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Abstract
Comparative studies on transesterification methods were presented in this work. Biodiesel is obtained from a chemical reaction called
transesterification (ester exchange). The reaction converts esters from long chain fatty acids into mono alkyl esters. Chemically, biodiesel
commonly is a fatty acid methyl ester. Vegetable oils can be transesterified by heating them with a large excess of anhydrous methanol
and an acidic or basic reagent as catalyst. A catalyst is usually used to improve the reaction rate and yield. In a transesterification reac-
tion, a larger amount of methanol was used to shift the reaction equilibrium to the right side and produce more methyl esters as the
proposed product. Several aspects including the type of catalyst (alkaline, acid or enzyme), alcohol/vegetable oil molar ratio, tempera-
ture, purity of the reactants (mainly water content) and free fatty acid content have an influence on the course of the transesterification. A
non-catalytic biodiesel production route with supercritical methanol has been developed that allows a simple process and high yield
because of the simultaneous transesterification of triglycerides and methyl esterification of fatty acids. In the catalytic supercritical meth-
anol transesterification method, the yield of conversion rises to 60–90% for the first 1 min.
Ó 2007 Elsevier Ltd. All rights reserved.
0196-8904/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2007.05.002
126 A. Demirbas / Energy Conversion and Management 49 (2008) 125–130
2.1.2. Methanolic sulfuric acid 2.3. Methylation of free fatty acids with diazomethane
Vegetable oils are transesterified very rapidly by heating (CH2N2)
in 10% sulfuric acid in methanol until the reflux tempera-
ture is reached. A solution of 1–2% concentrated sulfuric CH2N2 reacts rapidly with free fatty acids to give methyl
acid in methanol has almost identical properties to 5% esters. The CH2N2 is generally prepared in ethereal solu-
methanolic hydrogen chloride and is very easy to prepare. tion by the action of alkali (a 30% solution of KOH) on
A. Demirbas / Energy Conversion and Management 49 (2008) 125–130 127
which makes them inappropriate for typical industrial pro- R–C(=O)–O–H + CH2 N2 ! R–C(=O)–O–CH2 –H + N2
cesses [4]. ð5Þ
Notice that the diazomethane appears to insert itself be-
3.4. Sodium methoxide catalyzed transesterification
tween the O and the H of the O–H bond Eq. (5). The high
reactivity of diazomethane arises from the fact that it pos-
There have been given a number of detailed recipes for
sesses an exceedingly reactive leaving group, the nitrogen
sodium methoxide catalyzed transesterification [23]. The
molecule N2. A nucleophilic substitution reaction on the
methodology can be used on quite a large scale if need
protonated diazomethane molecule transfers a methyl
be. The reaction between sodium methoxide in methanol
group to the oxygen atom of the carboxylic acid while lib-
and a vegetable oil is very rapid. It has been shown that tri-
erating a very stable product (N2 gas). This process is very
glycerides can be completely transesterified in 2–5 min at
favorable energetically owing to the great stability of N2.
room temperature. The methoxide anion are prepared by
dissolving the clean metals in anhydrous methanol. Sodium
3.7. Non-catalytic supercritical alcohol transesterification
methoxide (0.5–2 M) in methanol effects transesterification
of triglycerides much more rapidly than other transesterifi-
Biodiesel, an alternative Diesel fuel, is made from
cation agents. At equivalent molar concentrations with the
renewable biological sources such as vegetable oils and ani-
same triglyceride samples, potassium methoxide effects
mal fats by non-catalytic supercritical alcohol transesterifi-
complete esterification more quickly than does sodium
cation methods [3]. A non-catalytic biodiesel production
methoxide. Because of the dangers inherent in handling
route with supercritical methanol has been developed that
metallic potassium, which has a very high heat of reaction
allows a simple process and high yield because of simulta-
with methanol, it is preferred to use sodium methoxide in
neous transesterification of triglycerides and methyl esteri-
methanol. The reaction is generally slower with alcohols
fication of fatty acids [5].
of higher molecular weight. As with acidic catalysis, inert
The parameters affecting the methyl esters formation are
solvents must be added to dissolve the simple lipids before
reaction temperature, pressure, molar ratio, water content
methanolysis will proceed [23].
and free fatty acid content. It is evident that at a subcritical
state of alcohol, the reaction rate is very low and gradually
3.5. Boron trifluoride catalyzed transesterification increases as either pressure or temperature rises. It was
observed that increasing the reaction temperature, espe-
The Lewis acid, boron trifluoride, in the form of its cially to supercritical conditions, had a favorable influence
coordination complex with methanol is a powerful acidic on the yield of ester conversion. The yield of alkyl ester
catalyst for esterification of fatty acids. One of the most increased with increasing molar ratio of oil to alcohol [5].
popular of all transesterification catalysts is boron trifluo- In the supercritical alcohol transesterification method, the
ride in methanol (12–14% w/v), and in particular, it is often yield of conversion rises to 50–95% for the first 10 min.
utilized as a rapid means of esterifying free fatty acids. Water content is an important factor in conventional
When it is compared critically with some of the other acidic catalytic transesterification of vegetable oil. In the conven-
catalysts under similar conditions, it does not even appear tional transesterification of fats and vegetable oils for bio-
to be any more rapid in its reaction. diesel production, free fatty acids and water always
produce negative effects, since the presence of free fatty
3.6. Esterification fatty acids with diazomethane acids and water causes soap formation, consumes catalyst
and reduces catalyst effectiveness. In catalyzed methods,
Diazomethane (CH2N2) reacts rapidly with free fatty the presence of water has negative effects on the yields of
acids to give methyl esters but does not affect transesterifi- methyl esters. However, the presence of water affected pos-
cation of other lipids. The reaction is not instantaneous, itively the formation of methyl esters in our supercritical
however, as has sometimes been assumed, unless a little methanol method.
methanol is present as a catalyst [19]. Carboxylic acids In the supercritical alcohol transesterification method,
{R–C(@O)–O–H} can be converted to methyl esters {R– the yield of conversion rises to 50–95% for the first
C(@O)–O–CH3} by the action of CH2N2. 8 min. In the catalytic supercritical methanol transesterifi-