C. R. Acad. Sci.

Paris, Série IIc, Chimie / Chemistry 3 (2000) 589 – 594

© 2000 Académie des sciences / Éditions scientifiques et médicales Elsevier SAS. All rights reserved
S1387-1609(00)01171-3/FLA

Surface chemistry and catalysis / Chimie des surfaces et catalyse

Synthesis of glycerol monooctadecanoate from

octadecanoic acid and glycerol. Influence of
solvent on the catalytic properties of basic oxides
Yannick Pouilloux*, Sébastien Métayer, Joël Barrault

Laboratoire de catalyse en chimie organique, UMR 6503, ESIP, 40, av. du Recteur-Pineau, 86022 Poitiers cedex, France

Received 11 April 2000, accepted 6 September 2000

Communicated by François Mathey

Abstract – The preparation of monoglycerides can be carried out in the presence of acid or basic catalysts. The use of basic

Nouvelles matières premières

catalysts could limit secondary reactions leading to product degradation. A comparison of solid basic catalysts (MgO, ZnO,
Na2CO3) has shown that zinc oxide is one of the best catalysts in the esterification of glycerol with stearic acid (octadecanoic
acid) since the usual bases favor soap formation (saponification). Moreover, the use of a well chosen solvent increases the

Alternative feedstocks
activity and the monoglyceride selectivity of zinc oxide due to the homogenisation of the reaction mixture and the limitation
of the thermal reaction. Finally these results show that the esterification rate is strongly dependent on both the catalyst and
on the solubility–solvation of reagents and products. © 2000 Académie des sciences / Éditions scientifiques et médicales
Elsevier SAS

glycerol esterification / monoglyceride / zinc oxide / stearic acid

Version française abrégée — Préparation de monooctanoate de glycérol à partir d’acide octadécanoı̈que et de

glycérol. Influence du solvant sur les propriétes catalytiques d’oxydes basiques. L’objectif principal de cette étude est
la préparation de monoester de glycérol à partir de glycérol et d’acides gras issus de la transformation des huiles végétales,
en utilisant des oxydes basiques comme catalyseurs. De par leurs propriétés physico-chimiques, les monoglycérides trouvent
de nombreuses applications dans l’industrie pharmaceutique, cosmétique, alimentaire ou dans le domaine de la détergence.
Cependant, les procédés actuels de fabrication utilisent des catalyseurs conventionnels, comme l’acide paratoluène sul-
fonique, ne conduisant qu’à des mélanges de glycérides. De plus les catalyseurs acides peuvent favoriser les réactions
secondaires de dégradation des produits formés (oxydation). La réaction d’estérification du glycérol par l’acide stéarique
(mélange équimolaire) a donc été étudiée à 110 °C, en présence de divers catalyseurs acides et basiques (NaOH, APTS, ZnO
et MgO). Cette première étude a mis en évidence le caractère sélectif de ZnO par rapport à MgO, en raison de propriétés
acido-basiques différentes, bien que la réaction ait été réalisée en milieu polyphasique. L’utilisation d’un solvant approprié,
qui permet d’homogénéiser le milieu réactionnel, modifie les propiétés catalytiques du catalyseur ZnO, en limitant la réaction
thermique généralement observée en l’absence de catalyseurs. En effet, en présence de bis(2-methoxyethyl) ether (diglyme),
l’activité et la sélectivité en monostéarate sont augmentées et le rendement en monoglycéride atteint 50 %. Les propriétés
physico-chimiques de ce solvant jouent donc un rôle primordial dans cette réaction, alors que le dimethylsufoxyde et le
dimethylformamide inhibent plutôt l’activité de ZnO, vraisemblablement par une importante solvatation des sites réactionnels.
© 2000 Académie des sciences / Éditions scientifiques et médicales Elsevier SAS
estérification du glycérolmonoglycéride / oxyde de zinc / acide stéarique

* Correspondence and reprints:

E-mail address: yannick.pouilloux@esip.univ-poitiers.fr (Y. Pouilloux).
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 Y. Pouilloux et al. / C. R. Acad. Sci. Paris, Série IIc, Chimie / Chemistry 3 (2000) 589 – 594
1. Introduction
Numerous compounds used in the chemical in-
dustry may be currently obtained from raw materials
such as vegetable oils. The specific properties of
these natural products (renewable, control of pro-
duction, etc) are of interest to the industry.
However, the development of the fat- and oil-in-
dustry will also lead to an important production of
side-products such as glycerol which could become
a cheaper raw material for chemistry. The glycerol
transformation into glycerol monoesters has signifi-
cant applications in food, pharmaceuticals, cosmetics
or in detergents chemistry [1].
The monoglycerides are generally obtained from:
(i ) the glycerolysis of triglycerides, (ii ) the hydroly-
sis of triglycerides or (iii ) the direct esterification of
glycerol with fatty acids [2] (scheme 1 ).
However, the industrial processes generally use
homogeneous acid or basic catalysts leading to a
mixture of mono-, di- and triglycerides (40:50:10).
Before their application, a molecular distillation must
be carried out to obtain a monoglyceride with a high
purity ( \ 90 %). In the industry, mineral acids (sul-
furic acid) or organic acids (paratoluene sulfonic
acid) are the most often used. But besides the envi-
ronmental problems, these catalysts favor side-reac-
tions from the degradation of the fatty acid
(oxidation, dimerisation) or from the glycerol (poly-
merisation, dehydration into acrolein, oxidation).
The use of less corrosive solid catalysts which are
more easily recyclable should improve the
processes.
In the literature, besides the enzymatic way [3, 4],
it was shown in our laboratory that cationic ex-
change resins could be used in the esterification of
glycerol with oleic acid in mild conditions (mono-
glyceride yield: 72 %), but these catalysts are less
active than the homogeneous acids [5, 6]. In other
studies [7, 8] it was demonstrated that the reaction
between glycidol and oleic acid in the presence of
anionic resins also gave a high yield of monoglyce-
rides. However the initial preparation of the glycidol
was an expensive step which decreases the interest
of the process for the synthesis of the monoglyce-
rides.
Scheme 1.
590
On the other hand, numerous examples of solid
acid catalysts, such as zeolites, are also reported in
the literature. For example, Aracil and Corma [9]
described a process for the synthesis of monoesters
from the esterification of polyols (i.e. glycerol) with
fatty acids in the presence of zeolites. They claimed
a monoglyceride yield of about 70 % when the reac-
tion is carried out at low pressure and at tempera-
tures between 100 and 190 °C, but the effect of the
nature of the zeolite is not clearly evidenced. More-
over, Bossaert [10] showed that at 110 °C, a sponta-
neous reaction between glycerol and lauric acid
occurred and became significant at higher tempera-
ture. More recently, Van Rhijn and coll. [11], modify-
ing mesoporous catalysts with sulfonic groups
obtained more active materials than zeolites in the
D-sorbitol esterification with lauric acid. In the reac-
tion of glycerol with lauric acid, they also showed
that the mesoporous MCM-41 modified with sulfonic
groups was more selective in the esterification
(monoglyceride yield of 52 %) than PTSA or HUSY
zeolite.
Although less used, some basic catalysts (hydrox-
ides, carbonates) have some activity in the esterifica-
tion reaction [12, 13]. Alkaline salts of fatty acids are
also used, but they are less efficient [14]. Several
authors [15, 16] have also studied the reaction be-
tween glycidol and lauric acid in the presence of
amine-modified MCM-41. The basic groups grafted
on the mesoporous catalysts increase the selectivity
to monoglyceride. However, this study was per-
formed in the presence of a solvent (toluene) with
about 36 % weight of catalyst, an amount which
cannot be considered as a catalytic one.
In order to avoid side reactions, it seems more
promising to study the direct esterification of the
glycerol with fatty acid (stearic acid) in the presence
of solid basic materials. In this paper we present the
catalytic activity of several homogeneous (NaOH)
and heterogeneous (MgO, ZnO) basic catalysts and
the effect of a solvent on the catalytic activity of zinc
oxide.
2. Experimental conditions
2.1. Catalytic test
The esterification of glycerol with stearic acid was
carried out at atmospheric pressure under nitrogen
in a glass reactor equipped with a mechanical stirrer
and heated with an oil bath. The experimental con-
ditions are the following: temperature 110 °C, reac-
tion duration: 24 h; molar ratio glycerol/stearic acid:
 Y. Pouilloux et al. / C. R. Acad. Sci. Paris, Série IIc, Chimie / Chemistry 3 (2000) 589 – 594
1; catalyst percentage (wt.%): 3. The samples of the
reaction medium were analysed by GPC equipped
with a FID detector and an on-column injector.
However, the analysis of the glycerol and products
requires a silylation step in order to protect hydroxyl
groups and to avoid their decomposition during the
analysis. The percentage of each compound was
determined by using standardisation methods with
hexadecane as an internal standard. The conversion
is estimated with regard to the initial and the final
content of stearic acid in the solution.
2.2. Results
2.2.1. Study of the esterification reaction of
glycerol with stearic acid using usual acid or
basic catalysts
First, the esterification of the stearic acid in the
presence of acid or basic catalysts generally used in
the industry was studied. The corresponding results
will be used as references for the evaluation of the
properties of solid catalysts.
First of all, table I shows that the thermal reaction
is not negligible at 110 °C since the conversion is of
about 30 % after 16 h.
The results also show that the paratoluene sulfonic
acid (PTSA) is more active than the sodium carbon-
ate. However, the low conversion observed over
basic catalysts may be due to a significant formation
of soap (20 %) during the reaction. Indeed, the
Table I. Esterification of glycerol with stearic acid, without catalyst, and over usual acid or basic catalysts.
Catalyst Time (h) Conversion (%) stearic acid
Without 16 29.8
Na2CO3 16 43.9
PTSA 16 89.4
1
T = 110 °C ; catalyst weight = 0,5 g ; gly/stearic acid = 1.
Table II. Esterification of glycerol with stearic acid over basic catalysts.
Catalyst BET surface area (m2·g–1)
MgO 151
ZnO 32
2
T = 160°C ; catalyst = 0.7 (wt.%); gly/stearic acid = 1, reaction time = 24 h.
stearic acid can easily react with the sodium carbon-
ate and form acid salts via a saponification reaction.
However, if the acid is the most active catalyst, the
monoglyceride selectivity is rather low (30 %).
The conversion and the selectivity to mono-, di-
and triglycerides obtained in the presence of basic
solid catalysts are reported in table II. It seems that
magnesium oxide is more active than zinc oxide in
the esterification reaction, but even if there is no
direct relation between the activity and the specific
surface area, this result could be due to a higher BET
surface of MgO. Indeed, MgO is twice as active as
ZnO. Nevertheless, regarding the acido-basicity mea-
surements (respectively determined by TPD of CO2
or of NH3), it also appears that the basicity of MgO is
higher than that of zinc oxide, which could explain
the higher activity of MgO in the esterification
reaction.
On the other hand, figure 1, which presents the
mono- and diglyceride selectivities versus the stearic
acid conversion shows that zinc oxide is much more
selective to monoglyceride than magnesium oxide.
This could be due to the specific amphoteric proper-
ties of ZnO (see table II), which influence the forma-
tion rate of the diglycerides. Indeed, two phases are
observed during the reaction and the affinity of the
catalyst for one of the two phases is greatly depen-
dent on the physico-chemical properties of the cata-
lyst. The relative reactivity of the primary or
Selectivity (%)
mono-a di-a triglyceridesa
46.6 47.9 5.5
68.5 29.7 1.8
32.3 64.2 3.5
Conversion (%) Basicity Acidity
(mmol · g–1 –1
catal) (× 10 )
67.5 3.5 3
36.5 0.4 4
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 Y. Pouilloux et al. / C. R. Acad. Sci. Paris, Série IIc, Chimie / Chemistry 3 (2000) 589 – 594

then leads to an important variation of activity and

Figure 1. Esterification of glycerol with stearic acid in the pres-
ence of ZnO and MgO. Selectivity to mono- and diglycerides
versus conversion. ZnO ( ); MgO (").
secondary hydroxyl groups to the mono- and to the
diesterification of the glycerol depends on the cata-
lyst’s basicity. We can expect that the formation of
the glycerol monostearate will be more significant in
the presence of ZnO rather than in the presence of
MgO due to the lower basicity of ZnO. In both cases,
the triester formation is very low.
2.2.2. Activity and selectivity of a zinc oxide
catalyst in the presence of solvents
As the reaction occurs in a polyphasic media
(lipidic phase, glyceric phase and solid catalyst), the
greater affinity of the catalyst for one phase implies a
modification of the adsorption rate of reactants (glyc-
erol, acid) and of products (monoglyceride) and
selectivity. Moreover, the addition of a solvent can
also modify significantly the catalytic properties of
the solid in changing the miscibility of reactants and
products. The solvent is also adsorbed at the surface
of the catalyst, modifying the coverage of reactants
and products as, moreover, the rate of the
esterification.
Four solvents with different physico-chemical
properties have been chosen in this study (table III):
toluene, dimethylsulfoxide (DMSO), N,N-dimethyl-
formamide (DMF) and bis(2-methoxyethyl)ether
(diglyme).
The results presented in table IV show the influ-
ence of the solvent on the thermal reaction (without
catalyst). The addition of each of these solvents
inhibits the thermal reaction since the conversion is
lower than 10 % instead of 30 % (see table I). On the
other hand, the results are very different in the
presence of the ZnO catalyst.
2.2.2.1. Activity
In the presence of dimethylsulfoxide (DMSO), a
significant decrease of the activity is observed owing
to an inhibition of the esterification reaction (figure
2a). With dimethylformamide (DMF), the activity is
similar to the activity obtained without solvent.
These two solvents could be preferentially adsorbed
at the surface of the zinc oxide (Lewis site) via the
oxygen atom of the sulfoxide SO or carbonyl CO
group and strongly modify the reactivity of the glyc-
erol and/or the acid.

Table III. Physico-chemical characteristics of solvents.

Solvent Dipole moment Boiling point (°C) Solubility (110 °C)

Glycerol Stearic acid

Toluene 0.31 110.6 dS S

DMSO 3.9 238 S S
DMF 3.86 153 S S
Diglyme 1.97 162 S S

Table IV. Influence of the solvent on the thermal reaction of the esterification of glycerol with stearic acid performed without catalysts.

Solvent Time (h) Conversion (%) Selectivity (%)

mono di tri

Toluene 16 6.0 98 2 –
N,N-DMF 16 5.5 100 – –
Diglyme 16 7.5 100 – –

3
T = 110 °C ; gly/stearic acid = 1 ; Vsolvent = 20 mL.

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 Y. Pouilloux et al. / C. R. Acad. Sci. Paris, Série IIc, Chimie / Chemistry 3 (2000) 589 – 594
Figure 2. Esterification of glycerol with stearic acide over ZnO in
the presence of solvents. Variation of stearic acid conversion
versus reaction time (a) and of selectivity to mono- and diglyce-
ride versus conversion (b).
Figure 3. Esterification of glycerol with stearic acid over ZnO in
the presence of diglyme. Influence of diglyme content on the acid
conversion and selectivity to monoglyceride.
Although toluene does not dissolve glycerol, an
increase of the conversion is observed when the
toluene is used (figure 2a). In this case, due to the
greater miscibility of monoglyceride in the toluene
phase containing stearic acid, this compound can
more easily react with stearic acid, giving diglyce-
rides. When using diglyme, the most interesting re-
sults are obtained because the acid conversion is
above 60 % after 16 h. In this case, the diglyme
seems to favour mainly the homogeneity of the
reaction media.
2.2.2.2. Selectivity
Figure 2b shows that the monoglyceride selectivity
increases when the reaction is carried out in a
monophasic media. Indeed, the monoglyceride se-
lectivity is of 82 % for a conversion of 63 % when the
diglyme is used as solvent. This result suggests that
the competitive adsorption of glycerol, stearic acid
and diglyme leads preferentially to the formation of
monoglyceride and inhibits the polyesterification.
On the other hand, when the media is polyphasic,
(without solvent, toluene), the formation of diglyce-
ride is favored, since the monoglyceride is more
miscible in the stearic acid phase rather than in the
glycerol phase.
2.2.3. Influence of the experimental
parameters on the catalytic properties of ZnO
The above results showed the original properties
of a mixed system using ZnO and diglyme. But it
was also necessary to determine the influence of the
solvent amount on the catalytic properties of ZnO.
Figure 3 shows that the acid conversion depends on
the solvent volume, an optimum value being ob-
tained for a solvent volume of 20 mL (which repre-
sents a percentage of 50 (wt.%) with regard to the
reactants).
For a lower amount of solvent, the acid conver-
sion is lower, due to the presence of two phases. For
a higher solvent content, a decrease of the conver-
sion is observed mainly due to a dilution effect.
Figure 4. Esterification of glycerol with stearic acid in the pres-
ence of [ZnO/diglyme]. Influence of the (glycerol/stearic acid)
ratio on the conversion and selectivity to monoglyceride.
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 Y. Pouilloux et al. / C. R. Acad. Sci. Paris, Série IIc, Chimie / Chemistry 3 (2000) 589 – 594
Table V. Influence of the nature of acid on the esterification of glycerol in the presence of [ZnO/diglyme].
Acid Conversion (%) Monoglycerideyield (%)
Stearic 63.3
Lauric 56.1
Oleic 45.1
4
T = 110 °C; catalyst weight = 0.5 g; gly/fatty acid = 1; reaction time = 16 h; Vsolvent = 20 mL.
2.2.4. Influence of the (glycerol/stearic acid)
ratio
Figure 4 shows that an excess of glycerol does not
change the conversion nor the selectivity. This sur-
prising result is different from that of previous stud-
ies, which showed that the addition of glycerol
decreased the conversion and increased the selectiv-
ity [6, 10]. On the other hand, an excess of stearic
acid leads to an increase of the acid conversion and
a decrease of the monoglyceride selectivity. In fact,
as the solvent volume is constant, and not optimised
for each experiment, some miscibility effects could
change the well-known kinetic effects resulting from
an excess of glycerol.
2.2.5. Influence of the nature of the fatty acid
on the activity and selectivity of ZnO
It was shown in previous studies [6] that the length
and the functionality of the hydrocarbon chain could
have an influence on the esterification reaction. In
this study, the reactivity of lauric acid (C12:0) and
oleic acid (C18:1) are compared to that of stearic
acid (table V). In the presence of diglyme the activity
of ZnO depends on the nature of the acid and varies
in the following order: oleic acidB lauric acidB
stearic acid. These results demonstrated that the
differences observed in previous studies when the
experiments were done without solvent could be
partly due to changes of miscibility of monoglyceride
with regard to glycerol or fatty acid.
3. Conclusion
The esterification of glycerol with stearic acid in
the presence of solid basic catalysts shows that zinc
oxide is a more selective catalyst than MgO, due to
different acid–base properties and to the presence of
a multiphasic reaction mixture.
594
Selectivity (%)
mono di tri
52 82.5 17.5 o
41 73.3 26.7 o
41 90.7 9.3 o
Therefore, the use of an appropriate solvent in
homogenising the reaction mixture modifies the cat-
alytic properties of ZnO. Indeed, in the presence of
bis(2-methoxyethyl) ether (diglyme), the activity and
the selectivity to glycerol monostearate are increased
even at low temperature (110 °C). But, the polarity of
the solvent also modifies the reactivity of the
reagents, products and of the catalyst. Indeed, if
diglyme improves the esterification reaction over
zinc oxide, DMSO and DMF inhibit the activity of the
catalyst by solvation of the active sites.
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