ENERGY EXPLORATION & EXPLOITATION · Volume 28 · Number 6 · 2010 pp.

499-512 499

Comparison of the biodiesel quality produced from

refined sunflower (Helianthus annuus L) oil and waste
cooking oil

Abdurrahman Saydut1*, Aylin Beycar Kafadar2, Yalcin Tonbul3, Canan Kaya2,

Firat Aydin2 and Candan Hamamci2
1
Dicle University, Engineering Faculty, Mining Engineering Department,
TR-21280 Diyarbakir, Turkey
2
Dicle University, Science Faculty, Chemistry Department, TR-21280 Diyarbakir, Turkey
3
Dicle University, Education Faculty, Primary Education Department, TR-21280 Diyarbakir,
Turkey
*
Author for corresponding. E-mail: saydut@dicle.edu.tr

(Received 6 September 2010; accepted 12 November 2010)

Abstract
A major hurdle in commercialization of biodiesel from vegetable oil, in
comparison to petroleum-based diesel fuel, is its cost of manufacturing,
primarily the raw material cost. Waste cooking oil is one of the economical
sources for biodiesel production. NaOH and KOH catalyzed processes for
prepared of biodiesel expressed of fatty acid methyl ester were comparatively
studied for refined sunflower (Helianthus annuus L) oil and waste cooking oil.
Transesterification was carried out using 100% excess methanol; i.e. molar ratio
of methanol to oil is 6:1 and catalyst concentration of 0.5% at 60oC. Fuel
properties and specifications such as viscosity, flash point, cloud point, pour
point, density, cetane number, and acidic value are determined and compared to
each other and petroleum diesel. This study characterizes the fuel properties of
biodiesel produced from refined sunflower oil and waste cooking oil using two
different catalysts (NaOH and KOH) to provide a comprehensive understanding
of biodiesels.

Keywords: Biodiesel, Refined sunflower oil, Waste cooking oil, Catalyst,

Transesterification

1. INTRODUCTION
Turkey cannot proceed to meet its energy demands by fossil resources solely. It has to
take the impact of an extensive usage of fossil fuels on the environment into
consideration. Disregarding the environment, results in cost-intensive problems which
lead to a decrease of the gross national product. For that reason, Turkey is obliged to
500 Comparison of the biodiesel quality produced from refined sunflower
(Helianthus annuus L) oil and waste cooking oil

align its energy policy with new and renewable energy resources. The main goal of
policies supporting renewable energy sources is to decrease the production of
greenhouse gases in a short term. The real objection should be to develop green
technologies and to provide that renewable energy becomes fully competitive in order
to ensure a less independent local energy supply in a clean and economical way (Balat,
2008; Ozgur, 2008). Energy plays a vital role in socio-economic development and
raising standards of human beings. Turkey is a rapidly growing country; both its
population and economy are expanding each year so its energy demand increases
correspondingly and this increasing demand has to be met for keeping sustainable
development in the economy and raising living conditions of mankind. Although
Turkey has many energy sources, it is a big energy importer. Turkey has a lot of
potential to supply its own energy, which could be put to use in order to avoid this
energy dependence. Additionally, Turkey is a country that has an abundance of
renewable energy sources and can essentially provide all energy requirements from
indigenous energy sources. Biomass is one of the most promising energy sources
considered to be alternative to conventional ones (Gokcol et al., 2009; Qin et al., 2009).
Among liquid biofuels, biodiesel derived from vegetable oils is gaining acceptance
and market share as diesel fuel in Europe and the United States (Demirbas, 2009).
Biodiesel is a renewable and environmentally friendly alternative fuel that can be used
in diesel engines with little or no modification. Low cost feedstocks, such as waste oils
used cooking oil and animal fats, are important for low cost biodiesel production
(Cetinkaya et al., 2005). Biodiesel has proven itself as a technically sufficient
alternative diesel fuel in the fuel market since the beginning of 1990s. Its applications
in automobiles, ships, and heating systems have been accepted by both European
countries and the USA (Cetinkaya and Karaosmanoglu, 2005). By several important
measures biodiesel blends perform better than petroleum diesel, but its relatively high
production costs and the limited availability of some of the raw materials used in its
production continue to limit its commercial application. Limiting factors of the
biodiesel industry are feedstock prices, biodiesel production costs, crude oil prices,
and taxation of energy products. A variety of biolipids can be used to produce
biodiesel. These are (a) refined vegetable oil feedstock; rapeseed and soybean oils are
most commonly used, though other crops such as mustard, palm oil, sunflower, hemp,
and even algae show promise; (b) waste vegetable oil; (c) animal fats including tallow,
lard, and yellow grease; and (d) non-edible oils such as jatropha, neem oil, castor oil,
and tall oil (Balat and Oz, 2008; Demirbas, 2009; Giwa et al., 2010; Qin et al., 2010).
The oil percentage and the yield per hectare are important parameters to consider as
biodiesel source (Singh and Singh, 2010).
Among the vegetable oil seeds that can be grown as domestic field crops,
cottonseed and sunflower seed are the major productions of Turkey. However, crop
productions are inconsistent according to harvest area, climatic conditions, etc. Turkey
is one of the major sunflower producers of the world (Altin et al., 2001). Diesel fuel
can contain both saturated and unsaturated hydrocarbons, but the latter are not present
in large enough amounts to make fuel oxidation problem. Petroleum-derived diesel is
composed of about 75% saturated hydrocarbons (primarily paraffins including n, iso,
and cycloparaffins), and 25% aromatic hydrocarbons (including naphthalenes and
ENERGY EXPLORATION & EXPLOITATION · Volume 28 · Number 6 · 2010 pp. 499–512 501

alkylbenzenes). The average chemical formula for common diesel fuel is C12H23,
ranging from approximately C10H20 to C15H28 (Singh and Singh, 2010).
Sunflower with high oil content is one of the more prominent oilseed crops for
biodiesel production. At one point, it was considered to be the second primary source
of edible oil next to soybean (Karmakar et al., 2010). Sunflower (Helianthus annuus
L.), belonging to the family Compositae, is a major oilseed, used for the production of
edible oil, with an annual production of 25.1 million tons .The composition of oleic,
linoleic and linolenic acids in oil has been an affect the oxidative stability. Sunflower
oil has approximately 70% linoleic acid and is highly susceptible to lipid oxidation
(Jelen et al., 2000). Heating speeds up the oxidative reaction, which is a major concern
for deep fat cooking operations (Muik et al., 2005; Sarin et al., 2010).
Transesterification (also called alcoholysis) is the reaction of a fat or oil with an
alcohol to form esters and glycerol. A catalyst is usually used to improve the reaction
rate and yield. Excess alcohol is used to shift the equilibrium toward the product
because of reversible nature of reaction. For this purpose primary and secondary
monohybrid aliphatic alcohols having 1-8 carbon atoms are used. Transesterification
reaction is quite sensitive to various parameters. The reaction is either incomplete or
the yield is reduced to a significant extent if the parameters are not optimized. These
parameters include free fatty acids (FFAs), water content, molar ratio of alcohol to oil,
catalyst, reaction temperature and stirring. Each parameter is equally important to
achieve a high quality biodiesel which meets the regulatory standards (Singh and
Singh, 2010; Banerjee and Chakraborty, 2009; Ozturk et al., 2010). There are many
kinds of catalysts that can be used in transesterification reaction. The main advantages
of using a strong alkali as a catalyst are shorter reaction time and less amount of
catalyst required in the manufacturing process of the transesterification reaction.
Therefore, a strong alkaline catalyst is widely used in the industry for mass biodiesel
production. For an alkali catalyzed transesterification, the glycericed and alcohol must
be substantially anhydrous because water makes the reaction partially change to
saponification, which produces soap.
Raw materials contribute to a major portion in the cost of biodiesel production. The
choice of raw materials depends mainly on its availability and cost (Singh and Singh,
2010). Used cooking oils are of increasing interest as inexpensive feedstock for
biodiesel production. Another possible use for used cooking oil feedstocks is as fuel
for generators (Cetinkaya and Karaosmanoglu, 2005; Aydin et al., 2011).
The high cost of biodiesel is the major obstacle for its commercialization; the
biodiesel produced from vegetable oil or animal fat is usually more expensive than
petroleum-based diesel fuel from 10 to 50%. Moreover, during 2007, the prices of
refined vegetable oils have nearly doubled in relation to the early 2000s (Demirbas,
2009). This is of great concern to biodiesel producers, since the cost of feedstock
comprises approximately 70-95% of total operating costs at a biodiesel plant (Leung
and Guo, 2006). Based on estimates from seven countries, a total of about 0.4 Mt of
waste oil is collected within the EU, mainly from catering industry, while the amount
that could be collected is estimated to be considerably higher, possibly from 0.7 to 1
Mt (Gonzalez Gomez et al., 2002). As waste cooking oils have been regularly poured
down the drain, resulting in problems for wastewater treatment plants and energy loss,
502 Comparison of the biodiesel quality produced from refined sunflower
(Helianthus annuus L) oil and waste cooking oil

or integrated into food chain by animal feeding, causing human health problems, their
use for biodiesel production offers solution to a growing problem of the increased
waste oil production from household and industrial sources all around the world
(Felizardo et al., 2006; Predojevic, 2008). The cost of biodiesel is mainly due to the
cost of refined vegetable oil. The use of WCO, instead of refined oil, to prepare
biodiesel is an effective way to reduce the raw material cost because WCO is
estimated to be about half the price of refined oil. In addition, the utilization of WCO
diminishes the problems of contamination, because the reusing of these waste greases
can reduce the burden of the government in disposing of the waste, maintaining public
sewers, and treating the oil wastewater. The fact is, so far, that only a very small
percentage of these oils has been collected and used for soap production (Zhang et al.,
2003; Haas, 2005; Encinar et al., 2007). Because of the limited petroleum reserves and
increased environmental concerns, alternate fuels from agricultural resources have
become increasingly important in the near future. From the viewpoints of resource
recycling and energy utilization, biodiesel fuel from waste edible oil for diesel engines
can be considered as one of green energies (Tsai et al., 2007). This study used refined
and waste cooking sunflower oil as the raw oil to mix with methanol and two strong
alkali catalysts (NaOH and KOH) to undergo a transesterification reaction.

2. EXPERIMENTAL
2.1. Production procedure for biodiesel
The refined and waste cooking oil (WCO) were originally sunflower oil, supplied by
the catering service of the Dicle University. Non-oil components of the WCO were
removed by separation.
Four different processes were carried out using virgin sunflower oil and waste
cooking oil as the raw material. Two of them were NaOH-catalyzed process, one using
refined oil and the other using waste cooking oil. The remaining two were KOH
catalyzed process. Biodiesel derived from refined sunflower oil and/or waste cooking
oil was prepared by reacting 300 g of oil, 60 g CH3OH (approximately 6:1 molar ratio)
and 1.5 g NaOH or KOH. The reaction was carried out for 2 h under reflux at 60°C
while stirring. The reactor was equipped with reflux condenser to condense back the
methanol escaping from the reaction mixture. The reaction mixture was then allowed
to stand overnight and the methyl ester layer was separated from the glycerol layer
using separatory funnel. Residual amount of glycerol in the crude methyl ester was
removed by centrifugation. Since both glycerol and alcohol are highly soluble in
water, water washing is very effective for removing both contaminants. It also can
remove any residual sodium salts and soaps. The mixture was washed three times with
deionized water and was subsequently centrifuged to remove the aqueous layer that
included the methanol, residual catalyst and glycerol. The residual methanol was
separated from the biodiesel via rotary evaporation under vacuum at 80oC for a period
of 1 h. Finally, a molecular sieve (3A) was added to each sample to adsorb a trace
amount of moisture (Casas et al., 2010; Duz et al., 2011; Hamamci et al., 2011).
A fixed amount of freshly prepared homogeneous alkali catalyst (NaOH or
KOH)–methanol solution was added into the oils, taking this moment as the starting
time of the reaction. When the reaction reached the preset reaction time, heating and
ENERGY EXPLORATION & EXPLOITATION · Volume 28 · Number 6 · 2010 pp. 499–512 503

stirring were stopped. The products of reaction were allowed to settle overnight.
During settling two distinct liquid phases was formed: crude ester phase at the top and
glycerol phase at the bottom. The crude ester phase separated from the bottom glycerol
phase was then washed by cold or warm de-ionized water several times until the
washed water became clear. The excess methanol and water in ester phase were then
removed by evaporation under atmospheric condition. After that weight of the ester
was taken for product yield calculation. When the reaction temperature closes or
exceeds the boiling point of methanol, the methanols will vaporize and form a large
number of bubbles then inhibit the reaction. Although a reflux condenser was used in
the experiment to avoid methanol losses, the WCO conversion efficiency significantly
decreased at temperatures more than 60°C. All materials should be substantially
anhydrous. Water caused soap formation, which consumed the catalyst and reduced
catalyst efficiency. The resulting soaps caused an increase in viscosity, formation of
gels and made the separation of glycerol difficult.

2.2. Characterization of biodiesels

Kinematic viscosity at 40oC was obtained using Koehler Kinematic Viscosity Bath
Model K 23377 while in warm water bath (ASTM D-445). Pour point (ASTM D-97)
and cloud point (ASTM D-2500) were determined simultaneously using Tanaka Mini-
Pour/Cloud Point Tester Model MPC-101A/101L. For flash point (ASTM D-93),
Tanaka Automatic Flash Point Tester Model APM-6T-A was used. Heating value
(ASTM D-2015) was determined using IKA Calorimeter System C 2000 basic control
calorimeter. Measurements of the density at 15oC by Metler-Toledo densimeter
(ASTM D-941). C and S were determined by Carlo Erba 1108 Model elemental
analyzer and Eltra CS 500 Carbon Sulfur Determinator. The iodine number, cetane
number was calculated, while the acid value was obtained by titration (Ma and Hanna,
1999; Antolin et al., 2002; Meher et al., 2006; Saydut et al., 2008; Kaya et al., 2009).
Acid value or neutralization number, is expressed in mg KOH required to neutralize 1
g of fatty acid methyl esters and is set to a maximum value of 60.5 mg KOH/g in the
European norm (EN 14214). The procedure involves titration of the diluted sample
with ethanolic potassium hydroxide solution using a Metrohm 702 SM Titrino. This
procedure was developed according to UNE-EN 14104 (Ramos et al., 2009; Casas et
al., 2010)

3. RESULTS AND DISCUSSION

In this study, biodiesel production from the refined sunflower oil and WCO were
carried out in the laboratory scale reactor. Alkali catalysts used in transesterification
can be potassium hydroxide and sodium hydroxide (Phan and Phan, 2008).
Four different processes were carried out using refined sunflower oil and waste
cooking oil as the raw material. Two of them were NaOH-catalyzed process, one using
refined oil and the other using waste cooking oil. The remaining two were KOH-
catalyzed process using refined oil and the other using waste cooking oil. The
esterification reaction was carried out at 60oC and 6:1 molar ratio of methanol to oil.
Transesterification reaction was incomplete with 200 rotations per minute (rpm) with
mechanical stirring. Mixing of reactants at 200 rpm with mechanical stirrer was
504 Comparison of the biodiesel quality produced from refined sunflower
(Helianthus annuus L) oil and waste cooking oil

performed to get the optimum yield. Not much information on mode of stirring is
available. However, a better yield with mechanical stirring has been reported than with
magnetic mode of stirring.
From the technical assessment, all of these processes proved to be feasible for
producing a high quality biodiesel product and a top-grade glycerine by-product under
reasonable operation conditions. Transesterification is the reaction of oil with an
alcohol to form esters and glicerol. A catalyst is usually used to improve the reaction
yield and rate. Because the reaction is reversible, excess alcohol is used to chift the
equilibrium to products side. Methanol was used in the experiments of this study
because of its low cost and its physical and chemical advantages: shortest chain
alcohol and polar. Although 3:1 molar ratio of alcohol to oil is needed to complete a
transesterification stoichiometrically, the ratio needs to be higher to drive the
equilibrium to a maximum yield, in practice. Higher molar ratios result in greater ester
conversion in a shorter time. Scientists found that the molar ratio of 6:1 of methanol
to plant oils gave the best conversion. The reaction can be catalyzed by alkalis such as
NaOH, KOH, carbonates and corresponding sodium and potassium alkoxides
(methoxide, ethoxide, propoxide and butoxide), amides or hydrides; acids such as
sulfuric acid, phosphoric acid, hydrochloric acid or organic sulfonic acid and
biocatalysts such as lipases. Alkali-catalyzed production is much faster than the others
and is most often used commercially. Sodium hydroxide and potassium hydroxide
were chosen to catalyze the reaction they are cheaper and are used widely in large
scale processing. Amount of base catalyst used was 0.5% w/w of oils chosen in the
experiments. The conversion rate increases with reaction time. Temperature clealy
influenced the reaction rate and yield of esters. 2 h and 60oC were optimized as
reaction time and reaction temperature respectively in our study. Carbon numbers of
the hydrocarbons present in the diesel fuels are mostly in the ranges of 12–22
(paraffins, olefins, naphthenes and aromatics). On the other hand, oils including
vegetable oils and animal fats are principally glycerides (i.e.triglycerides) formed
from the glycerol and higher fatty acids (C12–C22) such as lauric, myristic, palmitic,
stearic, oleic, linolenic, and linoleic acids (Tsai et al., 2007; Srivastava and Prasad,
2000; Barnwal and Sharma, 2005; Singh and Singh, 2010).
The fuel properties of biodiesel produced from these catalysts, such as ester content,
kinematic viscosity and acid value, were measured and compared. With intermediate
catalytic activity and a much lower cost sodium hydroxide was found to be more
superior than the potassium hydroxide. The catalyst, sodium or potassium hydroxide
was dissolved in methanol just before starting the transesterification reaction in an
attempt to prevent the moisture absorbance. The higher heating values of biodiesels are
relatively high. These of biodiesels (39-41 MJ/kg) are slightly lower than those of
gasoline (46 MJ/kg), petrodiesel (43 MJ/kg), or petroleum (42 MJ/kg), but higher than
coal (32-37 MJ/kg) (Demirbas, 2009). The reduction in calorific value for the biodiesel
and its blends compared to diesel was due to the presence of oxygen in the biodiesel.
Biodiesels are characterized by their viscosity, density, cetane number, cloud and pour
points, flash point, ash content, sulfur content, carbon residue, acid value, and higher
heating value. The most important parameters affecting the ester yield during the
transesterification reaction are the molar ratio of alcohol to vegetable oil and reaction
ENERGY EXPLORATION & EXPLOITATION · Volume 28 · Number 6 · 2010 pp. 499–512 505

temperature. The viscosity values of vegetable oil methyl esters decrease sharply after
transesterification. Compared to D2 fuel, all of the produced methyl esters are slightly
viscous. The flash point values of the produced biodiesels are significantly lower than
those of vegetable oils. There is high regression between the density and viscosity
values of vegetable oil methyl esters. The relationships between viscosity and flash
point for vegetable oil methyl esters are considerably regular. These parameters are all
specified through the biodiesel standard, ASTM D 6751. This standard identifies the
parameters the pure biodiesel must meet before being used as a pure fuel or being
blended with petroleum-based diesel fuel. The EN 14214 is an international standard
that describes the minimum requirements for biodiesel produced from vegetable oil fuel
stock. Biodiesel, specifications (ASTM D 6751) and (EN 14214) are given in Table 1
(Demirbas, 2009).

Table 1. Biodiesel specifications according to ASTM D6751, and EN 14214

standards.

In most parts of the world edible oils are used in cooking pans or fryers and after a
variable time of use are discarded. These waste cooking oils have different properties
from those of refined and crude vegetable oils. The presence of heat and water
accelerates the hydrolysis of triglycerides and increases the content of free fatty acids
(FFA) in the oil. The FFA and water content have significant effects on the
transesterification reaction negatively. They also interfere with the separation of fatty
acid esters and glycerol. Especially, the viscosity of the oil increases considerably,
506 Comparison of the biodiesel quality produced from refined sunflower
(Helianthus annuus L) oil and waste cooking oil

because of the formation of dimeric and polymeric acids and glycerides in used
cooking oils (Table 2). Iodine values decrease while saponification value and density
increase. At present there is no systematic method of processing used oils from
households and most of the used oil is mostly thrown through the home drains and
ends up in wastewaters that are then discharged to surface waters, leading to water
pollution. Moreover, more than 80% of the oil is consumed at home; the control of this
disposal behavior becomes a huge problem because of the large volumes involved
(Alcantara et al., 2000; Tomasevic et al., 2003; Marmesat et al., 2007; Enweremadu
and Mbarawa, 2009).

Table 2. Fuel properties of biodiesels produced from refined sunflower oil and
waste cooking oil using two alkaline catalysts (NaOH and KOH).

To determine if the biodiesel produced met the specifications of the standard EN

14214, several samples of biodiesel were submitted to a series of tests. The standard for
biodiesel states that the fuel should have a density between 0.860 and 0.900 gcm-3. This
property is important mainly in airless combustion systems because it influences the
efficiency of atomization of the fuel. The results obtained showed that for all the
conditions studied, the biodiesel produced in this study had a density in the range of
0.8722-0.8953 gcm-3.
Even more than density, this is an important property regarding fuel atomization,
as well as fuel distribution. For biodiesel to be used in diesel engines, the kinematic
ENERGY EXPLORATION & EXPLOITATION · Volume 28 · Number 6 · 2010 pp. 499–512 507

viscosity must be between 3.5 and 5.0 mm2s-1. The kinematic viscosity of the biodiesel
samples produced in this work ranged from 3.59 to 4.30 mm2s-1.
The number of double bonds of fatty acids is related to the iodine value. This
parameter describes the content of unsaturated fatty acids and is only dependent on the
origin of the vegetable oil. A limitation of unsaturated fatty acids may be necessary
because the higher heating of unsaturated fatty acids results in polymerization of
glycerides. This can lead to the formation of deposits or to the deterioration of the
lubricating oil (Encinar et al., 2007).
The iodine value is an important measure that allows determination of the
unsaturation degree of the fuel. This property greatly influences fuel oxidation and the
type of aging products and deposits formed in diesel engines injectors. According to
EN 14214 (2003), methyl esters used as diesel fuel must have an iodine value below
120 g I2 per 100 g of sample. Analyses of the produced biodiesels revealed iodine
values between 92.40 and 101.67. Waste cooking oil biodiesel has a lower iodine
number and a higher acid number. EN 14214 specifies that biodiesel must have a flash
point higher than 120°C. The produced biodiesels revealed flash points between
146°C and 164°C.
The catalytic conversion of waste cooking oil by the transesterification process into
biodiesel fuel has the advantage of both economic and environmental benefits. In this
regard, the biodiesel fuel has been demonstrated to be successfully produced from
waste cooking oils by an alkali-catalyzed transesterification process, and can be
considered as alternative fuels in diesel engines and other utilities. Biodiesel is
particularly useful in mining and marine situations where lower pollution levels are
important.
Although being collected from different sources, there was little difference in
properties among the WCO samples in terms of chemical and physical properties. This
could then assist the implementation of biodiesel production process from waste
cooking oils. The high cost of vegetable oils, which could be up to 75% of the total
manufacturing cost, has led to the production costs of biodiesel becoming
approximately 1.5 times higher than that for diesel (Ma and Hanna, 1999; Zhang et al.,
2003; Phan and Phan, 2008). Nevertheless, the price of waste cooking oils (WCO) is
2–3 times cheaper than refined vegetable oils. Consequently, the total manufacturing
cost of biodiesel can be significantly reduced (Zhang et al., 2003). In addition, a
similarity in the quality of biodiesel derived from WCO and from vegetable oils could
be achieved at an optimum operating condition (Cetinkaya and Karaosmanoglu, 2004;
Phan and Phan, 2008). The conversion of this amount of WCO into fuel also
eliminates the environmental impacts caused by the harmful disposal of these waste
oils, such as into drains (Phan and Phan, 2008; Utlu, 2007).
There are several end-uses for waste cooking oils, such as the production of soaps
or of energy by anaerobic digestion, thermal cracking (Zaher, 2003) and more recently
the production of biodiesel, a fuel that can be used as a mineral diesel substitute for
engines. The recent concerns with sustainability, environment, and raw material costs
have made the use of waste cooking oils attractive to the industry, especially if
stimulated with economic benefits associated with the use of blends of biodiesel and
fossil diesel (Zhang et al., 2003). Vegetable oils used in industrial or household
508 Comparison of the biodiesel quality produced from refined sunflower
(Helianthus annuus L) oil and waste cooking oil

cooking undergo degradation by hydrolytic and oxidative reactions, both processes

being responsible for changes in the chemical and physical properties, as compared to
the fresh oil (Costa Neto et al., 2000). During cooking, the viscosity and acidity of the
oil increases, and the oil becomes darker and develops an unpleasant odour. Prior to
the transesterification proceeding, the waste cooking oil from local suppliers must be
tested for its acid value, iodine value and water content. Acid value is indicative of the
content of free fatty acids, which are easily saponified with caustic catalyst (i.e.
sodium hydroxide) to form saponifiable matters. Iodine value (IV) is used to measure
the extent of unsaturated fatty acid, which has a decreasing trend as the quality
deterioration of edible oil increased. Water content in the feedstock will give cause to
form bulk solids in the alkali-catalyzed process, resulting in a negative impact on the
downstream processing.
Cetane number (CN) signifies the ignition delay time of the fuel on its injection into
the combustion chamber. A higher CN of esters is desired, which is an indication of
short ignition delay. However, with an increase in CN, IV decreases. IV is an
indication of the level of unsaturation and its lower value leads to solidification of
esters at lower temperature. Hence, an upper limit of 65 has been specified in
American Society for Testing and Materials (ASTM). The minimum value of CN
assigned by US biodiesel standard is 47 (Sharma and Singh, 2009). Low cetane
numbers have been associated with more highly unsaturated components (C18:2 and
C18:3). Polyunsaturated fuels that contain high levels of these components include
soybean, sunflower and grape seed oils. In addition, these biodiesels showed high
iodine values. Furthermore, the oxidation stability decreased with the increase of the
content of polyunsaturated methyl esters. Biodiesel of almond, olive, corn, rapeseed
and high oleic sunflower oils had the global better properties because they have the
greater monounsaturated content (Ramos et al., 2009; Sharma and Singh, 2009).
Higher amount of free fatty acids leads to higher acid value (neutralization
number). Vegetable oils should have free fatty acids within a desired limit for alkaline
transesterification, beyond which either the reaction will not take place or the yield
will be too less. The FFA level in the oil should be below a desired level (ranging from
less than 0.5% to less than 3%) for alkaline transesterification to take place (Sharma
and Singh, 2009).
In food cooking, vegetable oils are used at very high temperatures. This process
causes various chemical reactions such as hydrolysis, polymerization and oxidation.
Therefore, the physical and chemical properties of the oil change during cooking. The
percentage of FFAs has been found to increase due to the hydrolysis of triglycerides
in the presence of food moisture and oxidation. Increases in viscosity were also
reported due to polymerization, which resulted in the formation of higher molecular
compounds. Other observations were that the acid value and density of the waste
cooking oil increased, but the iodine value decreased. Unsaturated bonds undergo
chemical reaction at high temperatures in a deep cooking process which increases the
saturation degree of waste cooking oil, leading to a lower iodine number. Also, during
a deep cooking process, the presence of heat and water accelerates the hydrolysis of
triglycerides and increases the content of free fatty acids in oil.
On average, 1 L of residual cooking oil can be processed into 0.9 L of biodiesel
ENERGY EXPLORATION & EXPLOITATION · Volume 28 · Number 6 · 2010 pp. 499–512 509

(Siriwardhana et al., 2009). The products formed during cooking, such as free fatty
acid and some polymerized triglycerides, can affect the transesterification reaction and
the biodiesel properties. Apart from this phenomenon, the biodiesel obtained from
waste cooking oil gives better engine performance and less emission when tested on
commercial diesel engines (Kulkarni and Dalai, 2006). Waste cooking oil is known to
undergo more severe oxidation during the cooking process. Thus, more oxidized
chemicals and free fatty acids are present in waste cooking oil biodiesels. This
explains the differences in composition of vapor phases between sunflower biodiesel
and waste cooking oil biodiesel.

4. CONCLUSIONS
(1) The increasing production of waste cooking oils from household and
industrial sources is a growing problem all around the world.
(2) This paper studied the influence of the physical and chemical properties of
the refined sunflower oil and waste cooking oils on the alkaline-catalyzed
transesterification process that produce the maximum ester content.
(3) The production of biodiesel from used waste cooking oils is feasible by basic
catalyzed transesterification and the biodiesel produced has the quality
required to be a diesel substitute.
(4) The cost of biodiesel is the main hurdle to commercialization of the product.
The waste cooking oil used as raw material is primary option to be considered
to lower the cost of biodiesel. Compared to vegetable oils, the cost of waste
cooking oils is anywhere from 60 % less to free, depending on the source and
availability.

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