Eur. J. Lipid Sci. Technol.

2011, 113, 1533–1540 1533

Research Article
Synthesis and characterization of mono-acylglycerols
through the glycerolysis of methyl esters obtained from
linseed oil

Gracélie A. S. Schulz, Kelly C. da Silveira, Daniela B. Libardi, Maria do Carmo R. Peralba

and Dimitrios Samios

Centre for Fuels Biofuels Lubricants and Oils - CECOM, Institute of Chemistry, Universidade Federal do Rio
Grande do Sul, Av. Bento Gonçalves, Porto Alegre, Brazil

Here we investigate the production and characterization of mono-acylglycerols through the glycerolysis
of biodiesel, a methyl ester mixture, obtained from linseed oil. The biodiesel employed was derived from
linseed oil through transesterification according to transesterification double step process [1]. The
efficiency of H2SO4, CaO, and NaOH as catalysts was evaluated for the production of mono-
acylglycerols. The glycerolysis reactions were performed by varying the molar ratio of the reagents
(biodiesel:glycerol), the type and amount of catalyst, reaction time and temperature. Systematic
evaluation of reaction yield is shown as a function of these parameters. Reaction products were
characterized through IR spectroscopy, hydrogen NMR, and the GC techniques. The study of three
different catalysts indicated that the most efficient was 5% NaOH in a 1:5 biodiesel–glycerol molar ratio
with 10 h reaction time. The reaction reached a maximum of 85% biodiesel conversion with a mono-
acylglycerol yield of 72% at 1308C.

Keywords: Biodiesel / Glycerolysis of biodiesel / Linseed oil / Mono-acylglycerols / Transesterification

Received: February 21, 2011 / Revised: August 9, 2011 / Accepted: August 26, 2011
DOI: 10.1002/ejlt.201100079

1 Introduction crop [2]. The production of biodiesel by transesterification is

Biodiesel is a biodegradable non-toxic fuel derived from
renewable sources. This fuel is a mixture of fatty acid alkyl
esters obtained by transesterification of tri-acylglycerol or
esterification of fatty acids with low molecular mass alcohols
[1]. Biodiesel is produced from animal fats or vegetable oils,
which can be obtained from various raw materials such as
castor oil, palm oil (palm), sunflower oil, babaçu oil, peanuts,
jatropha, and soybeans among others. Vegetable oils contain
a wide variety of tri-acylglycerols. The exact composition of
vegetable oils strongly depends on the characteristics of each
Correspondence: Professor Dimitrios Samios, Centre for Fuels Biofuels
Lubricants and Oils - CECOM, Institute of Chemistry, Universidade Federal
do Rio Grande do Sul, Av. Bento Gonçalves, 9500, P. O. Box 15003, Porto
Alegre 91501-970 RS, Brazil
E-mail: dsamios@iq.ufrgs.br
Fax: þ55 5133087304
Abbreviations: CBD, biodiesel mass conversion; GC, gas
chromatography; 1H NMR, hydrogen nuclear magnetic resonance; IR,
infrared spectroscopy; ME, methyl ester; TDSP, transesterification
double step process
the subject of several review articles [3–9] in which details of
catalysis and new catalysts are discussed.
In general, transesterification can be catalyzed both by
acids and bases [1, 10]. However, the reaction catalyzed by
bases using sodium or potassium hydroxides or alkoxides can
be carried out at temperatures near alcohol boiling point and is
faster than the transesterification catalyzed by acids [10, 11].
The transesterification double step process (TDSP) [1]
mechanism, recently proposed, uses a two-step procedure
including a KOH base catalysis followed by an acid catalysis
with H2SO4. This procedure is a high-yield and efficient
methodology for the production of excellent quality biodiesel.
The industrial production of biodiesel [12] is accompanied
by a large amount of glycerin as a by-product. Therefore,
the development of uses of this glycerin surplus is required
[9, 13]. The biodiesel glycerolysis, aiming the production of
mono-acylglycerols, constitutes one of the possible routes for
glycerol consumption.
Different routes are available for production of mono-
acylglycerol [10, 11] using vegetable oils and fats as starting
products. The first one is the transesterification of vegetable
oils or animal fats with glycerol, catalyzed by a base at
elevated temperatures such as 2558C [14]. In this case the

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1534 G. A. S. Schulz et al.
transesterification of tri-acylglycerols does not occur in a
single step but with tri-acylglycerols quickly turning into
di-acylglycerols and finally yielding mono-acylglycerols.
The second route is through esterification of fatty acids
with glycerol catalyzed by acids such as sulfuric acid and
p-toluenesulfonic acid [2]. The third one is the hydrolysis
in the presence of strong acids [4]. Normally, since the three
hydroxyl groups of glycerol have similar reactivity, a mixture
of mono-, di-, and tri-acylglycerols is obtained when either
basic or acidic catalysts are employed. Studies show that the
mono-acylglycerols can also be obtained using different proc-
esses including homogeneous and heterogeneous acidic and
basic [15, 16] catalysis with new catalysts such as lipases and
ion exchange resins [17–20]. There is a small number of
studies on biodiesel glycerolysis [21–28] and relatively low-
temperature processes are still to be explored. The interest
in the production of mono-acylglycerols arises from the
formation of huge amounts of glycerin during biodiesel
production and from the economical importance of mono-
acylglycerols.
There are two main driving forces defining the character
of this work. The first one is related to the environmental
questions raised by the glycerol surplus from the biodiesel
production and the second one concerns the importance of
mono-acylglycerols in the areas of construction (including
solvents, paints, coatings, and resins), food, beverage, and
pharmaceutical [29–31] industries. This study aims to evalu-
ate the chemical viability of the biodiesel glycerolysis process.
2 Materials and methods
2.1 Materials
The biodiesel used in the glycerolysis reaction, presenting
99.0% methyl ester, was produced according to the TDSP
[1]. Chemicals were purchased as follows: purified linseed oil
and double-distilled glycerin with 99.0% purity from
Farmaquimica-Brazil; methanol and H2SO4 from FMaia-
Brazil, KOH 85%, NaOH, CaO, and n-heptane from
Synth-Brazil; anhydrous sodium sulfate and cyclohexane from
Nuclear-Brazil; deuterated acetone and hexane 99.3% from
Tedia-Brazil; and He 99.99% from White Martins-Brazil.
The internal standard for GC measurements tricaprin
(1,2,3-tricaproylglycerol), the external standards (monoo-
lein, diolein and triolein), and the derivatives N-methyl-N-
(trimethylsilyl) trifluoroacetamide were purchased from
Sigma–Aldrich with 99.9% purity.
2.2 Characterization techniques
The 1H NMR analyses were performed in a Varian INOVA
instrument operating at 300 MHz. Samples were prepared
using 15 mg of product dissolved in deuterated acetone.
The IR spectroscopy was carried out in a Varian model
640-IR Spectrometer with a resolution of 4 cm
1. Thin film
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Eur. J. Lipid Sci. Technol. 2011, 113, 1533–1540
samples were used for qualitative IR investigation using KBr
plates.
The analysis of the glycerolysis products was carried
out by GC using the standard technique EN 14105. A
Shimadzu GC-2010 chromatograph equipped with on-
column injector, FID detector, and a DB1-HT column
(25 m  0.32 mm  0.1 mm) was used. Chromatographic
conditions were: detector temperature 3908C; injector
temperature: 608C during 1 min, 208C/min until 3808C,
remaining isothermally for 20 min. The oven temperature
program was: 608C during 1 min, 158C/min until 1808C,
78C/min until 2308C, and 108C/min until 3708C, remaining
isothermally for 12 min. Three solutions were used for quan-
titative analysis of glycerolysis products: a standard solution,
a solution containing the biodiesel (with the biodiesel used
in the reaction), and a solution containing the products
(solution with glycerolysis products). The standard solution
was prepared by mixing 10 mL of linolenic acid methyl ester,
100 mL of tricaprin, 250 mL of monoolein, 100 mL of
diolein, 80 mL of triolein, 8 mL of n-heptane, and 100 mL
of N-methyl-N-(trimethylsilyl) trifluoroacetamide (derivative
reagent). The solutions for analyzing biodiesel were com-
posed by a mixture of 10 mg of biodiesel, 100 mL of tricaprin,
8 mL of n-heptane, and 100 mL of N-methyl-N-(trimethyl-
silyl) trifluoroacetamide. The solutions for analyzing
products were composed of 10 mg of the obtained product,
100 mL of tricaprin, 8 mL of n-heptane, and 100 mL of
N-methyl-N-(trimethylsilyl) trifluoroacetamide. Aliquots of
0.5 mL of these solutions were injected.
2.3 Reaction procedure
2.3.1 Transesterification reaction: Production of
linseed oil biodiesel
The transesterification reaction to obtain methyl-esters from
linseed oil was performed in two steps. The first stage con-
sisted of basic catalysis using catalyst KOH followed by acid
catalysis with H2SO4.
Initially, the alkali KOH was dissolved in methanol (25 g
KOH in 1 L methanol) at a temperature near 458C for the
formation of methoxide (conjugated base). A volume of
200 mL of purified linseed oil together with 80 mL meth-
oxide was placed in a simple reactor equipped with a reflux
device. The solution with the active species was added to the
fatty acid with vigorous and constant agitation. The tempera-
ture was gradually increased approximately to 688C, which is
near the boiling point of methanol, and refluxed for 1 h. After
the basic catalysis step, the system was cooled to 258C and
two phases were formed. The less dense phase with clear
color includes the biodiesel, while the denser phase, with a
dark color, contains the glycerol surplus. The second step of
the TDSP procedure started after the separation of the
previous phases. Immediately after the separation, 60 mL
methanol and 1.5 mL sulfuric acid 18 mol/L, were added
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Eur. J. Lipid Sci. Technol. 2011, 113, 1533–1540 Mono-acylglycerols obtained from glycerolysis of biodiesel 1535

to the less dense phase with mild heating until 688C. Then,
the system remained at reflux for 1 h. Finally, after the period
of acid reaction, the system was again cooled naturally and
the formation of two phases occurred. As before, the upper
phase contained biodiesel, while the lower one consisted of
glycerol, alcohol, water, catalyst, and traces of other byprod-
ucts. In order to separate the alcohol the biodiesel phase was
washed with ice water and the residual alcohol removed by
vacuum evaporation. Small traces of water were removed
using anhydrous sodium sulfate followed by filtration. The
final product was high-purity biodiesel (99%) as analyzed by
1
H NMR.
The tests conducted at temperatures of 40, 60, 70, and
908C with different biodiesel:glycerol ratios and concen-
trations of the three catalysts did not produce promising
results. In other words, the conversion of biodiesel to
mono-acylglycerols was less than 1% or not detectable by
GC. Considering the thermodegradability of the reactants, a
systematic study was conducted at 1308C, a temperature
where biodiesel and glycerol are thermo-resistant in the pres-
ence of air. Tables 1–3 present the yields in mono-acylgly-
cerols for H2SO4, CaO, and NaOH and the respective
conditions, namely the biodiesel to glycerol ratio, the reaction
time, and the catalyst concentration.

2.3.2 Glycerolysis reaction: Production of 3 Results and discussion

acylglycerols
In this study a series of reaction tests were performed, includ-
ing different reactant compositions, two basic and one acid
catalyst with different concentrations and different tempera-
tures in the range between 40 and 1308C.
The reactions were performed in an open reactor system
with stirring and heating using a thermally controlled silicone
bath. The linseed biodiesel, the glycerin, and the catalyst were
mixed using excess of glycerin in order to shift the equilibrium
to a greater production of mono-acylglycerols. The biodie-
sel:glycerol ratio is given in Table 1. After the glycerolysis
reaction, the product was mixed with cyclohexane in order to
separate the glycerol. The mixture with cyclohexane pre-
sented two phases. The denser phase includes mainly the
glycerol, while the less dense phase is mainly composed by
acylglycerols and traces of biodiesel. This phase was carefully
separated and the cyclohexane was eliminated by vacuum
evaporation. The purification procedure was repeated at least
three times and the products were analyzed with no further
treatment. The 1H NMR, IR, and GC techniques were used
for product analysis.
3.1 The transesterification process
It was demonstrated that the TDSP enables to achieve sig-
nificant conversion of vegetable oils into methyl esters using
basic catalysis followed by acidic catalysis. The quality of the
biodiesel used in this study, was tested according to standard
methods [1]. The mixture of methyl esters produced was
used as a starting reagent for the production of mono-
acylglycerols in the proposed glycerolysis reaction.
3.2 The glycerolysis process
The glycerolysis of biodiesel is one promising important
method [32] offering great potential for production of pure
and good mono-acylglycerols quality. The proposed reaction
(Fig. 1) is reversible. The biodiesel glycerolysis reaction is
performed with an excess of glycerol in order to shift thermo-
dynamic equilibrium towards the formation of mono-acyl-
glycerols. Following the formation of mono-acylglycerols,
occurs the production of di- and tri-acylglycerols. The tests

Table 1. Synthesis of mono-acylglycerols at 1308C using H2SO4 as catalyst with the yield determined by GC analysis

Biodiesel: Biodiesel Yield Yield Yield

Catalyst glycerol ratio Time conversion mono-acylglycerols di-acylglycerols tri-acylglycerols
(w/w%) (w/w%) (h) (%) (%) (%) (%)

0.5 1:5 0.5 – – – –

0.5 1:5 2 – – – –
0.5 1:5 4 – – – –
0.5 1:5 5 – – – –
1 1:3 4 – – – –
1 1:4 6 5  0.7 4  0.5 – –
1 1:5 15 5  0.6 3  0.5 – –
5 1:5 2 7  0.6 5  0.5 2  0.7 –
5 1:5 4 14  0.5 12  0.4 2  0.6 –
5 1:5 6 14  0.6 11  0.5 3  0.6 –
5 1:5 10 14  0.5 10  0.5 2  0.6 2  0.6
5 1:5 15 14  0.5 8  0.5 3  0.5 3  0.5

Observation: (–) concentration lower than 1%.

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1536 G. A. S. Schulz et al. Eur. J. Lipid Sci. Technol. 2011, 113, 1533–1540

Table 2. Synthesis of mono-acylglycerols at 1308C using CaO as catalyst with the yield determined by GC analysis

Biodiesel: Biodiesel Yield Yield Yield

Catalyst glycerol ratio Time conversion mono-acylglycerols di-acylglycerols tri-acylglycerols
(w/w%) (w/w%) (h) (%) (%) (%) (%)

0.5 1:5 0.5 – – – –

0.5 1:5 2 – – – –
0.5 1:5 4 – – – –
1 1:4 4 – – – –
1 1:3 4 – – – –
1 1:5 6 10  0.6 9  0.6 1  0.6 –
1 1:5 15 13  0.6 11  0.5 2  0.7 –
5 1:5 2 51  0.5 23  0.5 26  0.5 2  0.7
5 1:5 4 71  0.4 39  0.5 28  0.5 4  0.6
5 1:5 6 72  0.5 39  0.4 27  0.5 5  0.6
5 1:5 10 72  0.4 42  0.5 24  0.5 6  0.6
5 1:5 15 76  0.4 48  0.4 22  0.6 6  0.5
5 1:6 6 17  0.5 14  0.6 2  0.6 1  0.7

Observation: (–) concentration lower than 1%.

were conducted using an excess of glycerin according to the
acid route with sulfuric acid as the catalyst and the basic route
with calcium oxide and sodium hydroxide.
Reactions were conducted at a lower temperature
(T ¼ 1308C) when compared to vegetable oil glycerolysis
(T ¼ 250–2608C) [14]. Further, the use of methyl esters
allows final product to be separated by fractional distillation,
which is easier than separating the products of tri-acylglycerol
glycerolysis [32].
In Tables 1–3 the reactions tests with H2SO4, CaO, and
NaOH, respectively, are shown. According to these tables a
large amount of mono-acylglycerol was produced together
with a small amount of di-acylglycerols and a not significant
production of tri-acylglycerols. A simple comparison of these
data indicates that the highest value of biodiesel conversion is
that from the experiment with 5% NaOH, glycerol:biodiesel
ratio equals to 5 and reaction time of 10 h.
The product obtained was evaluated by IR to confirm the
formation of mono-acylglycerols (Fig. 2) through the charac-
teristic bands according to Bakare et al. [32].
The spectrum showed in Fig. 2 confirms the formation
of mono-acylglycerol by the presence of vibration bands

Table 3. Synthesis of mono-acylglycerols at 1308C using NaOH as catalyst with the yield determined by GC analysis

Biodiesel: glycerol Biodiesel Yield Yield Yield

Catalyst ratio Time conversion mono-acylglycerols di-acylglycerols tri-acylglycerols
(w/w%) (w/w%) (h) (%) (%) (%) (%)

0.1 1:5 0.5 – – – –

0.2 1:5 0.5 – – – –
0.5 1:5 0.5 – – – –
0.5 1:5 2 – – – –
0.5 1:5 4 – – – –
1 1:4 4 – – – –
1 1:3 4 – – – –
1 1:5 6 11  0.6 6  0.6 3  0.5 2  0.6
1 1:5 15 25  0.5 18  0.5 5  0.4 2  0.7
5 1:5 2 8  0.6 7  0.6 – –
5 1:5 4 84  0.4 65  0.5 19  0.5 –
5 1:5 6 85  0.4 69  0.5 16  0.5 –
5 1:5 10 85  0.5 72  0.4 13  0.6 –
5 1:5 15 85  0.4 68  0.6 13  0.5 4  0.6
5 1:6 6 42  0.5 35  0.4 5  0.7 2  0.6

Observation: (–) concentration lower than 1%.

The bold was used to highlight the best result obtained in the synthesis of monoglyceride.

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Eur. J. Lipid Sci. Technol. 2011, 113, 1533–1540
Figure 1. Scheme of the methyl esters glycerolysis reaction.
3370–3470 (O–H), 3009 (C–H, unsaturation), 2924 (C–H,
saturation), 1747 (C –– O), 1249 and 1165 (C–O–C), and
1655 cm
1 (CH –– CH). The spectrum has a broad absorption
peak and a higher absorbance ratio between OH (3450 cm
1)
and CH2 (2960 cm
1) with a high proportion of hydroxyls,
indicating the presence of mono-acylglycerols.
The formation of MAGs as shown by 1H NMR is
depicted in Fig. 3.
The peak at 5.30–5.54 ppm is characteristic of double
bond hydrogens (g). A small signal (b) included in this area is
originated from the central glycerol hydrogen. The peak
appearance (a and k) in the region between 3.46 and
4.22 ppm [32] is characteristic of the mono-acylglycerols
formation. The occurrence of a partial reaction was checked
by looking for the sharp peak at 3.67 ppm, characteristic of
biodiesel. The hydrogen (h) of conjugated double bonds
appears at the peak around 2.85 ppm. The sharp peak in
this area (2.83 ppm) is characteristic of water remained in the
sample analyzed in deuterated acetone. The broad peak at
2.30 ppm represents the hydrogen (c) of CH2 attached to the
carboxylic group of the biodiesel chain. Still, Fig. 3 shows that
the chain of the fatty acid is maintained in the initial region of
the spectrum between 0.88 and 2.20 ppm indicating the
hydrogens (d, e, and f) and the terminal groups (i) omega
three and non-omega three.
GC was used for the analysis of all obtained products.
1
Figure 3. H NMR spectrum of the product obtained with 72% yield of mono-acylglycerol at 1308C using NaOH as catalyst shown in Table 3.
ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Mono-acylglycerols obtained from glycerolysis of biodiesel 1537
Figure 2. IR spectrum of the product obtained with 72% yield of
mono-acylglycerol at 1308C using NaOH as catalyst shown in
Table 3.
Figure 4 includes three chromatograms which permit the
quantification of the glycerolysis products. The comparison of
the respective chromatograms defines the methodology for the
evaluation of the biodiesel conversion and the respective acyl-
glycerols yield. All three chromatograms include internal stand-
ard tricaprin at the same concentration. The chromatogram A
is the one composed with the external standards linolenic acid
methyl ester, monoolein, diolein, and triolein including the
internal standard tricaprin. The chromatogram B is the bio-
diesel before reaction including internal standard tricaprin. The
chromatogram C is the sample prepared with the product
obtained in the test using 5% NaOH, biodiesel:glycerol 1:5
ratio and 10 h time. According to chromatogram A, the lino-
lenic acid methyl ester (a) appears in 10.4 min retention time.
The biodiesel used (chromatogram B) includes a mixture of
C16 and different C18 methyl esters (a1, a2, a3) with retention
times between 9 and 13 min. These peeks (a1, a2, a3) appear in
the chromatogram C as residual biodiesel. Mono-acylglycerols
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1538 G. A. S. Schulz et al.
Figure 4. Chromatograms of samples analyzed: 1 – sample of the
product obtained with 72% yield of mono-acylglycerol (Table 3) and
internal standard tricaprin; 2 – sample of external and internal stan-
dards mix (nonoolein, diolein, triolein, and tricaprin); and 3 – sample
of pure biodiesel before the reaction.
(b1, b2) appear in chromatogram A in the range between 14
and 17 min. Small amounts of mono-acylglycerols (b1, b2) are
present in chromatogram B and a significant increase is
observed in chromatogram C. The presence of tricaprin (c1,
c2, c3) in all three chromatograms ensures the accuracy of the
retention times. In chromatogram A diolein appears (d) after
25 min and as it can be seen there are no traces of di-
acylglycerols in biodiesel and a small quantity is detected in
chromatogram C. The triolein (e) is detected in chromatogram
A after 31 min but tri-acylglycerols are not present in the used
biodiesel or the analyzed sample. In order to evaluate quanti-
tatively the obtained products the chromatography response
factors (rF) of the involved species have to be considered.
Using the results of biodiesel before the reaction and that
of the products, one can obtain the biodiesel mass conversion
(CBD), according to Eq. (1):


1
SAES
CBD ¼  100
SAEBD
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Eur. J. Lipid Sci. Technol. 2011, 113, 1533–1540
P
In this equation, AEBD is the summation of the peak areas
corresponding P to methyl esters of the biodiesel before the
reaction, and AES is the summation of the peak areas
corresponding to methyl esters in the sample after the reac-
tion. The mono-, di-, and tri-acylglycerol yield (%) must be
expressed in relation to the CBD.
The mono-, di-, and tri-acylglycerol yield (%) (YMG,
YDG, and YTG, respectively) were calculated according to
Eqs. (2–4):
CBD  ðSAMG =rFMG Þ
YMG ð%Þ ¼
½ðSAMG =rFMG Þ þ ðSADG =rFDG Þ þ ðSATG =rFTG Þ
(2)
CBD  ðSADG =rFDG Þ
YDG ð%Þ ¼
½ðSAMG =rFMG Þ þ ðSADG =rFDG Þ þ ðSATG =rFTG Þ
(3)
CBD  ðSATG =rFTG Þ
YTG ð%Þ ¼
½ðSAMG =rFMG Þ þ ðSADG =rFDG Þ þ ðSATG =rFTG Þ
(4)
In these equations, AMG, ADG, and ATG are the respective
areas. The corresponding response factors are given by rF.
The respective yield (%) values of the mono-, di-, and tri-
acylglycerols, for H2SO4, CaO, and NaOH, are given in the
Tables 1–3, respectively.
According to the obtained results and having in mind
that the aim of the study is to establish the optimum
conditions for mono-acylglycerol production, in other
words maximum yield in mono-acylglyrerol, one observes
that tests with biodiesel:glycerol ratios less than 1:5 were
not efficient. Increasing the ratio to 1:6, result in a decrease
in the production of mono-acylglycerols. Additionally
very small amounts of catalyst and small reaction times
are not favorable to the production of mono-acylglycerols
at temperatures around 1308C and working with a
greater reaction time, the mono-acylglyceride yield decreased
from 72 to 68% as showed in the case of NaOH catalyst
(Table 3).
The results in Tables 1–3 are graphically summarized in
Fig. 5, where the yields of mono-, di-, and tri-acylglycerols
and the (1
X) parameter, where X is the biodiesel con-
version, are presented as function of time, for the
catalysts H2SO4 (Fig. 5a), CaO (Fig. 5b), and NaOH
(Fig. 5c). In Fig. 5d all mono-acylglycerol yield values for
the experiments with different reaction times are presented
versus the respective biodiesel conversion. The graphical
comparison demonstrated that the most efficient catalyst
was NaOH followed by CaO, having the former higher
specificity resulting 72% of mono-acylglycerols. These
results demonstrated the viability of producing mono-
(1) acylglycerols using relatively low temperature biodiesel
glycerolysis. The question of activity and selectivity of
the catalysts is still open. However, a kinetic study of the
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Eur. J. Lipid Sci. Technol. 2011, 113, 1533–1540
Figure 5. Overview of the biodiesel glycerolysis by H2SO4 (a), CaO (b), and NaOH (c): biodiesel conversion (&) and yield of the mono- ( ),
di- (*), and tri-acylglycerols (~) versus time. Yield of mono-acylglycerols versus biodiesel conversion (d) using NaOH (*), CaO ( ),
and H2SO4 (~) after 10 h reaction time.
biodiesel glycerolysis with the three different catalysts would
provide more details in relation to activity and selectivity of
these systems.
4 Conclusions
The biodiesel glycerolysis reaction was presented as an
alternative for the production of mono-acylglycerol synthesis.
High-purity biodiesel methyl esters obtained by the TDSP
method were used and different acidic (H2SO4) and basic
catalysts (CaO, and NaOH) were tested.
With respect to the catalysts, it is demonstrated that the
most efficient one was the NaOH followed by CaO. It was
confirmed that NaOH, compared to the other two catalysts,
presents high specificity with a yield of 72% of mono-acyl-
glycerols. The most efficient molar ratio biodiesel/glycerol
was 1/5.
In addition, the system used in the synthesis of mono-
acylglycerols presents certain gains in terms of the simplicity
of the reaction performed under mild conditions of tempera-
ture with lower reaction times using an open reactor system
without the need of an inert atmosphere or high tempera-
ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Mono-acylglycerols obtained from glycerolysis of biodiesel 1539


tures. This report highlights the possibility of efficient use of
glycerol with biodiesel in the synthesis of mono-acylglycerols,
as these products are still of great importance for several
industrial sectors like the food, pharmaceutical, and paint
industries.
The authors gratefully acknowledge the ‘‘Conselho Nacional de
Desenvolvimento Cientı́fico e Tecnológico’’ CNPq and FINEP
Brasil for financial support.
The authors have declared no conflict of interest.
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