Progress in Energy and Combustion Science: C. Brunschwig, W. Moussavou, J. Blin

Progress in Energy and Combustion Science 38 (2012) 283e301
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Progress in Energy and Combustion Science

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Review
Use of bioethanol for biodiesel production

C. Brunschwig a, W. Moussavou a, J. Blin a, b, *
a
Institut International d’Ingénierie de l’Eau et de l’Environnement (2iE), Rue de la Science, 01 BP 594, Ouagadougou 01, Burkina Faso, France
b
Centre de Coopération Internationale en Recherche Agronomique pour le Développement (CIRAD), UPR Biomasse Energie, TA B-42/16, 73 rue Jean-François Breton,
34398 Montpellier Cedex 5, France
a r t i c l e i n f o a b s t r a c t
Article history: Faced with the energy crisis and environmental degradation, due to the massive use of fossil energy
Received 13 April 2011 sources, biodiesel is an attractive alternative to diesel fuel. With a view to developing local biodiesel
Accepted 1 October 2011 production, using bioethanol as a sustainable reactant for biodiesel production, rather than methanol, is
Available online 15 December 2011
leading to increasing interest, notably in emerging countries. Indeed, bioethanol, which is less toxic than
methanol, is produced from local and renewable agricultural resources, being more sustainable and
Keywords:
providing access to greater energy independence. However, some issues are limiting the process like
Biodiesel
purification problems, or the presence of water in bioethanol leading to a drop in yield. Although several
Bioethanol
Ethyl esters
studies have already been published on ethyl ester production, most of them primarily focus on
Transesterification homogeneous alkaline catalysis, and report various data. Therefore, this paper aims at presenting
Catalysis a review of previous studies on the subject.
Fuel characteristics The aim of this article was to analyze all the literature data available on ethyl ester production, to gain
a clearer insight into the advances made in the process, and bring out prospects for developing ethyl
ester production, along with the limitations.
This paper compares the different catalytic pathways that have been investigated for ethyl ester
production. It discusses the effect of the main reaction parameters on the yield, the purification issues,
and the characteristics and specifications of ethyl esters. This study shows that all authors formerly
agreed in saying that ethyl esters separation and purification were a limiting stage. But these limitations
can be overcome as high yields over 90% can be obtained by optimizing all the reaction parameters.
Moreover, the negative effect of the water contained in bioethanol remains controversial.
Finally, ethyl esters proved to be a viable alternative to diesel fuel being more sustainable than methyl
esters. Some aspects of their production are worth a closer look for shifting the use of bioethanol to
large-scale production.
Ó 2011 Elsevier Ltd. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2
2. Transesterification process to produce ethyl esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4
2.1. Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2. Nature and characteristics of raw materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2.1. Triacylglyceride sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2.2. Bioethanol, a green reactant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3. Catalysis to produce ethyl esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5
3.1. Homogeneous catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1.1. Homogeneous alkaline catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1.1.1. Alkaline metal hydroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.1.2. Alkaline metal alkoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1.2. Homogeneous acid catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
* Corresponding author. Institut International d’Ingénierie de l’Eau et de l’Environnement (2iE), Rue de la Science, 01 BP 594, Ouagadougou 01, Burkina Faso, France.
Tel./fax: þ33 226 76 16 75 59.
E-mail address: [email protected] (J. Blin).
0360-1285/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pecs.2011.11.001
284 C. Brunschwig et al. / Progress in Energy and Combustion Science 38 (2012) 283e301
3.2. Heterogeneous catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

3.3. Enzymatic catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4. Effect of main factors on ethyl ester yield . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8
4.1. Reaction time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.2. Ethanol: oil molar ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.3. Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.4. Amount of catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.5. Stirring speed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.6. Purity of reactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.6.1. Free fatty acid content . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.6.2. Water content . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
5. Purification of ethyl esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10
5.1. Phase composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5.2. Factors affecting separation of the glycerol and ester phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5.3. Crude ethyl ester purification methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
5.3.1. Water washing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
5.3.2. Dry washing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
5.3.3. Membrane extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
6. Ethyl ester characteristics and specifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12
6.1. Ethyl ester fuel properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
6.1.1. Kinematic viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
6.1.2. Higher heating value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
6.1.3. Cetane number . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
6.1.4. Flash point . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
6.1.5. Low temperature properties (pour and cloud points) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
6.1.6. Oxidative stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
6.2. Effect of contaminants on ethyl ester uses and handling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
6.3. Ethyl ester specifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
6.4. Ethyl ester analysis methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
6.5. Environmental and economic impacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
6.5.1. Environmental impact . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
6.5.2. Economic impact of biodiesel use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
7. Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .15
8. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .15
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1. Introduction To avoid adapting vehicle engines, one alternative consists in

chemical modification of vegetable oils by transesterification to
In order to cope with growing demand for energy, the depletion obtain biodiesel. This biofuel has fuel characteristics similar to
of fossil fuel resources and environmental problems raised by fossil those of diesel fuel. It can therefore easily be used as a pure fuel
fuel use, countries wishing to limit their energy dependence on or blended with diesel fuel in diesel engines, without any major
petroleum exporting countries are developing alternative energy engine modifications [4]. Only a few seals or hose adaptations
sources, such as biofuels [1]. As early as the 19th century, Mr may prove necessary, as biodiesel is an excellent rubber solvent.
Rudolph Diesel developed the first biofuels using vegetable oils in Biodiesel is therefore a very interesting alternative to diesel fuel.
compression ignition engines [2]. Vegetable oils are easy to It contributes toward sustainable development [5] as i) it makes
produce as they are obtained by simple pressing of oil-bearing it possible to use locally available, renewable resources [6] and ii)
biomass prior to decanting and filtration. However, using vege- it reduces greenhouse gas emissions when compared to diesel
table oils in diesel engines designed to run on diesel fuel raises fuel [7], without sacrificing engine performance [4,8]. In the
certain problems. Indeed, partly due to their high viscosity and transesterification reaction, triacylglycerides (commonly called
partly due to their low cetane number compared to diesel fuel, triglycerides) in vegetable oils are converted into fatty acid alkyl
vegetable oils are harder to pump, inject and ignite in diesel esters called “biodiesel” in the presence of short chain alcohol
engines. Moreover, the use of vegetable oils may generate the and a catalyst, with glycerol as a by-product (Fig. 1). The trans-
accumulation of gums in the inner parts of the diesel engine due to esterification reaction proceeds generally with a catalyst to
the presence of phospholipids in the fuel, depending on the increase reaction speed. Catalysts used for the transesterification
pressing temperature and on the nature of the biomass used of triacylglycerides are usually classified as homogeneous,
upstream [3]. Some modifications therefore have to be made to the heterogeneous or enzymatic catalysts depending on the mecha-
engine. The aim of the modifications is to maintain a high vegetable nism [9,10].
oil temperature to lower viscosity and improve ignition [3] and On an industrial scale, biodiesel is primarily synthesized from
thereby ensure durable engine operation. Using vegetable oils as methanol, itself a refinery residue and therefore mostly synthesized
fuel is particularly adapted to static engines. Once that type of from fossil resources [11]. The resulting biodiesel carbon is there-
engine has been started up, they are sized to operate permanently fore not of 100% vegetable origin. With the enthusiasm for biofuels
at a high regime, hence at high temperatures. However, it is difficult over the last twenty years, technologies for synthesizing biodiesel
to use vegetable oil for vehicle engines, which undergo substantial from methanol have been very widely studied and optimized in
variations in load, resulting in wide temperature ranges inside the industrialized countries. This resulted in highly efficient and
combustion chamber. increasingly perfected processes that are only cost-effective on
C. Brunschwig et al. / Progress in Energy and Combustion Science 38 (2012) 283e301 285
O O
O R1 R O R1 OH
O O
catalyst +
O R2 + 3 ROH R O R2 OH
O O
O R3 R O R3 OH
triacylglycerides alcohol alkyl esters glycerol
Fig. 1. Typical transesterification of triacylglycerides with alcohol into alkyl esters R ¼ CH3 methyl esters; R ¼ CH3CH2 ethyl esters.
a large scale [12]. The most preferred ones are with continuous flow with any limitations. Based on a bibliographical analysis, our
because they require less investments and operating costs [13]. method opted for a comparative approach, comparing the produc-
Nowadays, an ever-increasing number of stakeholders in tion of ethyl esters with that of methyl esters. After providing a brief
emerging countries that do not have petroleum refineries to get reminder of a few general aspects of the biodiesel transesterification
methanol are seeking to develop their own biodiesel processes, process, the article presents the different possible catalysis path-
using simple technologies that utilize local resources. To that end, ways for ethyl ester production, along with the main reaction
replacing methanol by ethanol in a more sustainable biodiesel parameters influencing yield. This study then shows what the
synthesis is arousing a great deal of interest [14]. In that way, critical factors are during ethyl ester purification. Lastly, the char-
processes using homogeneous catalysis seem to be the most acteristics and specifications of ethyl esters are discussed.
promising ones as they do not require highly perfected technology,
consume less alcohol and energy [12]. However, future stakeholders 2. Transesterification process to produce ethyl esters
should keep in mind that the environmental and economical benefit
of homogeneous over heterogeneous catalysts should be balanced 2.1. Background
by the fact that they require more purification steps [12].
Ethanol, as a reactant for biodiesel production can be locally The transesterification is the reaction of triacylglycerides con-
available as it is synthesized by alcohol fermentation from renew- tained in oils or fats with reactive molecules called acyl-acceptors,
able agricultural resources which are rich in sugar or starch [11]. such as alcohols or acetates. The slow and equilibrium reaction is
Thus, the carbon of synthesized ethyl esters is of 100% vegetable usually speeded up by the presence of catalysts (Fig. 1).
origin. The higher reactivity of ethanol is discussed in Section 2.2.2. The acyl-acceptors are mostly i) primary or secondary short-
Its better solvent properties imply some technical limitations but chain alcohols containing between 1 and 8 carbon atoms, or ii)
not so critical if reaction parameters are properly optimized: i) the acetates such as methyl acetate [15,16]. The alcohols that give the
presence of emulsions in the final reaction medium, ii) and the best biodiesel yields are unbranched alcohols, with low steric
difficult recovery of ethanol. Moreover the presence of water in hindrance, such as methanol, ethanol, propanol, butanol, and amyl
bioethanol, due to the formation of a 95/5 ethanol-water azeotrope alcohol [17e19] as they give low activation energy intermediates
during rectification [13] leads to secondary reactions which could [20]. The most widely used alcohols, for cost reasons, are first
consequently lower yields [15]. methanol, but also ethanol, which give methyl esters and ethyl
Many researchers, who are aware of the opportunities for esters respectively [17,21].
developing local biodiesel production using ethanol and of the Triacylglycerides are successively converted into diac-
associated socio-economic and environmental advantages, are ylglycerides, monoacylglycerides then glycerol, giving rise at each
seeking to optimize the process to overcome these limitations. stage to the release of 1 mol of alkyl esters. Water content in the
One sign of that enthusiasm is that the number of publications reaction medium has to be limited as it promotes hydrolysis, which
on optimizing the ethyl ester production process has risen reduces transesterification yield [9,17,22,23]. Water hydrolyses tri-
substantially in the last five years. But data available in the litera- acylglycerides into free fatty acids, which are converted into soaps
ture for ethyl ester production is found: if the reaction medium is alkaline [9].
Once the reaction is complete, two phases usually co-exist, the
i) Either sporadically in general literature reviews on biodiesel ester-rich phase and the glycerol-rich phase, which are separated
production, which mostly focus on the synthesis of methyl by simple gravity, or by other techniques such as centrifugation or
esters and only mention ethyl ester synthesis in passing, membrane filtration [22]. In the case of ethanolysis (i.e trans-
without specifying any particularities, esterification with ethanol), one single pseudo homogenous phase
ii) Or in technical articles specific to biodiesel production with is frequently observed .The reaction medium is then purified to
ethanol, which concentrate on a given single aspect of the eliminate contaminants, namely glycerol, residual alcohol, the
process: optimizing yields in line with reaction parameters, catalyst and residual soaps and glycerides.
analysing the composition of the phases and their separation,
or evaluating the impact of biodiesel physico-chemical 2.2. Nature and characteristics of raw materials
properties on engine performance or emissions. These
specialized articles focused on various aspects of the process 2.2.1. Triacylglyceride sources
that require a review. Conventionally, the triacylglyceride sources used for biodiesel
production are grouped into several categories according to their
The main purpose of this document was to review all the work origin and the specificities of their fatty acid composition. Cate-
undertaken and published on the production of ethyl esters, in order gories differ depending on the authors, but can be typically sum-
to bring out prospects for developing the different processes, along med up as follows:
i) Edible and non-edible vegetable oils According to studies undertaken between 2006 and 2009,
ii) Animal fats the costs of producing bioethanol during this period are worth at
iii) Used frying oils (or waste oil) least the double of methanol derived from fossil fuels, respectively
iv) Other sources of oils, such as micro-algae, bacteria, fungi from 0.25 USD/L to 0.95 USD/L [69e72] and 0.14e0.23 USD/L
[24,25] [72e74]. Moreover, authors showed that costs are highly variable
depending on the biomass. This uncertainty about the evolution of
Although the literature reviews show that research work makes production costs is one of the main reasons why methanol from
use of all triacylglyceride sources as biodiesel [1,10,24,25], vege- fossil fuels is still preferred. However, in the near future bioethanol
table oils remain the triacylglyceride sources mostly used today production costs are expected to be more competitive with the
throughout the world for industrial methyl ester production. The improvement of existing technologies or/and with the develop-
main oil-bearing plants from which they are extracted are grown in ment of 2nd generation biofuel processes. Those convert all
several agro-climatic zones: biomasses into bioethanol by fermentation of cellulose and hemi-
celluloses [70].
i) Soybean oil in the USA and South America, The high cost of bioethanol production compared to methanol
ii) Rapeseed oil in Europe and Canada, depends directly on its production process, which uses biomass as
iii) Sunflower oil in Europe and in tropical countries, the raw material, the main sources of which are plants rich in
iv) Palm oil and copra oil in tropical countries [1]. sugars and starches [11,70,71]. The bioethanol production process
follows three major stages: i) extraction of simple fermentable
According to Demirbas et al. [24], the availability of oilcrop sugars either by hydrolysis of starch or by pressing/washing of
resources is a decisive factor for the biodiesel production process, sugar-bearing biomass, ii) fermentation of simple sugars in an
since accessing and purchasing the raw material currently accounts ethanol-water mixture at around 20 by biocatalysts, iii)
for 70%e80% of the total cost of biodiesel [24,26]. separation-distillation operations to concentrate the ethanol
Crude vegetable oils are not recommended as a source of tri- [13,71]. A first distillation operation is carried out to obtain
acylglycerides for biodiesel application as they contain, in partic- a mixture composed of 95% ethanol, just short of the ethanol-water
ular, phospholipids and free fatty acids, which can reduce azeotrope (95.6%, 78.1 C). Various techniques exist for exceeding
transesterification yield. Consequently, vegetable oils have to be this azeotropic barrier to obtain more than 99% high-purity anhy-
degummed, neutralized, washed and dried to remove phospho- drous ethanol: conventional azeotropic distillation techniques with
lipids and free fatty acids [13,21]. Vegetable oils that have only been a carrier solvent, gradually replaced by the molecular sieve dehy-
degummed are also an acceptable source of triacylglycerides [21], dration technique [13], or more recent permeation or pervapora-
though the recommended maximum free fatty acid content is tion techniques [75].
around 1% [27]. Conventional bioethanol dehydration processes are very
Ideally for biodiesel applications, according to Pinzi et al. [28], energy-intensive. Their energy consumption amounts to 31%e64%
a vegetable oil must be composed of i), large quantities of mono- of the heating value of anhydrous ethanol depending on the
unsaturated fatty acids, ii) small quantities of polyunsaturated fatty process used, i.e. 9e18 MJ/kg of ethanol [76]. Due to the costs
acids and iii) controlled quantities of saturated fatty acids. This type generated by dehydration, bioethanol on the market can contain up
of fatty acid composition makes it possible to obtain an optimum of to 4% water depending on the suppliers.
the different properties sought for biodiesel, such as a high heating While bioethanol is a promising reactant for biodiesel applica-
value and good oxidative stability [28] (see Section 6.1). Table 1 tions, its water content can be a limiting factor. Indeed, most of the
summarizes the main research results for ethyl ester production bibliographical reviews mention that the water content of the
by chemical catalysis using a wide range of triacylglyceride sources. reaction medium has a negative effect on yield [18,23,24,77] as
To optimize ethyl ester production, many studies have focused on water causes secondary hydrolysis reactions that induce both
the vegetable oils typically used for methyl ester production, such as a drop in yield and more complicated purification. Nevertheless,
soybean oil [29e38], rapeseed oil [39e47], sunflower oil [45,48,49], there is a clear lack of precise data on the effect of water content,
palm oil [50e52] and copra oil [53,54]. Despite common belief, it is notably on the production of ethyl esters (Section 4.6.2). Data
very interesting to see that the yields achieved with ethanol are over remain very sparse and contradictory [41,78] and although there
90% in most of the studies. Some more exotic oils, which are also are no official specifications, the water content required as
attracting interest in their production zone, have also been tested a precaution for bioethanol is 0.1% [13].
for ethyl ester production: castor oil [27,29,30,55e58], Jatropha Reactivity of ethanol compared to methanol is very controver-
curcas oil [59], cottonseed oil [57,60,61], rice bran oil [54], mustard sial in the literature and generalities cannot be drawn as reactivity
seed oil [48,62], candlenut oil [63], cardoon oil [19], coffee oil [64], depends on many factors. Some authors argue that ethanol is less
grape seed oil [65], linseed oil [45], neem oil [66], radish oil [67]. The reactive than methanol [44] leading to lower yields. In fact, eth-
yields reached are also high (>90%) and competitive with those of oxide ions are more nucleophile (1.0) than methoxide ions (0.82)
the most common oils (Table 1). but they have lower mobility due to their carbon chain length [79].
However, the better solvency of ethanol implies the formation of
2.2.2. Bioethanol, a green reactant emulsions (and soaps) linked to the properties of ethanol that may
Bioethanol is a very promising reactant for biodiesel pro- complicate mass transfers [80], as well as further purification [81]
duction, when compared to methanol: firstly, it is not toxic and is even if not so critical for final yield.
a “green” reactant. Indeed, the bioethanol production through the
fermentation of biomass, a locally available and renewable raw 3. Catalysis to produce ethyl esters
material, makes bioethanol a more sustainable reactant than meth-
anol which is nowadays industrially produced from fossil fuels [11]. The ethanolysis is slow and balanced, so catalysts are used to
In the future, renewable methanol or biomethanol could be accelerate the reaction rate. The catalysis pathways studied and
produced from biomass, either by fermentation or thermal conver- presented in the literature for ethyl ester production are usually
sion. The last process is the most promising but has to be optimized to classified into homogeneous, heterogeneous, or enzymatic due to
increase yields and become economically viable [68]. their specific activity [9,10].
Table 1
Optimization of the production of ethyl esters and various feedstocks by chemical catalysis.
Catalysis Oil Ethanol: Catalyst Catalyst amount T( C) Time (h) f (rpm) Yield (%) Ref
oilmolar ratio (%wt oil)
Homogeneous candlenut 7.5:1 KOH 1.5 room 1 600 99 [63]
alkaline cardoon 12:1 NaOH 1 75 2 e 95 [19]
9:1 KOH 1 75 2 e 90 [19]
castor oil 11:1 KOH 1.75 30 1.5 e 86 [27]
>19:1 NaOEt >1.3 or 0.8e1.2 room 0.5 600 94 [55]
3:1 NaOH 0.5 70 3 400 96 [30]
5.7:1 KOH 1.1 reflux 2 e 30 [29]
6:1 NaOH 0.1 80 6 e 55 [57,58]
6:1 KOH 0.1 80 10 e 55 [57,58]
6:1 NaOMe 0.1 80 6 e 81 [57,58]
6:1 KOMe 0.1 80 6 e 78 [57,58]
6:1 K2CO3 0.1 80 10 e <50 [57]
6:1 CaCO3 0.1 80 10 e no catalytic [57]
activity
castor seed 0.5:1 to 1.5:1 NaOEt or KOEt 0.3e1.5 45e55 0.5e1.5 e 98e100 [56]
coconut 6:1 NaOH 0.75 room 0.1 sonication 98 [53]
9:1 NaOH 1.0 78 0.01 e 100a [54]
coffee 6:1 NaOMe 1.0 25 2.0 600 87 [64]
cotton 20:1 KOH 1.07 25 0.5 600 98 [60]
6:1 NaOH 1.0 60 1.25 e 89 [61]
6:1 NaOH 0.1 80 1 e 80 [57]
6:1 NaOMe 0.1 80 1 e 88 [57]
grapeseed 6:1 KOMe 1.0 60 1 e 97 [65]
Jatropha curcas 6:1 KOH 3.0 75 1.5 e 99 [59]
linseed (flax) 6:1 NaOMe 0.25 70 2 e ND [45]
mustard 7:1 KOH 1.5 32 1 600 91 [48]
7:1 KOH 1.5 20 1 600 100 [48]
6:1 KOH 1.5 35 1 600 98 [62]
neem 10:1 NaOH 0.7 75 6.5e8 e >88 [66]
palm 3.4:1 KOH 1.0 60 2 e 96 [50]
1st step 24:1 1st step H2SO4 1st step 4 70 1st step 1 e 80a [142]
2nd step 4:1 2nd step KOH 2nd step 1.5 2nd step 0.08
palm (tucum) 6:1 NaOH 1.0 60 0.5 e 90 [52]
radish 1st step 11.7:1 NaOH 1st step 0.4 45 1 600 99 [67]
2nd step 6:1 2nd step 0.03
rapeseed 6:1 NaOH 1.0 80 0.25 e 94 [41]
6:1 KOH 0.89 25 1.5 10000 92 [39]
10:1 KOH 1.66 25 1.5 10000 99 [40]
4.5:1 NaOMe 0.5 room 2 high 98 [43]
6:1 KOH 1.0 room 2 high 92 [43]
rapeseed (canola) 6:1 NaOMe 0.25 70 2 e ND [45]
6:1 KOH 1.0 70 2 e ND [44]
rice bran 9:1 NaOH 1.0 78 0.01 e 83a [54]
soybean 12:1 NaOH 0.3 70 1 600 97 [31]
12:1 KOH 1.0 70 1 600 [31]
12:1 KOH 0.8 40 0.3 e 95 [33]
10.5:1 NaOH 1.0 70 2 e 93 [32]
9:1 NaOH 0.5 30 1 400 95 [30]
3:1 NaOH 0.5 70 3 400 93 [30]
34:6 KOH 1.1 reflux 2 e 96 [29]
12:1 KOH 1 30 1 600 95 [38]
sunflower 7:1 NaOH 2.0 room 1 600 88/98b [49]
5:1 KOH 1.5 20 1 600 98 [48]
6:1 NaOMe 0.25 70 2 e ND [45]
used frying 9:1 NaOH 1.0 78 0.01 e 94a [54]
oil (palm)
used frying oil 12:1 KOH 1.0 78 2 e 74 [83]
(olive, sunflower)
used frying oil 12:1 NaOH 1.0 78 2 e 63 [83]
(olive, sunflower)
used frying oil 12:1 KOMe 1.0 78 2 e 64 [83]
(olive, sunflower)
used frying oil 12:1 NaOMe 1.0 78 2 e 59 [83]
(olive, sunflower)
Homogeneous cotton 6:1 HCl 0.25% mol 80 6 e 60 [57]
acid castor oil 6:1 HCl 0.25% mol 80 8 e 78 [58]
6:1 H2SO4 0.25% mol 80 4 e 68 [58]
rapeseed 6:1 H2SO4 1.3% mol 85 3 500 27 [47]
used frying oil 3.6:1 H2SO4 0.1 73 40 e 67a [89]
used frying 6:1 H2SO4 2.25% mol reflux 3 e e [88]
oil (palm)
used frying 6:1 HCl 2.25% mol reflux 3 e e [88]
oil (palm)
(continued on next page)
Table 1 (continued )
Catalysis Oil Ethanol: Catalyst Catalyst amount T( C) Time (h) f (rpm) Yield (%) Ref
oilmolar ratio (%wt oil)
Heterogeneous beef tallow 100:1 ion-exchange resin 20% mol 64 18 e 70 [93]
-sulfonated polystyren
SPS#218
rapeseed 16:1 Mixed oxide Mg2CoAl 2.0 200 C, 5 e 97 [46]
(canola) 25 atm
rapeseed 6:1 Heteropolyacid 1.7% mol 85 3 500 27 [42,47]
H3PW12O40, 24H2O
soya 30:1 carbohydrate- equivalent to 70 30 e similar [36,37]
derived/sawdust 5% H2SO4 to H2SO4
e carbohydrate-derived/ equivalent 70 100 e >95 [34,35]
corn stover to 5% H2SO4
100:1 ion-exchange resin 20% mol 64 >80 e 80 [93]
-sulfonated polystyren
SPS#218
ND: not determined.

a
Microwave.
b
Ultrasound; bold letters are used for fixed parameters.
3.1. Homogeneous catalysis mechanism of homogeneous alkaline catalysis of ethanolysis is

divided into four main steps [9] (see Fig. 2):
Homogeneous catalysis during ethanolysis takes place either in
a biphasic reaction medium constituted of a lipid phase and an i) Step 1: the production of the active species i.e the alkoxide
ethanol phase in which the catalyst is dissolved beforehand or in ion RO (step 1a) which is a strong nucleophile which will be
a monophasic medium, depending greatly on the reaction param- detailed in following sections. Products such as water or
eters especially the ethanol/vegetable oil ratio and the catalyst methanol produced during this step could lead to secondary
concentration [43]. It is not so essential to stir the reaction medium reactions.
to optimize contact between the reactants and the reaction speed ii) Step 2: the nucleophilic attack of RO to the carbonyl group of
as in the case of methanolysis. During the ethanolysis, the initial triacylglycerides forming a tetrahedral intermediate
reaction medium moves towards another system comprising, in iii) Step 3: the intermediate breakdown leading to the formation
some cases, a phase rich in ethyl esters and a phase rich in glycerol of ethyl ester
[82]. In some other cases, depending on the reaction parameters, iv) Step 4: the regeneration of the RO species and production of
the final pseudo-homogeneous phase could remain stable. diacylglyceride (Fig. 2)
The homogeneous catalysts studied and presented in the liter-
ature for ethyl ester production are either alkaline or acid. The steps 2e4 are repeated twice for the other R2 and R3 radical
leading successively to monoacylglyceride and glycerol.
3.1.1. Homogeneous alkaline catalysis
Homogeneous alkaline catalysts are by far the catalysts most 3.1.1.1. Alkaline metal hydroxides. Alkaline metal hydroxides are in
frequently used for ethyl ester production. The homogeneous fact transesterification catalyst precursors as they react with
alkaline catalysts used for the transesterification reaction are clas- ethanol giving the active species that is the ethoxide ions
sified into two main classes depending on the reaction mechanism: CH3CH2O whereas alkaline metal alkoxides are already the reac-
catalyst precursors being alkaline metal hydroxides (NaOH, KOH), tion catalysts. There is simultaneously formation of water during
reaction catalysts being alkaline metal alkoxides, methoxides the production of active species CH3CH2O which leads to hydro-
(NaOCH3, KOCH3) or ethoxides (NaO CH2CH3, KO CH2CH3), and lysis and saponification reactions and lowers ethyl ester yields
more sporadically sodium or potassium carbonates (Na2CO3, [57,58]. However, alkaline metal hydroxides are most often used in
K2CO3) [15,23,83]. the majority of experiments with ethanol, as they are cheaper [23].
Calcium and potassium carbonates are not very efficient at all, or General conclusions on the relative efficiency of NaOH and
even inefficient for catalysing ethyl ester production. K2CO3 gave KOH for ethyl ester production cannot be drawn as specified by
a yield under 50%, whereas CaCO3 showed no catalytic activity, Meneghetti et al. [58]. It is highly variable depending on the
partly due the fact that they are insoluble in the reaction medium oils used, the reaction time and the concentration of hydroxides.
[57]. Fillières et al reported that sodium hydroxide gives a higher yield
More than 3/4 of the studies published on ethanolysis used than potassium hydroxide as it produces fewer soaps during
alkaline metal hydroxides or alkoxides to catalyse the reaction ethanolysis of rapeseed oil [41]. Likewise, sodium hydroxide
(Table 1). This type of catalysis gives high yields under certain gives higher yields than potassium hydroxide at the same amount
conditions: i) when the free fatty acid content is not too high, at (wt%) for the ethanolysis of cardoon oil [19], or castor oil [57], or
around 1%, ii) if reaction conditions are mild, notably with catalyst even at a lower amount in the case of soybean oil [31]. However,
concentrations of around 0.5e1% [27], iii) when the ethanol water in the case of ethyl ester production from frying oils reported
content is under 0.1% [13]. by Encinar et al. [83], potassium hydroxide proves to be more
All authors agree in saying that this catalytic pathway is efficient efficient than sodium hydroxide. It is useful to note that most of
but that the reaction conditions must absolutely be optimized studies are based on massic catalyst loadings (%wt) not on molar
[27,30,31,39,48,55,60,67,84e86]. Indeed, the reaction with ethanol ones. But due to NaOH lower molecular weight, the equivalent
is more difficult to implement than with methanol and optimiza- amount on a molar basis of 1% wt of NaOH is 1.4% wt of KOH [87].
tion of the different reaction parameters is a key factor in achieving This may explain why, in some studies, KOH give lower yields
high yields. The effects of different parameters on yield in homo- than NaOH at the same massic loadings, producing indeed less
geneous alkaline catalysis are discussed in Section 4.1. The global alkoxides.
step 1 ROH + B- RO- + BH
O O–
O R1 O R1
OR
O O
step 2 O R2 + RO- O R2
O O
O R3 O R3
O–
O R1 O–
OR
O O O
step 3 O R2 O R2 + R O R1
O O
O R3 O R3
O– OH
O O
step 4 O R2 + BH O R2 + B-
O O
O R3 O R3
Fig. 2. Homogeneous base-catalyzed mechanism for the transesterification of triacylglycerides; steps 1e4.
3.1.1.2. Alkaline metal alkoxides. Alkaline metal ethoxides are and transesterification simultaneously and are generally recom-
reaction catalysts that are expected to be very efficient because mended for high free fatty acid oils such as frying oils [9,17,89].
they do not lead to secondary reaction like methoxides. Reactions The main homogeneous acid catalysts used for the trans-
with methoxides (that are usually synthesized and sold in meth- esterification reaction are sulfuric acid, hydrochloric acid and, more
anol solution) lead to a mixture of methyl and ethyl esters, where rarely, sulphonic acid [15,23,91]. Only the first two acids have been
ethyl esters are expected to remain in higher quantity. As for tested for ethyl ester production and the efficiency of HCl compared
hydroxides, general conclusions are hard to be drawn on the rela- to H2SO4 cannot be generalized given the small number of studies.
tive efficiency of sodium and potassium alkoxides. Few studies have Enweramadu et al. [89] highlighted that sulfuric acid is more effi-
been undertaken to determine the efficiency of NaOCH3 compared cient than hydrochloric acid. On the other hand, Meneghetti et al.
to KOCH3 for ethyl ester production (and even none to our [57,58] showed that hydrochloric acid gives a 10% higher ethyl ester
knowledge on ethoxides). Moreover, results are contradictory: in yield than that obtained with sulphonic acid, but for a longer
an initial study, Meneghetti et al. [57,58] showed that NaOCH3 is reaction time.
more efficient than KOCH3 for producing ethyl esters from castor Homogeneous acid catalysis calls for more severe reaction
oil, whereas in a second study, Encinar et al. [83] showed that conditions than homogeneous alkaline catalysis for ethyl ester
KOCH3 is more efficient than NaOCH3 with frying oils, without any production (Table 1). For instance, an increase in the ethanol:
viable explanation. vegetable oil molar ratio, in the temperature, but especially in the
reaction time [47,57,58,88e90] from 3 h up to 40 h [89] makes it
3.1.2. Homogeneous acid catalysis possible to obtain relatively high yields. In one of the few
As for methyl ester production, most of the work on ethyl ester comparative studies of ethyl ester production by homogeneous acid
production has been done with homogeneous alkaline catalysts catalysis and homogeneous alkaline catalysis, Meneghetti et al
because, when compared with homogeneous acid catalysts, i) they found that certain acid catalysts, such as HCl or H2SO4, were more
do not corrode the equipment, ii) they are more reactive if the oil is efficient than the conventional alkaline catalysts KOH or NaOH.
not too acid, iii) operating conditions are less severe [9,17]. However, that efficiency, which was seen for low ethanol: vegetable
However, some work has been published on ethyl ester production oil molar ratios of around 6:1, and despite long reaction times
by homogeneous acid catalysis [47,57,58,88e90]. The homoge- exceeding 4 h, gave yields that did not exceed 78% [57,58]. These
neous acid catalysts have an important advantage with respect to same limitations of homogeneous acid catalysts were also found for
homogeneous alkaline catalysts: they can catalyze esterification methyl ester production [15] but anhydrous ethanol gives high
yields, better than methanol [91]. Therefore, more severe reaction Enzymatic catalysts are more environment-friendly as they
conditions (high ethanol/oil molar ratio, high temperature, long are of biological origin and their use calls for less energy, as oper-
reaction time) are to be applied in homogeneous acid catalysis to ating conditions are milder than with chemical catalysts [95].
ensure sufficient ethyl ester yields for potential industrial produc- However, several authors have shown in literature reviews that
tion [9,10,91,92]. enzymatic catalysts can be efficient for ethyl ester production
but some limitations must be overcome especially because ethyl
ester yield is affected by a large number of factors needed to
3.2. Heterogeneous catalysis
ensure optimum enzyme activity (temperature, pH, molar ratio,
amount of catalyst) [10,15,16,94,96]. Indeed, yields over 80% can be
When compared with homogeneous catalysis, heterogeneous
reached by optimizing the reaction parameters, though with long
catalysis offers the advantage of having less of an environmental
reaction times which can exceed 24 h or with the use of a co-
impact, thanks to the smaller amounts of wastewater produced.
solvent [15,95,96].
Indeed, the purification processes are simplified, as the solid cata-
lysts can be recovered by simple filtration and possibly recycled
[17]. Heterogeneous catalysis calls for severe reaction operating 4. Effect of main factors on ethyl ester yield
conditions, notably in terms of temperature and pressure, which
are more difficult to implement and require greater means than Due to relative scarcity of data concerning homogeneous acid,
homogeneous catalysis [13]. heterogeneous and enzymatic catalysis, most of the points dis-
On the contrary, few studies have been published on ethyl ester cussed hereinafter concern homogeneous alkaline catalysis unless
production by heterogeneous catalysis [34e37,42,46,47,93], both specified otherwise. According to many studies focusing on the
because they require specific equipment for severe reaction influence of reaction parameters on the ethanolysis (see all refer-
conditions, but also undoubtedly because heterogeneous catalysis ences in Table 1), the main independent variables that affect ethyl
for biodiesel production lies at the heart of major industrial stakes. ester production are [40]:
The heterogeneous catalysts used for ethyl ester production are of
various kinds (Table 1): very efficient mixed oxides [46], efficient i) The ethanol: vegetable oil molar ratio, MR
ion exchange resins [93], efficient sulfonated carbohydrate-derived ii) The reaction temperature, T
and charcoal catalysts [34e37] or less efficient heteropolyacids iii) The amount of catalyst (weight ratio of catalyst to vegetable
[42,47]. oil wt%), C
The performances of these catalysts for ethyl ester production iv) The purity of reactants (free fatty acid and water contents)
clearly depend on reaction conditions. This work highlights the
need to apply specific and severe reaction conditions, in order to These variables have a great effect on the yield and on the purity
counter diffusion phenomena limiting the reaction in a lipid phase/ of ethyl esters, as well as of methyl esters. Moreover, other variables
ethanol phase/solid catalyst triphasic medium and achieve high such as the reaction time t and stirring speed f are of less impor-
transesterification yield [46,93]. These conditions involve: tance especially in the case of ethyl ester production. Statistical
models are often used to understand and explain these effects. The
i) The amount of catalyst, which rises up to 20 mol % to oil [93], statistical models investigate the effect of three or four important
and the ethanol: vegetable oil molar ratio, which can rise to factors and use the design of experiment to draw a model of the
30:1 or even 100:1 [36,37,69,93]. yield within the ranges of parameters investigated. However, it is
ii) The temperature and the pressure, which can rise to 200 C important to note that these effects depend on the nature of the
and 25 atm respectively [46]. catalyst used, homogeneous, heterogeneous or enzymatic. As most
iii) The reaction time which can exceed 100 h [34e37]. of the work on ethyl ester production has been carried out in
homogeneous alkaline catalysis (Table 1), data about the effect of
Yields can then reach very high values of around 97%, as in the different factors on yield is more complete for that type of catalysis
study by Li et al. [46]. Such reaction conditions entail a very high than for the other types.
energy cost. Otherwise, if reaction conditions in heterogeneous
catalysis remain mild, ethyl ester production yields remain very low
4.1. Reaction time
[42,47].
Particular attention should be paid to the research work
The reaction time has a minor effect on the conversion rate of
undertaken by the Fictorie et al team at Dordt College, consisting in
ethanolysis in homogeneous alkaline catalysis. All authors are
using biomass as an ecological heterogeneous catalyst. Agricultural
unanimous in saying that there exists an optimum reaction time.
and forest waste (sawdust, corn stover) are converted into sul-
Yield increases at the start of the reaction, and then reaches
phonated activated charcoals, which catalyse ethyl ester produc-
a maximum before decreasing slightly. The optimum reaction time
tion. Transesterification yields seem to be as high as with sulfuric
for ethyl ester production in homogeneous alkaline catalysis varies
acid (>97%), which is very encouraging, but reaction times are still
between one and 3 h depending on the vegetable oil used under
very long [34e37].
normal stirring (Table 1) and is generally located at around one and
a half hours [40,50]. The reaction begins very rapidly due to the
3.3. Enzymatic catalysis good dispersion of ethanol in the oil. After only 10 min or so, the
yield already reaches an asymptotic value of over 90%, then the
Enzymatic catalysts are arousing increasing interest for ethyl reaction slows down and reaches equilibrium [97]. After 1 h, over
ester production, but they are not yet rivaling chemical catalysts. 95% of triacylglycerides have been converted into ethyl esters
The enzymatic catalysts of the transesterification reaction are (Table 1). Lastly, when close to equilibrium, for high reaction times
lipases or triacylglycerol acyl-hydrolases (E.C.3.1.1.3) produced of around 1 h30 to 2 h, the reverse reaction whereby ethyl esters are
either by microorganisms (fungi, bacteria), or by animals, or by hydrolysed into fatty acids leads to a drop in yield [17]. While the
plants. Commercially available preparations are mostly derived ethanolysis duration is positive at the start of the reaction, its effect
from microorganisms for cost reasons [94]. is more difficult to define once equilibrium has been reached [40].
4.2. Ethanol: oil molar ratio speed up the ethanolysis but can also promote secondary reactions
such as hydrolysis or saponification if too high.
The ethanol: vegetable oil molar ratio is one of the factors that A critical catalyst amount corresponds to optimum ethyl ester
has the greatest effect on ethyl ester yield. The optimum yield is yield in most studies. That critical amount is highly variable
obtained for molar ratio values generally varying from 6:1 to 9:1 according to the literature [27,30,40,60], between 0.25 wt% and
depending on the different authors (Table 1), though some values 3.0 wt% and is most often around 1.0 wt% (Table 1). Similar values of
ranging from 3:1 to 20:1 were found. The minimum ethanol: 1.0 wt% catalyst critical amount have been reported for methyl ester
vegetable oil stoichiometry is 3:1. Ethanol is introduced in excess, to production [85,99,100].
optimize yield and reduce reaction times. In fact, a sufficient amount Like the other reaction factors, the effect of the catalyst amount
of ethanol is required to break glycerol-fatty acid bonds, but that depends greatly on the other reaction conditions, particularly the
amount must not exceed a certain limit as, beyond it, the ethyl ester ethanol: vegetable oil molar ratio, and on the amount ranges
purification process becomes more difficult and more expensive [98]. investigated [40]. In all the statistical models published, the main
Several studies undertaken with design of experiments effect of catalyst amount is either positive or negative depending on
[31,48,55,60,67] showed that the effect of the molar ratio on ethyl other reaction parameters, but the catalyst amount-molar ratio
ester yields is strictly dependent on the other reaction conditions, interaction is very often negative [27,31,48,55,60,67]. These obser-
and notably on catalyst amount. This is demonstrated by molar vations back the existence of a critical catalyst amount, beyond
ratio-catalyst amount interaction values that are frequently which yield decreases. The existence of this critical catalyst amount
significant on the one hand, and negative on the other is explained by increasing competition between glyceride conver-
[31,48,55,60,67]. Consequently, to optimize yield, it is better to sion and free fatty acid conversion at high catalyst amounts [40].
avoid having simultaneously high molar ratio and high catalyst
amount. For low catalyst amounts, yield increases as the molar ratio 4.5. Stirring speed
increases [30]. For higher catalyst amounts, yield increases up to an
optimum, then decreases as the molar ratio continues to increase Stirring speed is one of the parameters that least affects ethyl
[27,50,55,60]. ester yield. Given the better miscibility of the reactants, ethanolysis
The limit between these two evolutions is defined by a critical is governed less by transfer phenomena than with methanol,
catalyst amount, which is around 1 wt% depending on the different making reaction medium stirring correspondingly less necessary
studies (Table 1). The competition between two phenomena [82]. The different optimization studies for reaction parameters
explains the existence of a critical ethanol: vegetable oil molar ratio confirm these findings (Table 1) as they do not consider the stirring
value. When the ethanol: vegetable oil molar ratio increases, its speed to be a relevant variable [30,31,48,55,60,64,67]. The stirring
effect is i) partly positive as the reaction equilibrium is displaced to speed is often fixed at around 600 rpm or even 400 rpm in relation
the right, favoring transesterification, ii) partly negative, as the with the reference value for the reaction with methanol.
solubility of glycerol in the ethyl ester-rich phase increases and Among the techniques for bringing the ethanol and vegetable oil
consequently the yield decreases. It is therefore necessary to identify phases into contact, stirring is the easiest and most frequently used
a critical ethanol: vegetable oil molar ratio in order to optimize yield. technique. Other methods, such as ultra-sounds or microwaves
have been tested, but are not recommended insofar as they require
4.3. Temperature more technical skill and give results for ethyl ester production that
are similar to those achieved by simple mechanical stirring [49].
Temperature plays a major role in every catalytic system being
positive by promoting phase transfers but also being detrimental 4.6. Purity of reactants
by promoting secondary reactions if the temperature is too high. In
the case of ethanolysis, the effect of temperature on ethyl ester yields Water and free fatty acids, the main two contaminants of the
is not systematic and depends significantly on the other reaction reactants, cause soap formation in homogeneous alkaline catalysis.
parameters (ethanol: vegetable oil molar ratio, catalyst amount and These soaps:
water content) but also on the temperature ranges investigated [40].
According to the different design of experiments we are aware i) Reduce catalyst efficiency as part of it is consumed by
of, temperature has a variable effect on yield: saponification,
ii) Reduce transesterification reaction yields,
i) it is either positive [19,30,62,83], the higher the temperature, iii) Increase viscosity, induce gel formation and, consequently,
the higher the yield cause difficulties during glycerol separation [9]. This point is
ii) negligible [38,67] compared to the other parameters, not as critical as it seems for further purification of ethyl ester
iii) or negative [40,48]. High temperatures are also propitious to and high yield could even be obtained even if phase separa-
the hydrolysis or saponification reactions that lead to tion is difficult.
cleavage of esters bonds [50]. This phenomenon at high
The water and free fatty acid contents have negative and
temperature is amplified by the presence of water.
synergistic effects on ethyl ester yields [9]. The water content in
the reaction medium must therefore be limited as much as
The temperature corresponding to optimum yield varies from
possible.
each system conditions and is usually fixed between 20 C and
80 C depending on the different studies and rarely exceeds the
ethanol boiling point (Table 1). This is also the case for reactions 4.6.1. Free fatty acid content
with methanol [30,85]. Free fatty acids (FFA) have a negative effect on ethyl ester yield
especially in homogeneous alkaline catalysis. FFA are contained in
4.4. Amount of catalyst vegetable oils and their presence is linked to i) oilseed storage, ii) oil
processing, or iii) oil storage [3]. The maximum free fatty acid
Along with molar ratio, catalyst amount is one of the factors that content recommended in oil for biodiesel production varies
most affects ethyl ester yield. The amount of catalyst can both considerably depending on the authors. According to Lam et al, the
maximum content varies between 0.5 wt% and 2.0 wt% [9], but In homogeneous acid catalysis, the water content is a more
Dorado et al. [99] claim that it can rise to 3.0 wt. More generally, the critical factor than in homogeneous alkaline catalysis [105]. This
acceptable maximum fatty acid content for biodiesel applications is may limit the applications for ethyl ester production with hydrated
fixed at around 2 mg KOH/g (i.e. approximately 1 wt%) [27]. bioethanol, as a water content of 0.5% implies yields below 90%
Refined oils generally contain less than 0.5 wt% free fatty acids. [105] and a water content of 5.0% totally inhibits the catalyst [91].
However, for frying oils, free fatty acid content can reach 15 wt% [9]. In heterogeneous catalysis, it is recognized that water can cause
In this case, it is necessary to pre-treat oils to neutralize free fatty catalyst inhibition or lixiviation. This phenomenon of lixiviation is
acids, so as not to sacrifice transesterification yield [21]. well known for methyl ester production and currently limits
Two major processes are used to neutralize oils with high free industrial applications [106] because water dissolves metal cations
fatty acid content. The first is a multiple-stage process [9,101] or active acid sites in the reaction medium, contaminating conse-
involving the esterification of free fatty acids in an acid medium, quently the final biodiesel [46,93,107]. Knowing that studies on the
followed by transesterification in an alkaline medium. The second effect of the water content on ethyl ester yield in heterogeneous
process, called deacidification by liquideliquid extraction (LLE), catalysis are very scarce [107], using hydrated bioethanol in
involves using an appropriate solvent, such as ethanol, to selec- heterogeneous catalysis therefore proves difficult and remains
tively extract free fatty acids from the oil. Deacidification can thus a challenge for researchers.
be combined with esterification in a single stage [102]. Finally, enzymatic catalysis seems to tolerate higher water
In homogeneous alkaline catalysis, the negative effect of free content than other processes. An optimum water content is needed
fatty acids on methyl ester yield was illustrated by Kwicien et al. to maximize lipases activity whilst minimizing the hydrolysis of
[103]. An increase in free fatty acid content from 0.45 wt% to triacylglycerides [94]. Because lipases are less inactivated by
over 6 wt% caused a drop in methyl ester yields, to the benefit of ethanol than by methanol [10,94] and tolerate water, they offer an
soap formation. Although such detailed works have not been interesting field of applications for ethyl ester production with
undertaken for ethyl esters, Encinar et al have shown however hydrated bioethanol.
that free fatty acids have similarly a negative effect on ethyl ester
yields as they do not exceed 74% with acid oils like used frying 5. Purification of ethyl esters
oils [83].
Homogeneous acid and enzymatic catalysts are less sensitive to Once the ethanolysis is complete, the ethyl ester phase has to be
the free fatty acid content than homogeneous alkaline ones, as they separated from the other contaminants and, first of all, from the
catalyse both esterification and transesterification. They are pref- glycerol phase. This separation is more difficult with ethyl esters
erable when using relatively acid oils, such as frying oils. than with methyl esters as usually one single pseudo-
homogeneous phase remains.
4.6.2. Water content
The water in the reaction medium during ethanolysis could be 5.1. Phase composition
as high as 5%, mostly coming from the bioethanol itself, or more
modestly from the vegetable oil. The water content is one of the After the ethanolysis, if the reaction parameters have been
main factors limiting ethyl ester [31] as well as methyl ester optimized, the reaction medium typically comprises two phases,
[9,23,24,77,98] yields and currently limit the use of 95% bioethanol which are usually separated by their density: i) an upper phase rich
at an industrial scale. The catalytic processes can tolerate water up in ethyl esters with a density of 880 kg/m3 and ii) a more polar
to a certain level that is highly variable, depending on the process. lower phase rich in glycerol with a density of 1050 kg/m3 [22]. The
Moreover, some strategies are being developed to limit the avail- glycerol-rich phase is clearly smaller in volume than the ester-rich
ability of water in the reaction medium, by using strong adsorbents phase. Zhou et al. [82] showed that this volume only amounts to 7%
or polar co-solvents [9]. of the total reaction volume when ethanol is used, whereas it
In homogeneous alkaline catalysis, water content is known to be amounts to 10% when methanol is used. The authors explain this
a very critical factor [18,23,24,77] although very little work has situation through the greater affinity of the glycerol-rich phase for
been undertaken to study its effect in the case of methanol, and the ethyl ester-rich phase than for the methyl ester-rich phase.
even less so in the case of bioethanol [41,78]. Water leads to The work by Cernoch et al. [40] led to the determination of the
secondary hydrolysis and saponification reactions which cause specific composition of the two phases after ethanolysis. They
a drop in yield and consume part of the catalyst. Although there are showed that typically i) ethyl esters and triacylglycerides are
no official specifications, several reviews mention a maximum mostly in the ethyl ester-rich phase and ii) glycerol and mono-
water content in the reaction medium of 0.1% for biodiesel appli- acylglycerides are mostly in the glycerol-rich phase. As for diac-
cations [10,13,16,98]. According to Ma et al. [18], the water content ylglycerides, they are equally distributed between the two phases
has a negative effect on methyl ester yield that is more critical than (Table 2).
the fatty acid content. This negative effect can be minimized To conclude, the upper “ester-rich” organic phase contains large
provided the reaction time is significantly increased [104], giving quantities of ethyl esters, but also some mono-, di-, and tri-
minimum secondary reactions and high methyl ester yields, even acylglycerides in decreasing order, glycerol, and residual ethanol.
for water contents ranging from 5% to 10%. This negligible water The lower glycerol-rich phase, for its part, is mainly composed of
content effect might be explained by the role played by water in
phase separation during purification. In the same way, water
proved to have a negative effect on ethyl ester yield as demon- Table 2
Typical compositions of ethyl ester phase and glycerol phase [40].
strated by Fillières et al. [41] who found that the use of 95% bio-
ethanol compared to 99.5% ethanol leads to a drastic reduction in Compound Ester phase Glycerol phase
yield from 95% to 30% with rapeseed oil, under the same operating Ethyl esters (wt%) >97 28e64
conditions. This negative effect can be minimized by introducing Triacylglycerides (wt%) 0.010e0.449 0.001e0.143
glycerol after the ethanolysis. Thus, a 8% water content leads to Diacylglycerides (wt%) 0.23e0.96 0.14e0.82
Monoacylglycerides (wt%) 0.50e0.94 3.34e5.77
a slight decrease in ethyl ester yield (from 97% to 96%) compared to Glycerol (wt%) 0.07e0.30 24e52
an anhydrous medium [78].
glycerol, then the excess ethanol, water, organic and inorganic salts reaction. Its separation plays a dual role in homogeneous catalysis:
(from the catalyst), a usually small quantity of esters, mono- a positive role as the by-product is eliminated from the system and
acylglycerides and some traces of di- and triacylglycerides. With the equilibrium is shifted to the right, a negative role as the catalyst
the use of alkaline metal hydroxides, vegetable colorings [108] give is highly soluble in the glycerol phase, which slows down the
a brown colour to this glycerol phase. The ethyl ester content can be reaction.
high in the glycerol phase if the amount of catalyst is too large or Several solutions were proposed for improving phase separa-
the ethanolysis temperature too high [40]. tion. The most obvious, as frequently mentioned in this review, is
a preventive solution that consists in optimizing the upstream
5.2. Factors affecting separation of the glycerol and ester phases reaction parameters to obtain a chemical composition conducive to
good phase separation [40]. Other curative solutions were also
According to Atadashi et al. [22], the main factors affecting the proposed by several authors if one single pseudo-homogeneous
separation of the phases are their chemical composition and the phase remains. They consist in treating the reaction medium
nature of the catalyst used. The particular difficulties linked to downstream by eliminating ethanol, by heating, by neutralizing
homogeneous alkaline catalysis will be discussed in this section as with acid and by adding glycerol. Decanting, which is routinely
it is the most common and most difficult in terms of phase sepa- carried out by simple gravity, can be facilitated by centrifugation.
ration due to the formation of emulsions. Bouaid et al. [62] mentioned that eliminating ethanol by evapora-
Ethyl ester production yields depend directly on effective tion under vacuum or distillation facilitates phase separation as
separation of the ester-rich and glycerol-rich phases [39] which can ethanol acts as a stabilizer. Phase separation can also be facilitated
properly be managed beforehand by optimizing reaction parame- at higher temperatures, at around 70 Ce80 C [39,40,78,113].
ters. In certain experiments, some researchers have found i) that it However, this needs to be rapid as the medium is once again con-
is very difficult to separate the phases at room temperature [30,67] verted into a single “pseudo-homogenous” phase after a few
even after 24 h’ decantation [64] ii) or even that the phases are minutes [40]. For better phase separation, some other authors
inversed. In reality, such phenomena are relatively frequent for recommend neutralizing the reaction medium with an acid, with
ethyl ester production. excess ethanol eliminated at a later stage [64]. Lastly, whilst not
Cernoch et al. [40] characterized the chemical composition of very economical, adding glycerol might prove to be a solution for
mixtures that were difficult to separate, forming a single gelatinous improving phase separation, while drying the reaction medium
“pseudo-homogeneous” phase. They showed that such mixtures [39,51,78,83].
are characterized by high concentrations of soaps, mono-
acylglycerides and diacylglycerides (Table 3). These compounds are 5.3. Crude ethyl ester purification methods
one of the main factors responsible for the formation of emulsions
in the reaction medium. In fact, as they possess both polar hydroxyl Purification of the reaction medium involves several stages
groups and apolar carbon chains, they are powerful surfactants and designed to isolate ethyl esters and eliminate the main contami-
emulsifiers [109] that can result in emulsions [40], or even an nants, namely mono-, di-, triacylglycerides, glycerol, ethanol, the
inversion of phases [110]. Zhou et al. [111] highlighted that the catalyst and soaps. Firstly, a large quantity of ethanol and glycerol
emulsions formed during biodiesel production with ethanol are has to be successively eliminated by evaporation and separation of
more stable than with methanol. In fact, a typical “ethyl esters” the phases. Next, treatments not specific to ethyl ester production
phase contains more diacylglycerides, monoacylglycerides, ethanol must be applied to eliminate residual contaminants. The literature
and glycerol than a typical “methyl esters” phase. reports three main types of treatment [17]: i) neutralization by
Although phase separation is primarily managed by the differ- water washing (or acidification), ii) dry washing, iii) membrane
ence in density, it also clearly depends on the chemical compo- extraction.
nents. First of all, the partial glycerides and soaps formed play
a major role, since they are responsible for emulsions. However, the 5.3.1. Water washing
existence of excess ethanol in the reaction medium may also cause Neutralizing by washing with water or slightly acidified water
phase separation difficulties. Excess ethanol, which is soluble in the [108] is the method most widely used to purify ethyl esters and
glycerol-rich phase, induces a drop in the latter’s density, eventu- biodiesel in general. It is the only method to give biodiesel with
ally leading to phase inversion. Such a situation can be avoided if characteristics meeting the requirements of international stan-
the composition of the reaction medium is far from the inversion dards [114]. Water washing consists in adding usually a quarter to
point that is specific to each reaction environment [112]. a half as much water as biodiesel [77]. Leung et al. [17] reported
In addition, the respective solubility of glycerol in ethyl esters separation of the aqueous phase and the ester phase either by
and of ethyl esters in glycerol is also a limiting factor for good phase decantation or centrifugation, but also on molecular sieves, or silica
separation [22]. Cernoch et al. [40] maintained that better ethyl gels. Elimination of the aqueous phase eliminates glycerol, the
ester yield necessarily depends on improving the affinity of ethyl catalyst, ethanol and residual soaps. During the successive washing
esters for the ester-rich phase rather than for the glycerol-rich operations, the aqueous phase becomes increasingly clearer and
phase. Work carried out by Zhou et al. [82,111] showed that sepa- the operation is repeated until a neutral pH is obtained.
ration of the glycerol-rich phase also influenced kinetics during the Stirring intensity during washing has a paramount effect on
biodiesel yield. If it is mild, three to four washing operations are
Table 3 required and biodiesel losses are under 10%. However, if stirring is
Concentration in mono-, di-, triacylglycerides and soaps of final reaction mixture of vigorous, a single washing operation is required, but biodiesel
easily, hardly separable and inseparable substances [40]. losses can reach 20% [86].
Substance Hardly and Easily Although water washing is effective in eliminating contami-
inseparable separable nants from biodiesel, it entails certain drawbacks. The large quan-
MG (% wt) 2.4e4.2 1.1e2.3 tity of wastewater generated increases costs and production times;
DG (% wt) 1.9e3.5 0.3e0.9 moreover the biodiesel also has to be dried. Furthermore, any
TG (% wt) 0.4e1.0 0.0e0.3 residual water can promote microbial growth in the biodiesel,
Soaps (% wt) 2.0e2.5 2.5e5.8
leading to the corrosion of storage tanks or engines, and causing the
formation of free fatty acids that are likely to polymerize [114,115]. However, ethyl esters must achieve minimum purity and fulfill
It is therefore essential to remove the water i) either by distilling international standards (Section 6.3) so as to still be classified as
the biodiesel [62], ii) or by adding drying agents such as anhydrous “biodiesel”.
sodium sulfate [17,113] or anhydrous magnesium sulfate and/or
oven drying at 107 C in a nitrogen stream [116]. 6.1. Ethyl ester fuel properties
5.3.2. Dry washing Biodiesel is a mixture of fatty acid esters. Its fuel properties are
Dry washing is an interesting alternative method, on a small influenced by the ester moiety derived from the alcohol (methyl/
scale, as no water is required. Adsorbents such as MagnesolÒ (a ethyl) but also by the structure of the fatty acid (degree of unsa-
commercial adsorbent composed of amorphous magnesium sili- turation and chain length) [119].
cate) or ion exchange resins are used to eliminate water, but also Ethyl esters can be characterized like other liquid fuels by
the other contaminants, from biodiesel [67,117]. One of the main numerous fuel properties: kinematic viscosity, density, heating
limitations of such adsorbents is their adsorbing capacity. It is value, cetane number, flash point, cloud point, pour point and
essential to have eliminated most of the residual alcohol during the oxidative stability. These fuel properties vary depending on the
earlier purification stages to avoid saturating the adsorbents. Ber- vegetable oil or fat used (Table 4). Compared to pure methyl
rios et al. [114] demonstrated that MagnesolÒ is more effective than esters and diesel fuel, pure ethyl esters present better fuel prop-
resins in eliminating residual alcohol. However, none of the prod- erties (Table 5) but they depend greatly on the purity r of the ethyl
ucts obtained meet the requirements of European standards. esters:
Moreover, it is difficult to recycle such a product which proves to be
poorly adapted to large-scale production processes [31]. 6.1.1. Kinematic viscosity
Fuel viscosity is a very important property because it impacts on
5.3.3. Membrane extraction both injection and combustion efficiency. High values of viscosity
Membrane extraction is a very promising method that effec- can induce poor fuel atomization, incomplete combustion, and
tively removes contaminants from biodiesel. This method consists carbon deposits on the injectors [83]. The kinematic viscosity of
in pumping biodiesel through a polysulfone [17] or ceramic [118] ethyl esters, from 2 to 6 mm2/s, is of the same order of magnitude as
type membrane. The membrane eliminates virtually all the glyc- that of diesel fuel. It is slightly greater than that of methyl esters due
erol from biodiesel, and all the more so the lower the ethanol to the greater molecular weight [83]. The higher the number of
content [118]. unsaturations and the shorter the carbon chain length, the lower
the ethyl esters viscosity [120]. Moreover, as shown by Cernoch
6. Ethyl ester characteristics and specifications et al, small contaminations of residual glycerides can greatly
increase ethyl ester viscosity [121].
Like other liquid fuels, ethyl esters are usually characterized by
their fuel properties. These fuel properties depend on the nature of 6.1.2. Higher heating value
the reactants used (alcohol and triacylglycerides) (see Section 6.1) Higher heating value (HHV) is an important property which
but also on the nature and contents of contaminants (Section 6.2). characterizes the energy content of a fuel. Ethyl esters have a higher
Table 4
Fuel properties of ethyl esters from various feedstocks.
Fuel property Kinematic Density HHV LHV Cetane Flash CFFP CP PP

viscosity (15 C) number point
(40 C)

Unit mm2/s kg/m3 MJ/kg MJ/kg e C C C C
Candlenut [63] 5.6 878 194 10
Cardoon [19] 3.4 870 40.0 49 188 3 6
Castor Oil [27,56] 4.6e17.4 912b919 151
Coconut [53] 2.6 880 51 112 5
Cotton [61] 5.2 877 40.6 52 175
Groundnut [19] 906 38.3 23
Jatropha [59,143] 4.0e5.5a 883e886 41.7 59 117e190 5
Linseed [45] 884 40.0 2 9
Mustard [48,62] 4.4e5.7 810e830
Olive [144] 38.2
Palm kernel [50] 4.8 883 40.6 37.3 167 6 2
Palm [51,52,142] 3.5a5.8 870e880 126e178 6e8 4e6
Radish [67] 5.0 872b 182e184 2
Rapeseed/canola 4.4 869e902 38.7e40.3 1 to 8 15 to 12
[19,44,45]
Soybean 4.4e4.9 876b925b 40.0 48 189e195 7 to 5 0e1 4 to 2
[19,29,31,38,60,124,144]
Sunflower [19,45,48,144] 4.6e4.9 850e873 38.6e39.7 49 187 1 8
Waste cooking oil 2.7e9.1 855e887 37.8e40.7 38e49 119e196 6 to 1 3 to 11 7 to 10
[83,88,89,144]
Tallow [124] 6.2 8 15 12
Grease [124] 6.0 0 3 9
HHV: Higher Heating Value; LHV: Lower Heating Value; CFPP: Cold Filter Plugging Point; CP: Cloud Point; PP: Pour Point.
a
Kinematic viscosity (30 C).
b
Density (20 C).
Table 5
Fuel properties of ethyl esters compared to methyl esters, crude oil and diesel fuel.
Fuel property Unit Oil [3,144,145] FAME [23e25,145] FAEE [19,27,31,38,44,45,50,51,53,59,61e Diesel fuel
63,67,69,83,89,124,142e144] [7,23e25,140]
Composition e TG C12eC22 FAME C12eC22 FAEE C12eC22 HC C10eC21
Kinematic viscosity (40 C) mm2/s 30e106 1.9e6.0 2.6e6.2 1.9e4.1
Density (15 C) kg/m3 915e940 860e894 810e919 750e850
HHV MJ/kg 37.5e40.6 39e41 38.2e41.7 43.0e46.5
LHV (NHV) MJ/kg 35.0e39.5 37.4e39.5 37.3e40.6 36.6e43.8
Cetane number e 35e45 48e65 48e59 40e55

Flash point C 240e330 100e170 112e196 60e80

Cloud Point C e 3 to 12 3 to 23 15 to 5

Pour Point C 1 to 31 15 to 10 15 to 12 35 to 15
TG: triacylglycerides; FAME: fatty acid methyl ester; FAEE: fatty acid ethyl ester; HC: hydrocarbons.
heating value of around 38e42 MJ/kg relatively close to that of methyl stability than methyl esters [125]. But they explained that these
esters although some publications mention slightly higher values for analytical results are not reliable as the standard method is not
ethyl esters [83] due to the additional C provided by ethanol [122]. The adapted, using material on a mass basis, not on a molar basis [125].
higher heating value of ethyl esters is around 10% lower than that of In another study on biodiesel of unrefined cottonseed oil, ethyl
diesel fuel (45 MJ/kg on average), due to its 11% oxygen content. esters proved to have better oxidative stability than that of methyl
Nevertheless, that oxygen content favors ignition [23]. The higher the esters due, in that specific case, to a higher gossypol content in the
chain length, the fewer the unsaturations, the higher the heating ethyl esters which acts as an antioxidant [60]. In fact, the oxidation
value [28]. Therefore, from the higher heating value point of view, stability of ethyl esters, as well as methyl esters, depends more on
long chain saturated triacylglycerides are more suitable. the polyunsaturated fatty acid contents than on the nature of the
acyl group (ethyl/methyl): it decreases with the increase of poly-
6.1.3. Cetane number unsaturated ethyl esters [123].
The cetane number is a parameter of fuel quality widely used to To conclude, ethyl esters have generally better fuel properties
characterize ignition delay and combustion quality for diesel than methyl esters, linked with the ethyl moiety. Moreover, these
engines. The higher the cetane number, the better the ignition fuel properties, which have different requirements, can be opti-
properties [123]. Ethyl esters have a cetane number of around mized by choosing the most suitable vegetable oil which contains i)
50e60 relatively close to those of methyl esters, although some large quantities of monounsaturated fatty acids, ii) small quantities
publications mention slightly higher values for ethyl esters [83] due of polyunsaturated fatty acids and iii) controlled quantities of
to the additional C provided by ethanol [122]. The cetane number of saturated fatty acids, for example almond, olive, corn, rapeseed or
ethyl esters depends on the feedstock used as well as for methyl high oleic sunflower oils [28].
esters. The longer and the more saturated the fatty acid carbon
chain, the higher the cetane number [123].
6.2. Effect of contaminants on ethyl ester uses and handling
6.1.4. Flash point
Ethyl esters have a higher flash point than that of diesel fuel According to standards, the presence of contaminants in bio-
which is safer for transport, storage and use [77] as described in diesel are restricted as they lead to severe operational problems
Section 6.2. The ethyl esters flash point is around the same value as when used in engines or during the storage and handling phases
that of methyl esters, between 100 and 200 C. It is higher than that [114]. In fact, to be classified as biodiesel, all methyl or ethyl esters
of diesel fuel, making ethyl esters less flammable than diesel fuel. must fulfill the standards (see Section 6.3 for details). The residual
This flash point can however be lowered by increasing ethanol contaminants that can be indifferently found in ethyl or in methyl
content [121]. esters are free fatty acids, residual glycerides, alcohol, water, metals
and glycerol which contents are linked with the purity of the
6.1.5. Low temperature properties (pour and cloud points) reactants, the nature of the catalysts, the synthesis and the purifi-
Low-temperatures properties of biodiesel are major issues for cation conditions. The impacts of these contaminants are found
temperate northern countries, but less a matter of concern for right along production and use processes:
southern countries. Cloud and pour points are usually used to
determine cold flow properties. The lower the cloud and pour i) During transport, with flammability problems in relation to
points, the better the cold flow properties. Compared to methyl a low flash point if the alcohol content is high.
esters, ethyl esters have improved low-temperatures properties ii) During storage, with i) flammability risks and ii) potential
[124] as they usually have a lower cloud point and pour point, corrosion of tanks when water and free fatty acid contents are
which improves cold start and storage [83]. Moreover, low high.
temperature properties of ethyl esters, as well as methyl esters, iii) For combustion, with the formation of deposits in the pres-
depend mostly on the degree of unsaturation of fatty acid. Reducing ence of metals or residual glycerides.
the saturated ester content can improve the cold flow properties of iv) For gas emissions, with the production of carcinogenic
ethyl esters [28]. substances such as acrolein when the glycerol content is too
high [114].
6.1.6. Oxidative stability
Oxidative stability is one of the major issues affecting the use of The medical study by Swanson et al. [126] concluded with
ethyl esters because of its content of polyunsaturated ethyl esters caution that, despite the presence of such contaminants, albeit in
[123]. Generalities about oxidative stability of ethyl esters small quantities, the exhaust emissions linked to biodiesel use are
compared to methyl esters cannot be drawn. In one study, Ramos less likely to present any risk to human health than those linked to
et al explained that ethyl esters are likely to have better oxidative diesel fuel use.
6.3. Ethyl ester specifications experience. Ethanol value specification in standards is the same as
for methanol in methyl esters. But the ethanol content needs
In order for ethyl esters to be usable as diesel fuel in engines, a specific test method that is currently under investigations for
their quality has to be guaranteed by standards that impose upper further adjustments in standard specifications [131]. Moreover,
limits on contaminant contents in biodiesels [115,127]. Today, with special attention should be paid to the specification of water
the exception of European standard EN 14214 [128] currently being content in ethyl esters because of the difficulty to dry bioethanol.
revised for October 2011, which specifically concerns methyl esters, The other analysis methods of the current biodiesel standards
the American standard ASTM D6751-09 [129] and the Brazilian seem to fit both for methyl or ethyl esters, only some limit values
standard ANP N 7/2008 [130] concern methyl esters or ethyl esters should be adjusted when more data and experience on the use and
indifferently [51]. The Indian BIS standard gives specifications handling of ethyl esters will be available. For example, the standard
adapted to the fuel characteristics of ethyl esters, with higher ranges 3.0e6.0 mm2/s proposed for the brazilian standard kine-
minimum values for the cetane number, flash point and viscosity matic viscosity seems to fit better to ethyl esters which have
than for methyl esters [53]. a higher innate kinematic viscosity. In the same way, the flash point
In these standards, a standardized analysis method is associated analysis limit value may need adjustments and may be more
with each fuel characteristic or each type of contaminant (Table 6). restrictive when using ethyl esters.
With a view to harmonizing standards linked to biodiesel
quality, a Europe-Brazil-USA tripartite panel of experts recently 6.4. Ethyl ester analysis methods
discussed draft joint specifications (Table 6) covering both methyl
and ethyl esters [131]. According to this panel of experts, some Many analysis methods were developed for determining bio-
standardized methods or values are problematic when switching diesel quality: by either quantifying the different biodiesel
methanol to ethanol in biodiesel production. This is the case for the compounds or by determining their fuel characteristics [115,127].
ethanol content in the ethyl esters for which, there is limited Most of the standardized analysis methods concern methyl esters
Table 6
Biodiesel specifications including methyl and ethyl esters proposed by standards [131].
Characteristics Unit Limit Brazil/USA/EU Method
ABNT NBR ASTM D EN/ISO

Aspect e LII Clear, impurity free e e e
(report analysis temperature)

Density at 20 C kg/m 3
850e900/e/860e900a 7148 1298 EN ISO 3675
14065 4052 e
EN ISO 12185
Kinematic Viscosity at 40 C mm2/s 3.0e6.0/1.9e6.0/3.5e5.0 10441 445 EN ISO 3104
Water Content, max. mg/kg 500/e/500 e 6304 EN ISO 12937
Total contamination, max. mg/kg 24/e/24 e e EN ISO 12662

Flash point, min. C 100/130/120 14598 93 EN ISO 3679
Water and sediment, max. %vol e/0.050/e e 2709 e
Ester Content, min % weight 96.5/e/96.5b 15342 e EN 14103
Carbon residue 100%, max % weight 0.05/0.05/0.30b 15586 4530 e
Sulfated ash, max. % weight 0.02/0.020/0.02b 6294 874 EN ISO 3987
Sulfur content, max. mg/kg 50/15(500)/10 e 5453 e
e EN ISO 20846
EN ISO 20884
(Na þ K) content, max. mg/kg 5/5/5 15554 UOP 391 EN 14108
15555 EN 14109
15553 EN 14538
15556
(Ca þ Mg) content, max. mg/kg 5/5/5 15553 UOP 389 EN 14538
15556
P content, max. mg/kg 10/10/10.0 15553 4951 EN 14107
Copper strip corrosion (3 h 50 C) max. e class 1/class 3/class 1 14359 130 EN ISO 2160
Cetane number min e Report/47/51 e 613/6890 EN ISO 5165

Cold Filter Plugging Point, max. C 19/report/national specification 14747 6371 EN 116
Acid number, max. mg KOH/g 0.50/0.50/0.50 14448 664 e
e e EN 14104
Free glycerol max. % weight 0.02/0.020/0.02b 15341 6584 e
e e EN 14105
e EN 14106
Total glycerol, max. % weight 0.25/0.240/0.25b 15344 6584 e
e e EN 14105
MG, DG, TG content max % weight Report/e/MG 0.80b; 15342 6584 e
DG 0.20b; TG 0.20b 15344 e
EN 14105
Methanol or ethanol, max. % weight 0.20/e/0.20b 15343 e EN 14110
Iodine value, max g/100 g Report/e/120 e e EN 14111
Oxidative stability (110 C), min. h 6/e/6 e e EN 14112
Linolenic acid methyl ester, max % mol e/e/12 e e EN 14103
Polyunsaturated (4 double bonds) % mol e/e/1 e e pr EN 14103
methyl esters, max
a
Density at 15 C.
b
% mol.
Table 7
Gas chromatography methods for determining residual glycerides and glycerol in ethyl esters.
Reference Analytes Oil type Calibration Column type Column Solvent Injection T det T oven Carrier Flow/
type dimensions gas Pressure
EN 14105 Silylated rapeseed, Internal apolar or 10e15 m0.32 mm heptane 1 mL on 380 C 50 C 1 min; He/H2 80 kPa
[133] FAME, GL, sunflower, 1,2,4- slightly polar 0.1 mm column 180 C 15 C/min;
MG, DG, soybean butanetriol; 230 C 7 C/min;
TG TG C10 370 C 10 C/min
ASTM GL, FAME, e slightly polar 10e15 m0.32 mm heptane 1 mL on 50 Ce370 Ce380 C
D6584 MG, DG, 0.1 mm column
[134] TG
[29] FAEE castor oil, Internal apolar VF- 2.2 m0.32 mm n-hexane 1 mL split 250 C 50 C 1 min; H2
soybean TG C8 1MS 15% 100:1 180 C 15 C/min;
C. Brunschwig et al. / Progress in Energy and Combustion Science 38 (2012) 283e301

240 C 230 C 7 C/min;
340 C 30 C/min
[57,58] FAEE cotton, Internal apolar DB-1 short 1 mL 150 Ce260 C H2
castor oil methyl 10 C/min
phtalate
[27] FAEE castor oil slightly polar 30 m0.25 mm e e e e e
0.25 mm
[40] FAEE, MG, rapeseed EN 14105 slightly polar ND e 1 mL on- 360 C 80 Ce350 C He 8.5 mL/min
DG, TG external VF-5 MS column (total)
MO, DO, TO WCOT fused 80 C
silica
[42,47] FAEE, MG, rapeseed Internal slightly polar 30 m0.32 mm n-heptane 0.5 mL split 340 C 80 C 1 min He
DG, TG octadecane VF-5HT 0.1 mm 10% 100:1
280 C
[30] FAEE castor oil Internal slightly polar 20 m0.18 mm 0.5 mL split 300 C 200 Ce310 C He
ethyl PE-5 0.25 mm 20:1 5 C/min
ricinoleate 290 C
[135] FAEE soybean Internal slightly polar 25 m0.32 mm heptane on column 380 C 50 C 1 min; He
FAEE, HP-5 0.1 mm 250 C 180 C 15 C/min;
squalene 230 C 7 C/min;
370 C 10 C/min
[30] FAEE soybean Internal slightly polar 30 m0.25 mm 0.5 mL split 300 C 200 C à 310 C He
MG C17/ DB-5 0.25 mm 20:1 5 C/min
DG C19 290 C
[59] FAEE/ Jatropha Internal slightly polar 5 m0.3 mm acetone 160 C; 230 C e
FAME curcas Ultra 2 0.53 mm 10 C/min;
330 C 30 C/min
[52] FAEE palm e polar BP-20 12 m0.25 mm split 260 C 10 Ce240 C e
100:1 10 C/min
250 C
[19] FAEE cardoon e polar BP-70 50 m0.22 mm hexane N2
[83] FAEE waste frying oil e polar PEG 50 m0.22 mm hexane 350 C 350 C 340 C N2 1 mL/min
(olive, 0.25 mm
sunflower)
[49] FAEE/ sunflower FAME/ polar acidified 25 m0.53 mm petroleum 3 mL e 180 C 2 min; He 5 mL/min
FAME FAEE mix PEG 1 mm ether 200 C 4
C/min
10 min
[64,136] FAEE/ coffee/ External polar acidified 25 m0.53 mm n-hexane 1 mL e 180 C 2 min, He 5 mL/min
FAME frying oil FAME mix PEG 1 mm 200 C 4
C/min
10 min
TG: triacylglycerides, DG: diacylglycerides, MG: monoacylglycerides, FAEE: fatty acid ethyl esters, FAME: fatty acid methyl esters.
297
but can be applied to ethyl esters. Such is the case, for example, Table 9
when determining the methanol content in methyl esters by GC- Estimated costs of biodiesel from different feedstocks.
FID EN14110 [132], which can be transposed to determine the Feedstock Main production Alkyl Cost
ethanol content in ethyl esters with few adjustments [129]. zone [23] esters (USD/L)
However, Cernoch et al. [40] highlighted the need to adapt Animal fats [24,98,140] e FAME 0.30e1.41
certain standardized analysis methods to ethyl esters, such as EN Rapeseed [24,98] EU, Canada FAME 0.32e0.69
Palm [140] Malaysia, Indonesia FAME 0.82e0.88
14105 [133] and ASTM D6584 [134] which use gas chromatography
Soybean [24,98,141] USA, Argentina, Brazil FAME 0.28e2.54
to quantify the glycerol and residual mono-, di- and triacylglyceride Sunflower [24] EU, tropical countries FAME 0.52
contents in methyl esters. In fact, those standardized methods are Castor oil [139] Brazil FAEE 0.92e1.56
suitable for biodiesel derived from vegetable oils such as sunflower, Diesel fuel [98] e e 0.67
rapeseed, soybean and palm and not suitable to biodiesel derived FAEE: fatty acid ethyl esters; FAME: fatty acid methyl ester.
from lauric acid oils such as coconut and palm kernel because of
peak overlapping of methyl esters and monoacylglycerides in GC
used (782.87 g/kWh) than when methyl esters are used (739.99 g/
analysis. Those limitations are even worse with ethyl esters,
kWh), but that CO2 comes entirely from renewable resources (oil
knowing that their overlapping zone with monoacylglycerides is
and bioethanol), and has no effect on the greenhouse effect.
wider than that of methyl esters with monoacylglycerides. As
Moreover, using ethyl esters helps to reduce NOx and CO emissions
a consequence, some adaptations of the analysis method are
and smoke density compared to methyl ester use [23,138] (Table 8).
needed either by changing the temperature gradient or by selecting
Lastly, ethyl esters also offer better biodegradability in aquatic
other more suitable GC stationary phases to better separate the
environment than methyl esters [138].
ethyl esters and monoacylglycerides.
All these modified methods proposed by different studies
6.5.2. Economic impact of biodiesel use
(Table 7) cover the use of gas chromatography to quantify ethyl
Today, the price of ethyl esters does not seem to be competitive
esters from two different angles. An initial analysis approach
with either the price of methyl esters or of diesel fuel. The fact that
consists in quantifying the classes of minor components (mono-,
only methyl ester production is carried out on an industrial scale
di-, triacylglycerides, and glycerol) and deducing from that the
primarily for cost reasons is already proof of that. Indeed, according
ethyl ester content, as recommended in the standards. To do that,
to the literature, the cost of methyl esters is lower than that of
the compounds are separated by whole classes on short apolar to
producing ethyl esters, mainly because methanol is cheaper than
slightly polar columns [40,42,47,133,134]. In fact, the quantification
bioethanol [72]. In fact, there is a serious lack of data concerning
of classes of compounds is necessary and sufficient for determining
ethyl esters production costs, except in Brazil where bioethanol is
whether biodiesel respects the specifications of the standards,
available in sufficient amounts to ensure a viable biodiesel
without the need to quantify individual compounds [115]. A second
production [139]. Moreover, the economic assessments of biodiesel
analysis approach consists in directly quantifying ethyl esters either
production available in the literature have been carried out i) in
on slightly polar columns [27,29,30,57e59,135], or on much more
various contexts with different oil and alcohol availability, ii) at
polar columns that are better adapted to within-class separation of
various production levels and iii) with various hypotheses (glyc-
compounds [19,44,49,51,52,64,65,83,136]. However, this analysis
erine purification, alcohol recovery) that lead to a wide range of
approach cannot be used to quantify residual glycerides or glycerol.
production costs which are listed in Table 9 [24,98,139e141].
For these two analysis approaches, internal calibration is mostly
Indeed, cost estimates for methyl ester production are highly
used to overcome fluctuations in sample concentrations, with
variable depending on the authors, ranging from 0.3 USD/L to over
highly variable standards depending on the bibliographical refer-
2.5 USD/L whereas ethyl ester production has been estimated at
ences: hydrocarbons [42,47,135], 1,2,4-butanetriol [133], glycerides
around 0.9e1.6 USD/L [139]. However, it is difficult to conclude
[29,30], or ethyl esters [30,133,135].
whether ethyl esters production costs are really higher than those
of methyl esters without a comparative study of methyl and ethyl
6.5. Environmental and economic impacts esters production in the same context. Lastly, as shown in many
studies [24,26], production costs of biodiesel are more driven by
6.5.1. Environmental impact vegetable oil prices (which amount to 70e80% of final biodiesel
Using ethyl esters as fuel offers environmental advantages, in price) than by alcohols prices. The cost of ethyl ester production will
comparison with diesel fuel use [137] but also, and especially, in only really be competitive in the short term with that of diesel fuel
comparison with methyl ester use [138]. Firstly, substituting diesel if oil prices come down substantially [73].
fuel with ethyl esters helps to reduce CO2 emissions by 782.26 g/
kWh [138]. This overall reduction in CO2 is estimated at 80% by
most of the publications [23], 10% of which occurs for combustion. 7. Overview
Thereafter, granted, CO2 production is greater when ethyl esters are
Through a literature analysis of all the work undertaken and
published on ethyl ester production, we have highlighted the
Table 8
Emissions of ethyl esters compared to diesel fuel and methyl esters. prospects for developing the process, along with the limitations
associated with several aspects: i) the transesterification reaction,
Emissions of ethyl esters Compared to diesel Compared to
ii) the purification stage, iii) the fuel characteristics of ethyl esters,
fuel [23,138,146] methyl esters [138]
iv) the environmental factors, v) the economic factors.
NOx (%) þ8 to þ23 2.0
CO (%) 48 to 4 1.5
An overview of this work reveals that the main development
HC (%) 67 to 45 þ21.0 prospects for the ethyl esters production and use compared to the
Smoke density (%) 73 4.2 methyl ester production depend on the following points:
Particulate matter (%) 69 to 47 NS
CO2 (g/kWh from fossil resources) 782.87 0.61
i) Use of ethanol may be safer and less toxic than methanol.
NS: Not specified. ii) Improved low-temperature properties of ethyl esters.
iii) Less environmental impact of ethyl esters production due to should be paid to them for future work on ethyl ester
local availability of bioethanol, its renewability, the reduction production.
in exhaust gas emissions, and better biodegradability of ethyl
esters.
iv) Low raw material import and transport costs, enabling
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Progress in Energy and Combustion Science 38 (2012) 283e301

Contents lists available at SciVerse ScienceDirect

Progress in Energy and Combustion Science

Use of bioethanol for biodiesel production

3.2. Heterogeneous catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

1. Introduction To avoid adapting vehicle engines, one alternative consists in

triacylglycerides alcohol alkyl esters glycerol

ND: not determined.

3.1. Homogeneous catalysis mechanism of homogeneous alkaline catalysis of ethanolysis is

step 1 ROH + B- RO- + BH

Fuel property Kinematic Density HHV LHV Cetane Flash CFFP CP PP

Characteristics Unit Limit Brazil/USA/EU Method

ABNT NBR ASTM D EN/ISO

C. Brunschwig et al. / Progress in Energy and Combustion Science 38 (2012) 283e301

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