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Ayhan Demirbas
Sila Science, Trabzon, Turkey
Article history: Methyl and ethyl esters as biodiesel fuels were prepared from linseed oil with
Received 26 November 2006 transesterification reaction in non-catalytic supercritical fluids conditions. Biodiesel fuel
Received in revised form is a renewable substitute fuel for petroleum diesel fuel made from vegetable or animal fats.
23 April 2008 Biodiesel fuel has better properties than that of petroleum diesel fuel such as renewable,
Accepted 26 April 2008 biodegradable, non-toxic, and essentially free of sulfur and aromatics. The purpose of the
Available online 6 June 2008 transesterification process is to lower the viscosity of the oil. The viscosity values of linseed
oil methyl and ethyl esters highly decreases after transesterification process. The viscosity
Keywords:
values of vegetable oils vary between 27.2 and 53.6 mm2 s 1, whereas those of vegetable oil
Linseed oil
methyl esters between 3.59 and 4.63 mm2 s 1. Compared with no. 2 diesel fuel, all of the
Biodiesel
vegetable oil methyl esters were slightly viscous. The flash point values of vegetable oil
Viscosity
methyl esters are highly lower than those of vegetable oils. The transesterification of
Transesterification
linseed oil in supercritical fluids such as methanol and ethanol has proved to be the most
Methanol
promising process. Methanol is the commonly used alcohol in this process, due in part to
Ethanol
its low cost. Methyl esters of vegetable oils have several outstanding advantages among
other new-renewable and clean engine fuel alternatives. The most important variables
affecting the methyl ester yield during the transesterification reaction are molar ratio of
alcohol to vegetable oil and reaction temperature. Biodiesel has become more attractive
recently because of its environmental benefits. Biodiesel is an environmentally friendly fuel
that can be used in any diesel engine without modification.
& 2008 Elsevier Ltd. All rights reserved.
rational heat engine’’. Rudolph Diesel designed the original Table 1 – Comparisons between catalytic methanol
diesel engine to run on vegetable oil. Dr. Rudolph Diesel used (MeOH) process and supercritical methanol (SCM) meth-
peanut oil to fuel one of his engines at the Paris Exposition of od for biodiesel from vegetable oils by transesterification
1900 [2].
Methyl, ethyl, 2-propyl and butyl esters were prepared from Catalytic MeOH process SCM
canola and linseed oils through transesterification using KOH method
and/or sodium alkoxides as catalysts. In addition, methyl and
Methylating Methanol Methanol
ethyl esters were prepared from rapeseed and sunflower oils agent
using the same catalysts [3]. Ethanol is a preferred alcohol in Catalyst Acid or alkali None
the transesterification process compared with methanol Reaction 303–338 523–573
because it is derived from agricultural products and is temperature (K)
renewable and biologically less objectionable in the environ- Reaction 0.1 10–25
ment. Success of rapeseed ethyl ester production would mean pressure (MPa)
Reaction time 60–360 6–15
that biodiesel’s two main raw materials would be agricultu-
(min)
rally produced, renewable and environmentally friendly [4,5]. Methyl ester 97 98
The emergence of the transesterification can be dated back yield (wt%)
to as early as 1846 when Rochieder described glycerol Removal for Methanol, catalyst, Methanol
preparation through ethanolysis of castor oil [6]. Since that purification glycerol, saponifieds
time alcoholysis has been studied in many parts of the world. Free fatty acids Saponified products Methyl
esters, water
Others researchers have also investigated the important
Process Complicated Simple
reaction conditions and parameters on the alcoholysis of
triglycerides, such as fish oils, tallow, soybean, rapeseed,
cottonseed, sunflower, safflower, peanut and linseed oils
[7–11].
A novel process of biodiesel fuel production has been the yield of the esters are: temperature, residence time and
developed by a non-catalytic supercritical fluids (methanol the mol ratio of oil to alcohol. The most important contribu-
and ethanol) method. The supercritical fluids have a high tion of the paper to biodiesel researchers is product char-
potential for both transesterification of triglycerides and acterization.
alcohol esterification of free fatty acids to methyl and ethyl
esters for diesel fuel substitute. In the supercritical methanol
transesterification method, the yield of conversion raises 97% 2. Experimental
for 10 min [12]. The objective of this study was to evaluate
biodiesel fuel from transesterification of linseed oil using 2.1. Samples used
non-catalytic supercritical methanol and ethanol method.
Biodiesel, an alternative diesel fuel, is made from renewable The samples of linseed oils from Turkish commercial sources
biological sources such as vegetable oils and animal fats by were used in the experiments. The samples were converted to
non-catalytic supercritical alcohol transesterification meth- methyl and ethyl esters by non-catalytic supercritical fluid
ods [2]. A non-catalytic biodiesel production route with (alcohol) transesterification method.
supercritical methanol has been developed that allows a
simple process and high yield because of simultaneous 2.2. Non-catalytic supercritical alcohol transesterification
transesterification of triglycerides and methyl esterification
of fatty acids [7]. The experiments of the supercritical alcohol transesterifica-
The parameters affecting on the methyl esters formation tion of linseed oil samples were performed in a laboratory
are reaction temperature, pressure, molar ratio, water content scale apparatus. The main element of this device was a
and free fatty acid content. It is evident that at subcritical horizontal cylindrical autoclave of stainless-steel, 350.0 mm
state of alcohol, reaction rate is so low and gradually height, 60.0 mm inner diameter and 120.0 mm outer diameter
increased as either pressure or temperature rises. It was inserted vertically into an electrically heated an external
observed that increasing the reaction temperature, especially heater and provided with an electrical heating system power
to supercritical conditions, had a favorable influence on the source, with changing heating rates and power was adjusted
yield of ester conversion. The yield of alkyl ester increased to give an approximate heating time of 25 min. The sample
with increasing the molar ratio of oil to alcohol [6]. In the was loaded from the bolt-hole into the autoclave, and the
supercritical alcohol transesterification method, the yield of hole was plugged with a screw bolt after each run. The
conversion raises 50–95% for first 10 min. Comparisons temperature of the autoclave was measured with thermo-
between catalytic commercial methanol process and super- meter and controlled at 72 K. Transesterification occurred
critical methanol (SCM) method for biodiesel from vegetable during the heating period.
oils by transesterification are given in Table 1. A simple autoclave for supercritical alcohol transesterifica-
The aim of this study was to experimentally investigate tion is shown in Fig. 1. In a typical run, the autoclave is
how affect the temperature and reaction time on biodiesel charged with a given amount of linseed oil and methanol or
yield from linseed oil at sub- and supercritical methanol and ethanol with changed molar ratios. After each run, the
ethanol conditions. The most important factors, which affect autoclave is cooled, and the autoclave is poured into a
ARTICLE IN PRESS
BIOMASS AND BIOENERGY 33 (2009) 113 – 118 115
collecting vessel. All the rest of the contents are removed wash solution at the rate of 28% by volume of oil and 1 g of
from the autoclave by washing with methanol or ethanol. tannic acid per liter of water is added to the ester and gently
Table 2 shows critical temperatures and critical pressures of agitated. Air is carefully introduced into the aqueous layer
various alcohols. while simultaneously stirring very gently. This process is
In a typical run, the autoclave was charged with a given continued until the ester layer becomes clear. After settling,
amount of vegetable oil (200–250 g) and alcohol (200–500 g) the aqueous solution is drained and water alone is added at
with changed molar ratios. 28% by volume of oil for the final washing [13].
A successful transesterification reaction produces two
liquid phases: ester and crude glycerin. Crude glycerin, the 2.3. Viscosity and flash point measurements
heavier liquid, will collect at the bottom after several hours of
settling. Phase separation can be observed within 10 min and Each sample of biodiesel was used for viscosity, flash point
can be complete within 2 h of settling. After settling is and density measurements. A Redwood no. 1 viscosimeter
complete, water is added at the rate of 5.5% by volume of with a measuring cup and a thermostat was used to measure
the methyl ester of oil and then stirred for 5 min and the the viscosity of all samples. The viscosity measurements were
glycerin is allowed to settle again. Washing the ester is a two- carried out at 313 K temperature. The temperatures were
step process, which is carried out with extreme care. A water checked with a digital thermometer within the thermostat
and the viscosimeter. At the beginning of each measurement
a volume of 50 ml of the sample was filled into the measuring
cup. Flash point measurements were carried out using a
Koehler mark apparatus (Table 3).
290 350
The properties of biodiesel are close to diesel fuels. The
biodiesel was characterized by determining its viscosity,
density, cetane number, cloud and pour points, character-
istics of distillation, flash and combustion points and higher
heating value (HHV) [8]. Some fuel properties of linseed oil
and biodiesels (methyl and ethyl esters) of linseed oil are
given in Table 4.
60 Table 5 shows ASTM standard (ASTM D6751) of biodiesels
from linseed oil. The ASTM Standards (ASTM D6751) of
Fig. 1 – Simple autoclave for supercritical transesterification. biodiesels from linseed oil are between ASTM limits. Im-
portant operating disadvantages of biodiesel in comparison
with petrodiesel are cold start problems, the lower energy
content, higher flash point and fuel pumping difficulty from
Table 2 – Critical temperatures and critical pressures of
higher viscosity. This increases fuel consumption when
various alcohols
biodiesel is used in comparison with application of pure
petrodiesel, in proportion to the share of the biodiesel
Alcohol Critical temperature Critical pressure
content. Taking into account the higher production value of
(K) (MPa)
biodiesel as compared with the petrodiesel, this increase in
Methanol 512.2 8.1 fuel consumption raises in addition the overall cost of
Ethanol 516.2 6.4 application of biodiesel as an alternative to petrodiesel.
1- 537.2 5.1 Table 6 shows the fatty acid compositions of linseed oil
Propanol sample. The linseed oil sample has higher linolenic acid content.
1-Butanol 560.2 4.9
Table 3 – Viscosity, density and flash point measurements of pure linseed oil and its esterified derivates
Fuel Viscosity (mm2 s 1) at 311 K Density (kg m 3) at 311 K Flash point (K)
Table 4 – Fuel properties of linseed oil and biodiesels (methyl and ethyl esters) of linseed oil
Property Test method Linseed oil methyl ester Linseed oil ethyl ester
Yield of ester, %
Cetane number (CN) is based on two compounds, namely
hexadecane with a Cetane of 100 and heptamethylnonane 60
with a Cetane of 15. The CN scale also shows that straight
chain, saturated hydrocarbons have higher CN compared
with branched chain or aromatic compounds of similar
molecular weight and number of carbon atoms. The CN of
biodiesel is generally higher than conventional diesel. The CN
40 Methyl ester at 503 K
is one of the prime indicators of the quality of diesel fuel. It
Methyl ester at 523 K
relates to the ignition delay time of a fuel upon injection into
Ethyl ester at 503 K
the combustion chamber. The CN is a measure of ignition
Ethyl ester at 523 K
quality of diesel fuels and high CN implies short ignition
delay. The longer the fatty acid carbon chains and the more
saturated the molecules, the higher the CN. The CN of 20
biodiesel from animal fats is higher than those of vegetable 0 2 4 6 8
oils. The CN of linseed oil was 28 (Table 4). Reaction time, min
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