease in
1118 Fuel 1998 Volume 77 Number 9110
Fuel properties and HHVs of vegetable oils: A. Demirbas
Table 4 Chemical properties and higher heating values (HHVs) determined and calculated from eqn (3)
Vegetable oil
Ailanthus
Bay laurel
Beech
Beechnut
Castor
Corn
Cottonseed
Crambe
Hazelnut kernel
Linseed
Peanut
Poppyseed
Rapeseed
Safflowerseed
H.O. Safflower
Sesame
Soybean
Spruce
Sunflowerseed
Walnut kemal
-
Iodine value (g YlOO g Saponification value (mg
oil) KOH/g oil)
Determined
107.18 206.34 39.38
69.82 220.78 39.32
105.15 202.16 39.59
110.64 193.52 39.82
88.72 202.71 37.41
119.41 194.14 39.64
113.20 202.7 1 39.44
99.83 178.59 40.62
98.62 197.63 39.83
156.74 188.71 39.33
119.35 199.80 39.45
116.83 196.82 39.59
108.05 197.07 39.73
139.83 190.23 39.52
88.57 206.82 39.61
91.76 210.34 39.42
120.52 194.61 39.63
96.08 207.79 39.44
132.32 191.70 39.57
135.24 190.82 39.56
lWc
80
60
I
0 : Linseed oil
A
: Poppyseed oil
0 : Hazelnut kemel oil
0
: Corn oil
/ I I I 1 I
lotI 150 200 250 300 350 400
Temperature, c
Figure 1 Distillation curves for some vegetable oils
heat content is the result of fewer hydrogen
atoms (i.e., greater unsaturation) in the
molecule. The higher heat combustion or
the higher heating content (HHC) of an oil
is the quantity of heat evolved when one
mole of a compound is burned to CO2 and
Hz0 at initial temperature and pressure.
Examination of data obtained for a great
many compounds has shown that the HHC
of an aliphatic hydrocarbon agrees rather
closely with that calculated by assuming a
certain characteristic contribution from
each structural unit. For open-chain
alkanes, each methylene group, -CH2-,
contributes very close to 46 956 kJ kg-.
The ultimate analysis of a vegetable oil
provides the weight percentages of carbon,
hydrogen and oxygen. The carbon, hydro-
gen and oxygen contents of various
common vegetable oils are 74.5-78.4,
10.6-12.4 and 10.8-12.0 wt%, respec-
tively. The HHV of vegetable oils5 ranges
from 37.27 to 40.48 kJ g-. The HHVs of
different vegetable oils vary by < 9%.
Figure I shows a comparison of the
distillation curves of linseed, hazelnut
kernel, corn and poppyseed oils. Some
26-34% by weight of fractions obtained
from the fractional distillation of the
vegetable oils are within the ASTM limits
given in Table 2 for diesel fuel (Figure 1).
When the ASTM D86 procedure was used
to distil the vegetable oils, they cleaved
into a two-phase distillate. Freliminary data
indicate a complex mixture of products
including alkanes, alkenes and carboxylic
compounds5. Typically, it was not possible
to distil all of the vegetable oil and some
HHV (kJg_)
Calculated Difference (%)
39.36 -0.05 1
39.3 1 -0.025
39.56 -0.076
39.84 +0.050
39.79 +6.389
39.68 +0.101
39.42 -0.05 1
40.61 -0.025
39.85 +0.050
39.34 +0.050
39.45 0.000
39.61 +0.050
39.73 0.000
39.53 +0.025
39.62 +0.025
39.43 +0.025
39.64 to.025
39.47 +0.076
39.59 +0.050
39.58 +0.050
brownish residue remained in the distilla-
tion flask. However, the soaps obtained
from the vegetable oils can be distilled into
hydrocarbon-rich products with higher
yields. These findings are in general
agreement with results given in the
literature.
The fuel properties of the vegetable oils
are given in Table 3. As can be seen in
Table 3 the vegetable oils were all extremly
viscous, with viscosities ranging from 10 to
20 times that of the ASTM upper limit
given for diesel fuels in Table 2. The cetane
ratings of most of the vegetable oils were
close to or exceeded the ASTM minimum
of 40 for diesel fuels.
Comparison with ASTM limits in Table
2 indicates that all of the vegetable oils met
ASTM limits for carbon residue, ash
content and total sulfur content.
Table 4 lists the chemical properties and
the determined and calculated HHVs of the
vegetable oils. Because castor oil contains
a hydroxyl group, its HHV is lower than the
others. Saponification values are milli-
grams of KOH necessary to saponify 1 g
of oil sample. The iodine value is the
amount of iodine (in grams) necessary to
saturate 100 g of oil sample.
Table 1 indicates the fatty acid composi-
tions of the vegetable oils. Palmitic (16:0)
and stearic (l&O) were the two most
common saturated fatty acids, with every
vegetable oil containing at least a small
amount of each one. Similarly, oleic (18: 1)
was the most common monounsaturated
fatty acid. All of the vegetable oils
contained some linolenic acid (l&2) and
many of the oils also contained some
linolenic acid (18:3).
In an earlier study, by investigating the
dependence of observed HHV on the
carbon, hydrogen and oxygen contents for
lignocellulosic fuels, the following
expression for calculation of HHV
Fuel 1998 Volume 77 Number 900 1119
Fuel properties and HHVs of vegetable oils: A. Demirbas
0 :cakulated
0 :Detamllnsd 62
I
39 40 41
Calculated HHV. kJ / g
Figure 2 Plot of determined HHV versus HHV calculated by using eqn (3) for the 19
vegetable oils given in Table 4
(kJ g-l) was suggested:
HI-IV = 33.5(C) + 142.3(H) - 15.4(O)
(2)
Thus the HHV of a fuel as a function of its
carbon content (C, wt%), hydrogen content
(H, wt%) and oxygen content (0, wt%) can
be calculated with eqn (2).
The saponification value (SV) of an oil
decreases with increase of its molecular
weight. On the other hand, the percentages
of carbon and hydrogen in an oil increase
with decrease in molecular weight. The
increase in iodine value (IV) (i.e., carbon-
carbon double bond, -C=C-, content)
results in a decrease in the heat content of
an oil. Therefore, for calculation of the
HHVs (kJ g-l) of vegetable oils, eqn (3) is
suggested and was used in this study:
HHV = 49.43 - [O.O41(SV) + O.OlS(IV)]
(3)
The HHVs calculated by using eqn (3) and
measured experimentally are given in
Figure 2. Eqn (3) represents the correlation
obtained by means of regression analysis.
The correlation coefficient is 0.9999. The
HHVs calculated with eqn (3) showed a
mean difference of only 0.0067%. In this
calculation the HHV of castor oil was not
taken into account.
CONCLUSIONS
The physical, chemical and thermal fuel
properties of the vegetable oils obtained in
the present research are in agreement with
results given in the literature.
The heating values of the vegetable oils
can be calculated by using the SVs and IVs
obtained from simple chemical analyses.
The experimental determination of heating
value and ultimate analysis requires special
instrumentation, whereas chemical analysis
data can be obtained relatively easily by
using common laboratory equipment. The
heat contents of the vegetable oils were
approximately 88% of those of diesel fuels.
Mathematical equations have been devel-
oped to calculate the HHVs of the vegetable
oils from chemical analysis data. The HHVs
calculated from these new correlations show a
mean difference from the measured values of
0.1 to 1.0%. Eqn (3) developed in this work
shows excellent agreement with experimental
results for the vegetable oils.
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1120 Fuel 1998 Volume 77 Number 9110