Fuel 264 (2020) 116817

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Fuel
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Full Length Article

Comparision of fuel properties of biodiesel fuels produced from different oils T

to determine the most suitable feedstock type
Fevzi Yaşar
Vocational School of Technical Sciences, Department of Chemistry and Chemical Process Technology, Batman University, 72100 Batman, Turkey

A R T I C LE I N FO A B S T R A C T

Keywords: Energy, having primary importance in ensuring the prosperity and development of countries, has recently be-
Energy come one of the most strategic parameters in the international arena. Although there is no problem with oil and
Biodiesel gas reserves for the next few decades, the issues such as searching for new alternative energy sources, producing
Feedstock and delivering them to consumers will be the most critical issues in energy sector. Today, almost all countries of
Fatty acid composition
the world (developed and developing) put in place new energy strategies to increase the share of alternative
Fuel properties
energy sources in their total energy consumption. Biodiesel is one of the most promising alternative energy
sources. Biodiesel can be produced from a lot of different feedstocks such as vegetable oils, waste frying oils and
fats, soapstock, algae, etc. However, produced biodiesel’s fuel properties significantly depend on the physico-
chemical properties and fatty acid composition of its feedstock. In this study, methyl ester biodiesel fuels were
produced by using the same transesterification reaction conditions from ten different vegetable oils including
soybean, sunflower, corn, cottonseed, canola, olive, safflower, hazelnut, rapeseed, and algae. These oils’ fatty
acid distributions and some critical fuel properties of biodiesel fuels obtained from these oils were detected and
compared with each other to determine the best feedstock type for biodiesel production. The highest ester
content value was measured for the biodiesel fuels produced from algae (98.7%) and olive oil (98.6%). In
addition, cetane numbers of these two biodiesels were the highest (59 for algae biodiesel and 58 for olive oil
biodiesel). The best cold flow properties were determined for biodiesel fuels obtained from algae, corn, and
canola oils with the cold filter plugging point (CFPP) values of −14 °C, −13 °C and −13 °C, respectively.

1. Introduction
The major part of all energy consumed worldwide comes from fossil
sources (petroleum, coal and natural gas). Fossil energy sources are
limited and can be found only in certain parts of the world [1]. The
decrease of fossil fuel reserves and the rising concerns about the vital
impacts of greenhouse gas emissions on the environment have created a
need for finding alternative energy sources to replace traditional ones
[2]. The scarcity of conventional fossil fuels, the increase of con-
centrations of combustion-generated pollutants in the atmosphere and
the rising costs of environmental problems in the world economy made
biomass sources more attractive [3]. Within the context of alternative
energy policies, the usage of agriculture-based various biomass sources
has found a wide application area all over the world, thanks to their
attractive properties such as compatibility with existing fuel distribu-
tion infrastructure, better exhaust emission profile, renewability, sus-
tainability, etc. The usage of biofuels especially in transportation sector
is so critical in terms of reducing greenhouse gas emissions. Biodiesel,
as an alternative diesel fuel, is made from renewable biological sources
such as vegetable oils and animal fats. This fuel is biodegradable, non-
toxic and has low emission profiles and better lubricity properties as
compared to petroleum diesel [4]. In addition to its environmental
benefits, well-organized and designed biodiesel production from agri-
cultural sources may improve the rural development and consequently
reduce immigration from villages to cities, which is a big problem for
developing countries [5]. However, biodiesel production from inedible
feedstocks, such as waste frying oils and fats, is more accurate in order
not to cause increases in edible vegetable oil prices and disturb the
balance in food supply [6,7]. In addition to waste feedstocks, algae can
also be considered as a potential biodiesel feedstock. Algae-based bio-
diesel, which is defined as the third generation biofuel, could be an
alternative energy source since it has many advantages. Algae are or-
ganisms that make use of sunlight and CO2 more effectively compared
to other oil plants, and their cleavage potentials and growth rates are
also quite high. It is very favorable that the agricultural areas are not
used during the cultivation of algae and they can reproduce with high
speed even in very small areas. Moreover, some algae species contain
more oil than field crops and they are not affected by seasonal changes

E-mail address: fevzi.yasar@batman.edu.tr.

https://doi.org/10.1016/j.fuel.2019.116817
Received 25 August 2019; Received in revised form 12 November 2019; Accepted 3 December 2019
Available online 20 December 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
F. Yaşar
and climatic conditions. These superiorities make algae very advanta-
geous feedstocks for biodiesel production [8]. As mentioned above,
biodiesel fuel can be produced from lots of feedstock containing tri-
glyceride. Feedstcok choice of the biodiesel industry is generally af-
fected from the annual vegetable oil production quantity of that
country. The most used feedstock is soybean in USA, rapeseed in Eur-
opean Union countries, palm oil in some tropical countries such as
Malaysia and Indonesia. Biodiesel is a fuel comprised of alkyl monoe-
sters of long chain fatty acids derived from the processed feedstock. It
should be strongly underlined that fatty acid composition of the feed-
stock does not significantly change during transesterification reaction
at which biodiesel fuel is obtained. Because of this, almost all critical
physico-chemical fuel properties of a biodiesel fuel (i.e. viscosity,
density, cetane number, iodine value, calorific value, lubricity, oxida-
tion stability, cold flow properties) strongly depend on the feedstock's
fatty acid characteristics such as the chain length and the number of
double bonds [9–11]. Canakci and Sanli [12] analyzed some critical
fuel properties of biodiesels produced from different biomasses and
compared them with those of petroleum-based diesel fuel. They have
concluded that freezing points of biodiesel fuels, especially produced
from fats having high saturation level, were unacceptably high. How-
ever, it was reported that if the branched-chain alcohols such as 2-
propanol were used in transesterification reactions, positive results in
the cold-low properties could be obtained. Ramos et al. [13] in-
vestigated the fatty acid compositions of various vegetable oils used in
biodiesel production. Also, they detected the fuel properties of biodiesel
fuels produced from these vegetable oils, and correlated them with the
fatty acid contents (degree of unsaturation) of the feedstocks. They
have reported that cetane number and oxidation stability values im-
proved with increasing carbon chain length and decreasing unsatura-
tion level (especially poly-unsaturated fatty acids). In addition, un-
saturated fatty acids caused higher iodine values and lower CFPPs.
Biodiesel fuels produced from almond, olive, corn, rapeseed and high
oleic sunflower oils had comparatively better properties because they
had more mono-unsaturated fatty acid content. Elangovan and Jeryr-
ajkumar [14] produced biodiesel fuels from different feedstocks by
varying the transesterification reaction conditions. In this study, they
measured kinematic viscosity, density, flash point, heating value, and
then calculated the correlation coefficients between these fuel proper-
ties. They mentioned that these fuel properties strongly depend on the
feedstock type and marginally affected from reaction parameters. In
addition, they observed strong positive correlation between these fuel
features and all of them increased with increasing carbon chain length
and degree of saturation. Dmytryshyn et al. [15] produced biodiesel
fuels from four vegetable oils (canola oil, green seed oil, processed
waste fryer grease and unprocessed waste fryer grease) by using me-
thanol and potassium hydroxide, and subsequently compared their fuel
properties such as density, viscosity, cloud point and pour point. They
reported that the highest methyl ester yield was obtained from canola
oil. The product yield with green seed oil was also satisfactory. The
most of the physico-chemical fuel properties of canola methyl ester and
green seed methyl ester were similar and not much different from those
of petroleum-based diesel fuel. Nevertheless, due to a low lubricity
property of the green seed methyl ester, the authors recommended lu-
bricity improver for this biodiesel fuel to protect the engine from fric-
tion and wear problems. In the literature there are numbers of studies
which characterize the fatty acid compositions of various vegetable oils
and measure the physico-chemical fuel properties of biodiesels obtained
from these vegetable oil feedstocks. However, in these papers, the
number of vegetable oil samples and measured fuel properties were
generally inadequate. The purpose of this study was to determine the
best vegetable oil as biodiesel feedstock. For this aim, the fatty acid
compositions of ten different vegetable oils were determined at first.
And then, the measured fuel properties of methyl ester biodiesels,
which were produced with the same transesterification reaction con-
ditions, were compared with each other’s and the specifications given in
2
Fuel 264 (2020) 116817
European Biodiesel Standard (EN-14214).
2. Materials and methods
In this study, biodiesel fuels were produced from ten different ve-
getable oils including algae, soybean oil, sunflower oil, corn oil, cot-
tonseed oil, canola oil, olive oil, safflower oil, hazelnut oil, rapeseed oil.
All of these vegetable oil feedstocks were purchased from various
companies in Turkey. Prior to transesterification reactions, the fatty
acid compositions of the vegetable oils were determined. The fatty acid
distributions of safflower oil, hazelnut oil, and rapeseed oil were cited
from the related literature. The fatty acid contents of the rest of the
vegetable oils were measured in Dicle University Science and
Technology Application and Research Center. For this purpose,
Shimadzu GCMS-TQ8030 gas chromatography device was used with
the AOCS Official method Cd 3A-63. Methanol (99.7% purity) and
potassium hydroxide (99.9% purity) was supplied by Sigma-Aldrich,
Turkey. Transesterification experiments were carried out in a 500 ml
four-necked batch reactor. The reactor was equipped with a reflux
condenser, to avoid methanol losses, a magnetic stirrer, a thermocouple
connected to a heater plate for temperature control, and two stoppers to
remove samples and to feed the raw materials, respectively. The reactor
was initially charged with the oil and preheated to the desired tem-
perature. The potassium hydroxide catalyst was dissolved in the me-
thanol and the resulting solution was added to the reactor. Reaction
conditions of methanol:vegetable oil molar ratio of 6:1, 0.75% w/w
potassium hydroxide, reaction temperature of 60 °C and reaction
duration of 60 min were kept constant in all transesterification reac-
tions. After the reaction time was completed, the reaction mixture was
transferred to the separation funnel. The mixture was left to rest for
overnight for complete glycerin phase separation. The glycerin accu-
mulated in the bottom was drained off. The methyl ester product was
washed four-times with deionized water, and subsequently, it was
centrifuged to remove the aqueous layer compound by methanol, re-
sidual catalyst, and glycerol. The residual methanol and water were
separated from the biodiesel fuel via rotary evaporation under vacuum
at 110 °C for 1 h. The obtained biodiesel fuels were stored in re-
frigerator at 4 °C. In order to compare the biodiesel fuels, which were
obtained from different vegetable oil feedstocks, their some critical fuel
properties (ester content, flash point, water and sediment content,
viscosity, density, sulfur content, copper strip corrosion, cetane
number, cold filter plugging point, carbon residue, acid number, free
and total glycerin, phosphorous content, distillation temperature, po-
tassium content and oxidation stability) were measured. These fuel
properties were detected in METU Oil Research Center, Batman
Refinery Fuel Analysis Laboratory of Turkish Oil Refineries Co.
(TUPRAS), Batman University Vocational School of Technical Sciences
Fuel Analysis Laboratory.
3. Results and discussion
3.1. Fatty acid compositions of vegetable oil feedstocks
There are three main types of fatty acids that can be present in a
triglyceride molecule: saturated (Cn:0), monounsaturated with one
double bond (Cn:1), and polyunsaturated with two or three double
bonds (Cn:2,3). Each biodiesel feedstock has its own fatty acid struc-
ture, and almost all of the critical fuel properties of any biodiesel fuel
strongly depend on the fatty acid contents of the feedstock from which
it is produced [16]. Because of this, fatty acid compositions of biodiesel
feedstocks should be investigated in detail. The fatty acid profiles of the
vegetable oils used in this study were summarized in Table 1. As seen,
vegetable oils investigated in this study were mostly comprised of
monounsaturated and polyunsaturated fatty acids. Based on the fatty
acid distribution, two additional parameters can also be calculated for
biodiesel feedstocks: the degree of unsaturation (DU), and long chain
F. Yaşar Fuel 264 (2020) 116817

Table 1
Fatty acid compositions of vegetable oils (wt.%).
Fatty acid C:D Closed Formula Algae Soybean Sunflower Corn Cottonseed Canola Olive Safflower [17] Hazelnut [18] Rapeseed [19]

Lauric C 12:0 C12H24O2 – – – – – – – – –

Myristic C 14:0 C14H28O2 – 0.07 0.08 0.02 0.69 0.05 – 0.10 0.13 –
Palmitic C 16:0 C16H32O2 15.64 11.43 5.93 12.23 21.47 6.23 13.27 6.70 5.82 3.49
Palmioleic C 16:1 C16H30O2 0.32 0.07 0.14 0.13 0.56 0.34 0.86 0.08 0.29 –
Stearic C 18:0 C18H36O2 2.10 4.03 3.44 2.62 2.61 2.49 3.69 2.40 2.74 0.85
Oleic C 18:1 C18H34O 54.89 24.85 36.22 31.40 18.21 61.46 68.00 11.50 79.30 64.40
Linoleic C 18:2 C18H32O2 19.56 55.33 52.95 51.21 55.45 22.12 12.48 79.00 10.39 22.30
Linolenic C 18:3 C18H30O2 4.88 3.34 0.38 0.85 0.15 5.11 0.76 0.15 0.46 8.23
Arachidic C 20:0 C20H40O2 2.24 0.25 0.23 0.32 0.06 1.43 0.48 – 0.16 –
Gadoleic C 20:1 C20H38O2 – – – – – – – – – –
Behenic C22:0 C22H44O2 0.33 0.57 0.46 0.13 0.14 0.37 0.24 – – –
Erucic C 22:1 C22H42O2 – – – – – – – – – –

saturated factor (LCSF). The required formulas used for DU and LCSF 3.2. Comparison of fuel properties of biodiesel produced from different
were given in Eq. (1), and Eq. (2), respectively. vegetable oils

DU = [monounsaturated Cn:1 (wt.%)] + 2
∗ [polyunsaturated Cn:2, 3 (wt.%)]
LCSF = 0.1 ∗ [C16: 0(wt.%)] + 0.5 ∗ [C18: 0(wt.%)] + 1.0
∗ [C20: 0 (wt.%)] + 1.5 ∗ [C 22: 0 (wt . %)] + 2
∗ [C 24: 0 (wt . %)]
All vegetable oil samples’ total saturation level, total unsaturation
level (TUS), mono- and poly-unsaturation level, DU and LCSF values
were given in Table 2. When fatty acid compositions are examined, it is
seen that the cotton seed oil had the highest saturated fatty acid con-
tent. Algae, and olive oil was in the second and the third order, re-
spectively. It is also seen that hazelnut, olive, rapeseed, canola and
algae oils have the highest mono-unsaturated oil compositions and the
lowest poly-unsaturated contents. In the literature, there are similar
studies which have been carried out to determine fatty acid contents of
vegetable oils. Ma et al. [20] reviewed the fatty acid distributions of
various oils for biodiesel production. The fatty acid structure of soy-
bean, sunflower, corn, cottonseed and rapeseed oils were similar to
those found in this study. Kostik et al. [21] investigated fatty acid
compositions of edible oils such as soybean, sunflower, corn, cotton-
seed, palm, olive, canola, and safflower in terms of saturated fatty acids,
monounsaturated fatty acids and polyunsaturated fatty acids. Their
results were very close to values given in Table 2. Orsavova et al. [17]
carried out a study on fatty acids composition of vegetable oils and their
contribution to energy content. They found similar results for the fatty
acid distributions of safflower, sunflower, rapeseed, and olive, and their
saturated and unsaturated rates. Demirbas [22] investigated the fatty
acid distributions of some vegetable oils which were commonly used in
biodiesel production including safflower, palm, sunflower, hazelnut,
soybean, corn, rapeseed and olive. The fatty acid structures of these oils
reported in his study were very close to the values given in Tables 1 and
2.
The fuel properties of all biodiesels produced from ten different
(1) vegetable oils and the specification values given in European Biodiesel
Fuel Standard (EN-14214) were given in Table 3. As can be seen in the
table, the most of the measured fuel properties were within the limits of
EN 14214. The degree of compliance of these parameters (Ester con-
tent, flash point, water and sediment, kinematic viscosity, density,
sulfur content, copper strip corrosion, cetane number, cold filter plug-
(2)
ging point, carbon residue, acid number, free glycerin, total glycerin,
phosphorus content, distillation, sodium/potassium, oxidation stabi-
lity) depends on the quality of vegetable oil (i.e. free fatty acid (FFA)
content, and water content), completeness of transesterification reac-
tion (conversion) and the suitability of purification steps after reaction
(i.e. the number of washing steps, temperature of washing water).
However, some of fuel properties were out of limit values. According to
the results of this study, it was observed that some fuel properties (ester
content, cetane number, cold filter plugging point and oxidation sta-
bility) of biodiesel are significantly affected from the feedstock prop-
erties.
3.2.1. Effect of water content of the feedstock on the ester content of
biodiesel
Water content of the processed feedstock is an important factor for
both of the acid- and alkaline-catalyzed transesterification reaction. It is
well known that the vegetable oils/fats used as raw materials for the
transesterification should be water-free since the presence of water has
negative effects on the reaction [23]. Water consumes the catalyst in
the reaction media and so reduces the catalyst efficiency. The presence
of water has a greater negative effect than that of free fatty acid (FFA).
Because of this, water content should be kept below 0.06% [24], much
lower than the recommended FFA content of 0.5% [25]. These pro-
blems may hinder the utilization of waste frying oils, fats and also crude
oils since they generally contain relatively high amount of water and
FFA [26]. Water concentration, which is formed during the pretreat-
ment reaction of feedstocks with high FFA, should also be considered.
When FFAs react with alcohol, water also forms together with
monoesters and forming water slows down or even finishes the

Table 2
Degree of saturation and unsaturation (wt.%), DU and LCSF values of vegetable oils.
Property Algae Soybean Sunflower Corn Cottonseed Canola Olive Safflower Hazelnut Rapeseed

Saturated 18.33 16.346 10.14 15.33 24.97 10.43 17.67 9.20 8.85 4.34
Monounsaturated 56.21 24.918 36.37 31.53 18.77 61.80 68.86 11.58 79.59 64.40
Polyunsaturated 25.44 58.668 53.33 52.06 55.59 27.23 13.22 79.15 10.85 30.53
TUS 81.65 83.586 89.7 83.59 74.36 89.03 82.08 90.73 90.44 94.93
DU 107.09 142.25 143.02 135.65 129.95 116.26 95.30 169.88 101.29 125.46
LCSF 5.36 4.25 3.23 3.05 3.73 3.85 4.01 1.87 2.11 0.774

3
F. Yaşar Fuel 264 (2020) 116817

Table 3
Properties of biodiesel from all vegetable oils (UNE-EN 14214).
Property Test Limits Units Algae Soybean Sunflower Corn Cottonseed Canola Olive Safflower Hazelnut Rapeseed

Ester Content EN 14103 98.5 min. % (w/w) 98.7 97.0 97.2 98.4 96.8 98.3 98.6 98.0 97.6 98.5
o
Flash point (closed cup) D 93 93.0 min C 140 170 178 172 175 137 177 180 171 172
Water and sediment D 2709 500 max. max ppm 190 216 214 197 218 200 200 204 210 196
Kinematic viscosity, 40 oC D 445 1.9–6.0 mm2/s 4.55 4.37 4.30 4.42 4.33 4.40 4.53 4.60 4.45 4.48
Density, 15oC 860–900 kg/m3 881 882 882 878 883 881 882 885 878 880
Sulfur Content EN 20846 10 max ppm 6.70 6.78 5.54 5.42 5.46 5.33 5.22 6.32 6.45 4.60
Copper Strip Corrosion D 130 No. 3 max – 2.1 2.3 2.2 2.1 2.3 2.0 2.2 2.3 2.2 2.1
Cetane Number D 613 47 min. – 59 51 50 56 56 55 58 53 57 54
CFPP EN 116 Report °C −14 −6 −4 −13 −12 −13 −12 −7 −12 −11
Carbon Residue D 4530 0.050 max. % w/w 0.038 0.041 0.042 0.040 0.038 0.032 0.023 0.042 0.032 0.033
Acid Number D 664 0.50 max. mg KOH/g 0.32 0.16 0.12 0.15 0.21 0.25 0.32 0.33 0.28 0.30
Free Glycerin D6584 0.020 max. % (w/w) 0.002 0.004 0.00 0.00 0.01 0.02 0.01 0.014 0.012 0.01
Total Glycerin D6584 0.240 max. % (w/w) 0.013 0.090 0.01 0.09 0.08 0.025 0.019 0.09 0.077 0.09
Phosphorus Content EN 14107 4 max. Ppm 3 3 2 2 3 2 2 3 2 2
Distillation, T90 AET D1160 360 max. °C 345 350 351 338 342 355 345 356 346 340
Sodium/Potassium, combined EN 14538 5 max ppm 2.3 2.5 2.4 2.2 2.3 2.1 2.3 2.4 2.3 2.1
Oxidation Stability EN 14112 3 min hours 2.3 1.5 0.9 1.3 1.88 1.90 2.3 2.4 2.1 2.2

Algea Rapeseed Corn Canola Olive

the injector nozzle. Because of this, the cetane number of diesel fuel
Safflower Hazelnut Sunflower Soybean Cottonseed should not be higher than 65 [30]. Icingur et al. [31] observed the
effect of cetane number on a direct injection diesel engine performance.
99.0
98.5 For this purpose, the fuels with 46.0, 51.0, 54.5 and 61.5 cetane
Ester Content (%)

98.0
97.5
97.0
96.5
96.0
95.5
190 196 197 200 200 204 210 214 216 218
Water Content (ppm)
Fig. 1. The change of ester content of biodiesel fuels with water content of the
feedstock.
pretreatment reaction [27]. Ester content value of a biodiesel fuel can
be accepted as an indicator of the quality of transesterification reaction
at which the biodiesel fuel is produced. If transesterification reaction is
not complete, produced biodiesel fuel’s ester content will be lower. Use
of biodiesel with low ester content in a diesel engine may cause serious
engine failures since the unconverted triglycerides might polymerize
and so plug fuel lines and injector nozzles [28]. The change of ester
contents of produced biodiesel fuels according to their water contents
was given in Fig. 1. The significant effect of transesterified feedstock’s
water content can be clearly seen in this figure. Methyl ester contents of
biodiesel fuels decreased with increasing water content of the feed-
stock. For example, methyl ester content (98.7%) of biodiesel fuel
produced from algae, which had the lowest water content among the
vegetable oils, was the highest.
number were tested at fuel injection pressure of 150 bar under full load
conditions. The results showed that the engine torque and power output
increased by 5 and 4%, when the cetane number was increased from
46.0 to 54.5. Nevertheless, when increasing the cetane number above
54.5, no significant increase was observed in the engine performance. It
is well known from the literature that biodiesel cetane number depends
on the feedstock used for fuel production. With increasing chain length,
decreasing branching and the degree of unsaturation, cetane number
increases [32–34]. These chemical structures increase the heating value
and viscosity as well, so there is a tendency for cetane number to in-
crease with viscosity and heating value [32]. Low cetane numbers have
been associated with more highly unsaturated components such as the
esters of linoleic (C18:2) and linolenic (C18:3) acids [35]. The cetane
numbers of all biodiesel fuels were measured and their relation with the
degree of unsaturation (DU) levels of their feedstocks was depicted in
Fig. 2. It is clear that the cetane number corresponds almost linearly to
the degree of unsaturation. Examining the figure, it is seen that the
cetane numbers of biodiesel fuels produced from algae, olive and ha-
zelnut oils, which have low unsaturation fatty acid content, are rela-
tively high as compared to other biodiesel fuels. The cetane numbers of
biodiesel fuels produced from safflower, soybean, rapeseed, sunflower
and corn oils having high levels of polyunsaturated fatty acids like
C18:2 and C18:3, are relatively low (Table 2). Knothe et al. [36] ob-
served high cetane numbers for methyl ester fuels comprised of high
amount of saturated fatty acids such as palmitic C16:0), stearic (C18:0),
arachidic (C20:0) and behenic (C22:0) acids. Algae biodiesel, rich in

3.2.2. Cetane number

The cetane number, which is an indicator of a diesel fuel's self-ig- Olive Hazelnut Algea Canola Rapeseed
Cottonseed Corn Soybean Sunflower Safflower
niting quality, allows the fuel to be easily ignited and burn quickly. It
can be defined as the measure of knock tendency of a diesel fuel. The 60
cetane number is related to the ignition delay time, which is the time 58
Cetane Number

interval between the start of injection and the start of combustion. As 56

the cetane number increases, the ignition delay decreases and the main 54
combustion phase (diffusion-controlled combustion) increases. Long 52
ignition delay is not acceptable since it causes diesel knock [29]. Cetane 50
number can also influence the cold engine start and subsequent white 48
smoke and noise emissions. Similar to low cetane number, too high 95 101 107 116 125 130 136 142 143 170
cetane number is inconvenient, as well [12]. If the cetane number of DU
diesel fuel is too high, this fuel may ignite in a short distance to the
injector nozzle and cause excessive heating of the injector. As a result of Fig. 2. The change of the cetane number of biodiesel fuel with DU of the
the intense heating, cooked fuel particles inside the injector may plug feedstock.

4
F. Yaşar Fuel 264 (2020) 116817

these compounds (Table 1), gave the highest cetane number. Van Rapeseed Safflower Hazelnut Corn Sunflower
Gerpen [37], who observed an increase in the cetane number with in- Cottonseed Canola Olive Soybean Algea
creasing methyl palmitate content in the blend, reported similar results. 0
Hazelnut, olive, corn and cottonseed biodiesels presented a cetane 0.77 1.87 2.11 3.05 3.23 3.73 3.85 4.01 4.25 5.36
number near to that of algae biodiesel. These biodiesels are rich in

CFPP (°C)
-5
monounsaturated fatty acids (C18:1, C20:1 and C22:1). The presence of
these monounsaturated compounds gave a high cetane number to those
biodiesels. In addition, the presence of long fatty acid carbon chain in -10
rapeseed biodiesel led to a high cetane number for this biodiesel
[32,36,38].
-15
LCSF
3.2.2.1. Cold filter plugging point. In the literature, three main
characteristics are generally defined to characterize the cold flow Fig. 3. The change of CFPP values of biodiesel fuels with LCSF of the feedstock.
properties of a fuel; cloud point (CP), pour point (PP) and cold filter
plugging point (CFPP). The CP can be defined as the first temperature at
more viscous and its cetane number raises [51,52]. Therefore, the
which the cloud layer, which is the indicator of the onset of
oxidized biodiesel starts to burn earlier than the unoxidized one, and
crystallization, on the fuel surface is seen when the fuel is cooled
NOx emission may increase. The chemical structure of biodiesel fuel is
[39]. The PP can be expressed as the lowest temperature at which the
the important factor in the oxidative stability. Oxidation is mainly
fuel still maintains its fluidity. At temperatures lower than this value,
caused from the presence of double bonds in the chains, that is,
the fuel is no longer in a liquid state due to excessive gelling [40]. These
feedstock rich in polyunsaturated fatty acids are much more
two definitions are insufficient for automotive fuels. Because a fuel that
susceptible to oxidation than the feedstocks rich in saturated or
can be pumped by the fuel pump (namely not yet reached its pour
monounsaturated fatty acids [34,53,54]. As biodiesel is oxidized, a
point) may plug the fuel filter and therefore the vehicle may not start.
series of changes in its properties occurs. Properties like acid value,
Because of this, the use of CFPP value is more useful for determining the
peroxide value, and viscosity increase, while the iodine value and ester
cold flow quality of an automotive fuel. CFPP is the lowest temperature
content decrease. All these changes affect the quality of biodiesel,
at which the fuel can pass through the fuel filter without causing
indicating why oxidation is a phenomenon of great importance in
plugging problem [41]. The cetane numbers of normal paraffin are
biodiesel technology, as mentioned above [55]. The changes in
quite high; however, their low temperature properties are not good.
oxidation stability of produced biodiesels with the viscosity and acid
Biodiesel fuels generally have poor cold flow properties than those of
numbers values were given in Fig. 4. As can be seen in the graphics,
petroleum-based diesel fuel. This leads to critical problems when fuels
oxidative stability increased with not only viscosity values but also acid
are used in cold weather. Since CP, CFPP, PP values of saturated hydro-
numbers. When the results obtained in this study are examined, it is
carbons are high, fuel crystalizes in unacceptably high temperatures.
seen that the biodiesel fuels obtained from safflower, olive and algae
For this, appropriate biodiesel fuel additive and fuel heating process
had the highest oxidative stability. In addition, it is seen that the
may be needed [37,38]. Cold flow characteristics of longer chain and
viscosity and acid number values of these biodiesels are higher than
more-saturated fatty acid methyl esters (FAMEs) are worse than those
those of other fuels; and these data are in accordance with the related
of having more unsaturated and branched-chain fatty acids. Fuels with
literature. In Fig. 5, the change of oxidation stability of produced
a high concentration of saturated fatty acids (SFAs) can have unsuitable
biodiesels with total unsaturation level (TUS) of the feedstocks can be
viscosities and poor cold-flow properties. At low temperatures,
saturated components of the fuel crystallize and cause precipitation
problems, such as clogged fuel lines, filters, pumps and injectors Su nfl ower Cottonseed Soybean Canola Co rn
[24,42–45]. Low-temperature properties depend mostly on saturated Hazelnut Rapeseed Olive Algea Safflower
ester content, and the effect of unsaturated ester composition can be 3.00
Oxidation Stability (h)

considered negligible [46,47]. In this sense, the CFPP of all the 2.50
biodiesel fuels was correlated with the parameter long chain 2.00
saturated factor (LCSF), which was calculated taking into account the
1.50
composition of saturated fatty acids and lending more weight to the
composition of fatty acids with a long chain (Table 2, Eq. (2)). In fact, 1.00
unsaturated compounds act essentially as solvents, in which the 0.50
saturated esters are dissolved and from which they precipitate with 0.00
4.30 4.33 4.37 4.40 4.42 4.45 4.48 4.53 4.55 4.60
the effect of the temperature [48]. The correlation between CFPP values
Viscosity (mm2/s)
of produced biodiesel fuels and LCSF levels of the vegetable oil
feedstocks was depicted in Fig. 3. As can be seen, the biodiesel fuels
with the lowest the CFPP were from algae, corn and canola oil. Sunflower Corn Soybean Cottonseed Canola
Hazelnut Rapeseed Algea Olive Safflower
3.2.2.2. Oxidation stability. Oxidation stability is one of the most 3.00
Oxidation Stability (h)

critical fuel properties affecting the long-term storage and usage of a 2.50
biodiesel fuel. It indicates the fuel’s resistance to auto-oxidation. The 2.00
temperature, the amount of oxygen and the material of the container 1.50
where the fuel is stored are the decisive parameters on the oxidation 1.00
reactions [49,50]. When oxidation reaction starts, the initial products 0.50
are hydroperoxides. As the oxidation continues, the peroxides may split 0.00
and form aldehydes, ketones and short chain acids that produce 0.12 0.15 0.16 0.21 0.25 0.28 0.30 0.32 0.32 0.33
unpleasant odors. Oxidation eventually deteriorates the fuel Acid Number (mgKOH/g)
properties because of gum formation. This formed gum does not
combust completely, and it results in carbon deposits in the Fig. 4. The change of oxidative stability of biodiesel fuels with viscosity and
combustion chamber. Moreover, as it oxidizes, biodiesel becomes acid number.

5
F. Yaşar
Cottonseed Algea Olive Soybean
Canola Sunflower Hazelnut Safflower
3.00
Oxidation Stability (h)
2.50
2.00
1.50
1.00
0.50
0.00
74.36 81.65 82.08 83.59 83.59 89.03 89.70 90.44 90.77 94.93
TUS
Fig. 5. The change of oxidation stability of biodiesel fuels with TUS of the
feedstock.
seen. As illustrated in the graphic, it is determined that oxidative
stability exhibited an increase with the increase in TUS level. When the
results obtained are examined, it is determined that the biodiesels
(safflower, olive, algae) with the highest oxidation stability had the
highest TUS values as well. It is also seen that these data confirm the
literature. Minor components in the FAME ingredient may have
contrast effects on the oxidative stability by catalyzing or inhibiting
the oxidation reactions. Namely, despite the above relationship
between the number of double bonds and oxidative stability, the
effects of minor components can easily counterbalance it. For this
reason, oxidative stability lends itself more than any of the other
properties to be improved by additives [56].
4. Conclusion
The basic target of this study was to investigate the effects of various
vegetable oils on the fuel properties of biodiesel fuels produced from
these vegetable oils, and to determine the most appropriate feedstock
for biodiesel production. In order to correlate the fatty acid composi-
tions of vegetable oils with the fuel properties, the degree of un-
saturation (DU) and long-chain saturated factor (LCSF) parameters
were calculated. Moreover, the parameters such as the effect of water
content of the processed feedstock on the ester conversion, change of
the cetane number of biodiesel with the degree of unsaturation, CFPP of
biodiesel versus LCSF, changes in oxidative stability of biodiesel fuels
with respect to viscosity and acid number were also investigated. In the
experiments, maximum ester content (98.5%) was obtained from algae
oil, which had the minimum water content. In addition, since algae oil
had the highest saturated fatty acid content same as cottonseed oil, it
was seen that it had the highest cetane number. Furthermore, algae oil
had the lowest CFPP value. It was observed that the biodiesels with the
highest oxidation stability were safflower, algae and olive. Also, the
viscosity and iodine numbers of these fuels were partially higher than
the other fuels. When the findings of this study are evaluated as a
whole, it can be concluded that algae oil-based biodiesel had the rela-
tively superior fuel properties over the biodiesel fuels obtained from the
vegetable oils feedstocks. In addition; algae have more oil compared to
other field crops, their growing process is easier, and they are not af-
fected by seasonal and climatic conditions. In addition, due to the fact
that they need no agricultural field during growth; and reproducing
very fast even in small areas, and they do not need fertile soils for
growing. They can adapt desert conditions, and they have a number of
advantages such as growing in nylon sacks or tanks nearby power plants
emitting carbon dioxide around. However, the influences of biodiesel
fuels produced from various algae oil types on the performance, com-
bustion and emission characteristics of modern diesel engines, which
are very sensitive to fuel quality, should be comprehensively in-
vestigated.
Fuel 264 (2020) 116817
Corn Author contribution section
Rapeseed
This is a single author study. No assistance was gained while per-
forming of experiments and typing of the paper.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
References
[1] Demirbas A. Importance of biodiesel as transportation fuel. Energy Policy
2007;35:4661–70.
[2] Banani R, Youssef S, Bezzarga M, Abderrabba M. Waste frying oil with high levels of
free fatty acids as one of the prominent sources of biodiesel production. J Mater
Environ Sci 2015;6(4):1178–85.
[3] Toba M, Abea Y, Kuramochib H, Osakob M, Mochizukia T. YoshimuraY.
Hydrodeoxygenation of waste vegetable oil over sulfide catalysts. Catal Today
2011;164:533–7.
[4] Sanlı H. Influences of biodiesel fuels produced from highly degraded waste animal
fats on the injection and emission characteristics of a CRDI diesel engine. Int J
Automot Eng Technol 2019;8(1):11–21.
[5] Demirbas A. Characterization of biodiesel fuels. Energy Sour Part A
2009;31:889–96.
[6] Hazar H, Uyar M. Experimental investigation of isopropyl alcohol (IPA) /diesel
blends in a diesel engine for improved exhaust emissions. Int J Automot Eng
Technol 2015;4(1):1–6.
[7] Sanlı H. An experimental investigation on the usage of waste frying oil-diesel fuel
blends with low viscosity in a Common Rail DI-diesel engine. Fuel
2018;222:434–43.
[8] Yasar F. Evaluation and advantages of algae as an energy source. J Turkish Chem
Soc Sect 2018;5(3):1309–18.
[9] Kegl B. Biodiesel usage at low temperature. Fuel 2008;87:1306–17.
[10] Sharma YC, Singh B. Development of biodiesel: current scenario. Renew Sust
Energy Rev 2009;13:1646–51.
[11] Mittelbach M, Remschmidt C. Biodiesel: the comprehensive handbook. Vienna:
Boersedruck Ges. M.B.H; 2004.
[12] Canakci M, Sanli H. Biodiesel production from various feedstocks and their effects
on the fuel properties. J Ind Microbiol Biotechnol 2008;35:431–41.
[13] Ramos MJ, Fernández CM, Casas A, Rodríguez L, Pérez A. Influence of fatty acid
composition of raw materials on biodiesel properties. Bioresour Technol
2009;100:261–8.
[14] Elangovan T, Jeryrajkumar L. Biodiesel and its properties from various feedstocks.
Int J Trends Eng Technol 2017;1(2).
[15] Dmytryshyn SL, Dalai AK, Chaudhari ST, Mishra HK, Reaney MJ. Synthesis and
characterization of vegetable oil derived esters: evaluation for their diesel additive
properties. Bioresour Technol 2004;92:55–64.
[16] Lang X, Dalai AK, Bakhshi NN, Reaney MJ, Hertz PB. Preparation and character-
ization of bio-diesels from various bio-oils. Bioresour Technol 2001;80:53–62.
[17] Orsavova J, Misurcova L, Ambrozova LV, Vicha R, Mlcek J. Fatty acids composition
of vegetable oils and ıts contribution to dietary energy ıntake and dependence of
cardiovascular mortality on dietary ıntake of fatty acids. Int J Mol Sci
2015;16:12871–90.
[18] Maguire LS, O’Sullivan SM, Galvin K, O’Connor TP, O’Brien NM. Fatty acid profile,
tocopherol, squalene and phytosterol content of walnuts, almonds, peanuts, ha-
zelnuts and the macadamia nut. Int J Food Sci Nutr 2004;55:171–8.
[19] Canakci M. The potential of restaurant waste lipids as biodiesel feedstocks.
Bioresour Technol 2007;98:183–90.
[20] Ma F, Hanna MA. Biodiesel production: a review. Bioresour Technol 1999;70:1–15.
[21] Kostik V, Memeti S, Bauer B. Fatty acid composition of edible oils and fats. J
Hygienic Eng Des 2013;4:112–6.
[22] Demirbas A. Biodiesel fuels from vegetable oils via catalytic and non-catalytic su-
percritical alcohol transesterifications and other methods: a survey. Energy Convers
Manage 2003;44:2093–109.
[23] Komers K, Machek J, Stloukal R. Biodiesel from rapeseed oil and KOH Composition
of solution of KOH in methanol as reaction partner of oil. Eur J Lipid Sci Technol
2001;103:359–62.
[24] Ma F, Clements LD, Hanna MA. The effects of catalyst, free fatty acids, and water on
transesterification of beef tallow. Trans Am Soc Agric Eng 1998;41:1261–4.
[25] Tomasevic AV, Marinkovic SSS. Methanolysis of used frying oil. Fuel Process
Technol 2003;81:1–6.
[26] Fregolente PBL, Wolf Maciel MR, Oliveira LS. Removal of water content from
biodiesel and diesel fuel using hydrogel adsorbents. Braz J Chem Eng
2015;32(04):895–901.
[27] Romano S. Vegetable oils-a new alternative. Trans Am Soc Agric Eng
1982;4:106–16.
[28] Schwab AW, Bagby MO, Freedman B. Preparation and properties of diesel fuels
from vegetable oils. Fuel 1987;66:1372–8.
[29] Meher LC, Vidya Sagar D, Naik SN. Technical aspects of biodiesel production by
transesterification–a review. Renew Sust Energy Rev 2006;10:248–68.
6
F. Yaşar
[30] Heywood JB. Internal combustion engines fundamentals. New York: McGraw-Hill
Inc; 1988.
[31] Icingur Y, Altiparmak D. Effect of fuel cetane number and injection pressure on a DI
diesel engine performance and emissions. Energy Convers Manage 2003;44:389–97.
[32] Demirbas A. Chemical and fuel properties of seventeen vegetable oils. Energy
Sources 2003;25:721–8.
[33] Goering CE, Schwab AW, Daugherty MJ, Pryde EH, Heakin AJ. Fuel properties of
eleven vegetable oils. Trans Am Soc Agric Eng 1982;25:1472–7.
[34] Graboski MS, McCormick RL. Combustion of fat and vegetable oil derived fuels in
diesel engines. Prog Energy Combust Sci 1998;24:125–64.
[35] Knothe G, Matheaus AC, Ryan III TW. Cetane numbers of branched and straight
chain fatty esters determined in an ignition quality tester. Fuel 2003;82:971–5.
[36] Knothe G, Bagby MO, Ryan III TW. Precombustion of fatty acids and esters of
biodiesel. A possible explanation for differing cetane numbers. J Am Oil Chem Soc
1998;75:1007–13.
[37] Van Gerpen JH, Cetane number testing of biodiesel. Liquid fuels and industrial
products from renewable resources. In: Proceedings of the Third Liquid Fuel
Conference 1996 pp. 15–17 September, Nashville, Tennessee.
[38] Bajpai D, Tyagi VK. Biodiesel: source, production, composition, properties and its
benefits. J Oleo Sci 2006;55:487–502.
[39] Bruna FA, Pedro HRP, Rita de Cássia PN, Elizabete FL. Influence of solvent solu-
bility parameter on the performance of EVA copolymers as pour point modifiers of
waxy model-systems. Fuel 2019;258:116–96.
[40] Veríssimo MIS, Teresa M, Gomes SR. Assessment on the use of biodiesel in cold
weather: pour point determination using a piezoelectric quartz crystal. Fuel
2011;90:2315–20.
[41] De Torres M, Jiménez-Osés G, Mayoral JA, Pires E. Fatty acid derivatives and their
use as CFPP additives in biodiesel. Bioresour Technol 2011;102:2590–4.
[42] Canakci M, Gerpen JV. Comparison of engine performance and emissions for pet-
roleum diesel fuel, yellow grease biodiesel and soybean oil biodiesel. Trans Am Soc
Agric Eng 2003;46:937–44.
[43] Demirbas A. Biodiesel production from vegetable oils via catalytic and noncatalytic
Fuel 264 (2020) 116817
supercritical methanol transesterification methods. Prog Energy Combust
2005;31:466–87.
[44] Dunn RO. Effect of antioxidants on the oxidative stability of methyl soyate (bio-
diesel). Fuel Process Technol 2005;86:1071–85.
[45] Stansell GR, Gray VM, Sym SD. Microalgal fatty acid composition: implications for
biodiesel quality. J Appl Phycol 2012;24:791–801.
[46] González Gómez ME, Howard-Hildige R, Leahy JJ, Rice B. Winterisation of waste
cooking oil methyl ester to improve cold temperature fuel properties. Fuel
2002;81:33–9.
[47] Imahara H, Minami E, Saka S. Thermodynamic study on cloud point of biodiesel
with its fatty acid composition. Fuel 2006;85:1666–70.
[48] Lopes JCA, Boros L, Krähenbühl MA, Meirelles AJA, Daridon JL, Pauly J, et al.
Prediction of cloud points of biodiesel. Energy Fuels 2008;22:747–52.
[49] Knothe G. Analyzing biodiesel: standards and other methods. J Am Oil Chem Soc
2006;83:823–33.
[50] Sui M, Li F. Effect of TEPA on oxidation stability and metal ion content of biodiesel.
Renew Energy 2019;143:352–8.
[51] Monyem A, Gerpen JV. The effect of biodiesel oxidation on engine performance and
emissions. Biomass Bioenergy 2001;20:317–25.
[52] Canakci M, Monyem A, Gerpen JV. Accelerated oxidation process in biodiesel.
Trans Am Soc Agric Eng 1999;42:1565–72.
[53] Neff WE, Selke E, Mounts TL, Rinsch W, Frankel EN, Zeitoun MAM. Effect of tria-
cyglycerol composition and structures on oxidative stability of oils from selected
soybean germplasm. J Am Oil Chem Soc 1992;69:111–8.
[54] Raghuveer KG, Hammond EG. The in Xuence of glycerine structure on the rate of
autoxidation. J Am Oil Chem Soc 1967;44:239–43.
[55] Zuleta C, Baena L, Riosa LA, Calderón J. The oxidative stability of biodiesel and its
impact on the deterioration of metallic and polymeric materials. J Braz Chem Soc
2012;23(12):2159–75.
[56] McCormick RL, Ratcliff M, Moens L, Lawrence R. Several factors affecting the sta-
bility of biodiesel in standard accelerated tests. Fuel Process Technol
2007;88:651–7.