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BIOMASS AND BIOENERGY 33 (2009) 113 – 118

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Production of biodiesel fuels from linseed oil using


methanol and ethanol in non-catalytic SCF conditions

Ayhan Demirbas
Sila Science, Trabzon, Turkey

art i cle info ab st rac t

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.

1. Introduction problems. The disadvantages of vegetable oils as diesel fuel


are: (a) higher viscosity, (b) lower volatility (higher flash
The use of vegetable oils as alternative renewable fuel point), and (c) the reactivity of unsaturated hydrocarbon
competing with petroleum was proposed in the beginning chains [1].
of 1980s. Vegetable oils have become more attractive recently The purpose of the transesterification process is to lower
because of its environmental benefits and the fact that it is the viscosity of the oil. The viscosity and flash point values of
made from renewable resources. Vegetable oils are a renew- linseed oil methyl and ethyl esters highly decrease after
able and potentially inexhaustible source of energy with an transesterification process. Transesterification of triglcerides
energetic content close to diesel fuel. The major problem is not a new process. Scientists E. Duffy and J. Patrick
associated with the use of pure vegetable oils as fuels, for conducted it as early as 1853. Life for the diesel engine began
diesel engines are caused by high fuel viscosity in compres- in 1893 when the famous German inventor Rudolph Diesel
sion ignition and resulting injector fouling and other engine published a paper entitled ‘‘The theory and construction of a

Tel.: +90 4622307831; fax: +90 4622488508.


E-mail address: ayhandemirbas@hotmail.com
0961-9534/$ - see front matter & 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2008.04.018
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114 BIOMASS AND BIOENERGY 33 (2009) 113 – 118

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
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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).

3. Results and discussion

3.1. Fuel properties of biodiesels

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)

Pure linseed oil 27.20 926.6 515


Linseed oil methyl ester 3.36 888.2 449
Linseed oil ethyl ester 3.67 885.3 454
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116 BIOMASS AND BIOENERGY 33 (2009) 113 – 118

Table 4 – Fuel properties of linseed oil and biodiesels (methyl and ethyl esters) of linseed oil

Property Linseed oil Methyl ester Ethyl ester

Distillation range (K) 520–638 503–658 510–663


Cetane number 28 55 59
Carbon residue (% by weight) 0.24 0.032 0.034
Ash (% by weight) 0.01 0.008 0.007
Sulfur (% by weight) 0.01 0.005 0.006
Iodine value (g I/100 g oil) 156.7 – –
Saponification value (mg KOH/g oil) 187.7 – –
Higher heating value (MJ kg 1) 39.84 41.82 42.18

Table 5 – ASTM standards (ASTM D6751) of biodiesels from linseed oil

Property Test method Linseed oil methyl ester Linseed oil ethyl ester

Flash point (K) D 93 449 454


Water and sediment (%vol) D 2709 0.03 0.03
Kinematic viscosity (mm2 s 1 at 313 K) D 445 3.36 3.67
Sulfated ash (%wt) D 874 0.003 0.002
Ash (% by weight) D 482 0.008 0.007
Sulfur (% by weight) D 5453 0.002 0.002
Sulfur (% by weight) D 2622/129 0.003 0.003
Cetane number D 613 55 59
Carbon residue (% by weight) D 4530 0.032 0.034
Carbon residue (% by weight) D 524 0.025 0.026
Distillation temp (90% volume recycle) D 1160 503–658 K 510–663 K

Table 6 – Fatty acid compositions of linseed oil


conversion of triglycerides into methyl or ethyl esters through
the transesterification process reduces the molecular weight
16:0 16:1 18:0 18:1 18:2 18:3
to one-third that of the triglyceride reduces the viscosity by a
5.1 0.3 2.5 18.9 18.1 55.1
factor of about eight. Viscosities show the same trends as
temperatures, with the lard and tallow biodiesels higher than
the soybean and rapeseed biodiesels.
Density is another important property of biodiesel. It is the
3.1.1. Viscosity of biodiesel weight of a unit volume of fluid. Specific gravity is the ratio of
Viscosity is a measure of the internal friction or resistance of the density of a liquid to the density of water. Specific gravity
an oil to flow. The internal frictions of methyl and ethyl esters of biodiesels ranges between 0.860 and 0.885 kg m 3. Fuel
are lower than those of triglyceride molecules. As the injection equipment operates on a volume metering system,
temperature of oil is increased, its viscosity decreases and it hence a higher density for biodiesel results in the delivery of a
is therefore able to flow more readily. Viscosity is measured slightly greater mass of fuel.
on several different scales, including Redwood no. 1 at 100F, Table 3 shows the viscosity, density and flash point
Engler degrees, Saybolt seconds, etc. The number of seconds measurements of pure linseed oil and its esterified derivates.
required for 50 ml of an oil to flow out of a standard Redwood The viscosity and density measurements of pure linseed oil
viscosimeter at a definite temperature. were 27.20 mm2 s 1 (or cSt) and 926.6 kg m 3 at 311 K, respec-
Viscosity is the most important property of biodiesel since tively. The viscosities of linseed oil methyl and ethyl esters
it affects the operation of fuel injection equipment, particu- were 3.36 and 3.67 mm2 s 1 and their densities were 888.2 and
larly at low temperatures when the increase in viscosity 885.3 kg m 3 at 311 K, respectively. It is obvious that the
affects the fluidity of the fuel. Biodiesel has viscosity close to viscosity and density measurements of the esters are highly
diesel fuels. High viscosity leads to poorer atomization of the lower than that oil pure linseed oil. While the measurements
fuel spray and less accurate operation of the fuel injectors. A decrease the flash points of the esters decrease from 515 to
novel process of biodiesel fuel production has been developed 449 or 454 K. The viscosity of linseed oil ethyl esters was
by a non-catalytic supercritical methanol method. The super- slightly higher than that methyl ester.
critical alcohol process is non-catalytic, simpler purification, Relationships between density and viscosity of vegetable
lower reaction time and lower energy use. Therefore, the oils were given in the literature [16]. An increase in density
supercritical alcohol method would be more effective and from 904.4 to 923.6 kg m 3 for vegetable oils decreases the
efficient than the common commercial process [14,15]. The viscosity from 53.6 to 27.2 mm2 s 1 and the decreases are
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BIOMASS AND BIOENERGY 33 (2009) 113 – 118 117

considerably regular. Relationships between density and 100


viscosity of vegetable oil methyl esters were given in the
literature [16]. An increase in density from 860 to 885 kg m 3
for vegetable oil methyl esters or biodiesels increases the
viscosity from 3.59 to 4.63 mm2 s 1 and the increases are
highly regular. There are high regressions between density 80
and viscosity values of vegetable oil methyl esters [16].

3.1.2. Cetane numbers of biodiesels

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

Fig. 3 – Plots of ester yield as treated with subcritical


3.2. Emission properties of biodiesels (at 503 K) and supercritical (at 523 K) methanol and ethanol
vs. reaction time. Molar ratio of linseed oil to alcohol: 1:41.
Biodiesel fuels have generally been found to be non-toxic and
are biodegradable, which may promote their use in applica-
tions where biodegradability is desired. Neat biodiesel and
biodiesel blends reduce particulate matter (PM), hydrocarbons methyl ester was higher than that of ethyl ester at all
(HC) and carbon monoxide (CO) emissions and slightly temperatures. The volatility of linseed oil was lower than
increase nitrogen oxides (NOx) emissions compared with those of methyl and ethyl esters at all temperatures.
petroleum-based diesel fuel used in an unmodified diesel
engine [17].
3.4. Effect of temperature and reaction time on ester yield
3.3. Distillation curves of biodiesels
Fig. 3 shows the plots for the yield of biodiesels (methyl and
ethyl esters) form linseed oil vs. transesterification time at
Fig. 2 shows the distillation curves of the diesel fuel and
different temperatures using supercritical alcohol (methanol
linseed oil methyl and ethyl esters. As seen in Fig. 2, the most
and ethanol) method. The alcohol transesterification reac-
volatile fuel was diesel fuel. The volatility of linseed oil
tions were carried out at subcritical (at 503 K) and super-
critical (at 523 K) conditions. It is evident that at subcritical
state of alcohol, reaction rate is so low and gradually
100 increased as either pressure or temperature rises. It was
90 Linseed oil Ethyl ester
observed that increasing the reaction temperature, especially
Methyl ester Diesel fuel
Yield of distillation, wt%

80 to supercritical conditions, had a favorable influence on the


70 yield of biodiesel without any catalyst. As the temperature
60 increased, the yield improved significantly. As shown in Fig. 3,
50 the yield of ester (biodiesel) sharply increased at first 3 min.
40 The yields of biodiesel are relatively low even after reaction
30 for 6 and 8 min. In the supercritical alcohol transesterification
20 method, the yield of ester raises 88–98% for first 8–12 min.
The molar ratio of methanol to waste cooking oil is also one
10
of the most important variables affecting the yield of esters.
0
400 450 500 550 600 650 700 Higher molar ratios result in greater ester production in a
Temperature, K shorter time. The samples of linseed oil were transesterified
1:41 vegetable oil-alcohol molar ratio in supercritical condi-
Fig. 2 – Distillation curves of diesel fuel, linseed oil, and tions. In this reaction, an excess of methanol was used in
methyl and ethyl esters of linseed oil. order to shift the equilibrium in the direction of the products.
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118 BIOMASS AND BIOENERGY 33 (2009) 113 – 118

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