Eur. J. Lipid Sci. Technol.

2008, 110, 825–830 825

Review Article
Design of new solid catalysts for the selective conversion of
glycerol

Joel Barrault, François Jerome

CNRS-Université de Poitiers, Laboratoire de Catalyse en Chimie Organique, UMR 6503, ESIP, Poitiers, France

Glycerol is now obtained as a co-product of biodiesel from renewable raw materials with a dramatically
increasing production. It follows that one of the most important breakthroughs is to find new catalytic
processes for chemical valorizations. The present paper gives a short overview of selective esterification,
transesterification or etherification of glycerol via the use of new heterogeneous catalysts. The selectivity
control is mainly the result of the synthesis of mesoporous materials for which acidic or basic properties as
well as the surface hydrophilic-lipophilic balance were optimized.

Keywords: Alkyl ethers / Glycerol / Glyceryl ethers / Monoglycerides / Polyglycerols / Solid catalysts

Received: February 29, 2008; accepted: April 29, 2008

DOI 10.1002/ejlt.200800061

1 Introduction catalysts, a quite important property governing the adsorption

of polyhydroxylated compounds and the surface coverage of a
During the last decade, there was an important industrial catalyst with regard to, e.g., hydrophobic reagents such as fatty
development of vegetable oils especially for the production of acids or esters, (iv) the immobilization of molecular catalysts
biofuels. The production of glycerol, the main co-product of onto a solid support, and (v) the coating of silica-supported
biofuel formation via transesterification, was also greatly sulfonic acidic catalysts with hydrophobic ionic liquids. All
increased so that it was necessary to develop new and innova- these materials were used for the selective preparation of
tive transformations of glycerol into valuable products. In glycerol esters or ethers (Fig. 1).
recent reviews [1–5] the transformation of glycerol into
chemicals such as surfactants [2], fuel additives [6], acrolein
[7, 8], glycerol carbonate [9], etc. was reported.
In our laboratory we decided more than 10 years ago to
study new strategies involving heterogeneous catalysis, to get
either new performances for known reactions or new reactions
and new products. In order to use glycerol as building block,
we have to find selective catalysts for the functionalization of
one among the three hydroxyl groups of the glycerol molecule,
without the assistance of protective agents while keeping a
significant rate of reaction.
In this paper, we report some of the original approaches
developed in our laboratory consisting in (i) the preparation
of porous materials, (ii) the control of the acidity or the basi-
city, (iii) the consideration of the surface hydrophilicity of the

Correspondence: Joel Barrault, CNRS-Université de Poitiers, Labora-

toire de Catalyse en Chimie Organique, UMR 6503, ESIP, 40 avenue du
Recteur Pineau, 86022 Poitiers, France.
E-mail: joël.barrault@univ-poitiers.fr
Fax: 133 5 49413999 Figure 1. Some selective transformations of glycerol.

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.ejlst.com

826 J. Barrault et al.
2 Monoglycerides from glycerol via
glycerolysis or esterification
Synthesis of monoglycerides is commercially achieved either
by glycerolysis of animal and vegetable fats and oils or by
direct esterification of glycerol with fatty acids [10]. These
catalytic processes require strong base catalysts such as KOH,
NaOH or Ca(OH)2 and lead to the formation of mono-
glycerides in a limited purity due to the side production of di-,
triglycerides and soap. Recently, alternative methods involving
immobilized enzymes were also reported and seem to be
promising despite a relatively complex work-up [11, 12].
Heterogeneous catalysts also offer many advantages, like
easy separation of the catalyst from the reaction products and
recycling. Corma et al. reported that the glycerolysis of the
1,2,3-tri-(cis-9-octadecenoyl)glycerol (trioleine) and rapeseed
oil can be performed over solid basic catalysts such as sepio-
lite-Na-Cs, Cs-exchanged MCM-41, MgO and hydrotalcites
[13]. From these heterogeneous catalytic routes, glycerol
esters were obtained in 90% yield with a 75% selectivity to
monoglycerides. However, high temperature and a glycerol/
triolein molar ratio of 12 were necessary to reach such results.
Mesoporous silica functionalized either with acid or basic
groups [14–17] or slightly basic Y-zeolites [18, 19] led to more
than 80% selectivity to monoglycerides, starting from a glyc-
erol/fatty acid molar ratio of 1. However, these high selectiv-
ities were only obtained at 20% conversion and rapidly
decreased to 40–50% at total conversion.
3 Monoglycerides from glycerol
transesterification over basic catalysts
The use of solid basic catalysts such as magnesium oxide and
rare earth oxides has shown that a relationship exists between
the intrinsic basicity of these materials and the transesterifica-
tion rate [20]. Nevertheless, the ester distribution was quite
similar to that resulting from a homogeneous reaction.
More recently, a friendly high-yielding selective synthesis
of monoglycerides, starting from an equimolar mixture of
fatty methyl esters and unprotected glycerol, was reported
[21]. This one-pot reaction without solvent was catalyzed
at low temperature by two guanidine derivatives (Fig. 2):
7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (Me-TBD)
and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) [2.5 mmol/g
polystyrene (PS)] bound to a PS network (PS-TBD).
In the presence of Me-TBD, unprotected glycerol reacted
with various fatty methyl esters giving glycerol esters with over
95% yield and a selectivity to monoglycerides of about 60%
(see example of methyl dodecanoate in Table 1). As described
in the literature, 1-monoglycerides were mainly produced
against 2-monoglycerides in a 9 : 1 ratio [11, 12].
Over PS-TBD, monoglycerides were produced with 96%
yield and 62% selectivity (Table 1), with the efficiency of the
solid catalyst being lower than that of the homogeneous one.
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Lipid Sci. Technol. 2008, 110, 825–830
Figure 2. 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-
1,5,7-triazabicyclo[4.4.0]dec-5-ene (Me-TBD) and P1-phospha-
zene.
Table 1. Catalytic activity of guanidine derivatives (glycerol/methyl
dodecanoate molar ratio of 1, 110 7C, solvent free).
Catalyst Time Yield Monoglycerides Diglycerides Triglycerides
[h] [%]§ [%]$ [%]$ [%]$
Me-TBD 2 100 62 33 5
PS-TBD 8 96 62 6
§
Global yields of glycerol esters were determined by GC.
$
Yield of each glyceride.
A strong non-ionic P1 phosphazene base [22, 23] (Fig. 2)
with a pKa value higher than 27 is also a very promising orga-
nocatalyst for the selective transesterification of fatty methyl
esters with glycerol [24] in the presence of a solvent. Among
various organic solvents, the association of the catalyst with
acetonitrile was the best solution to control the selectivity of
the transesterification reaction. Moreover, due to the precipi-
tation of the different targeted fatty glycerides during the cat-
alytic process, the purification step was very easy and it was
possible to recycle acetonitrile. From this reaction performed
at room temperature, it was possible to selectively obtain either
monoesters or diesters of glycerol (isolated yield of 80% in
each case) depending on their solubility in the solvent.
Whereas all reported transesterification catalytic processes
produced a mixture of regioisomers, in that case the regios-
electivity (a-monoglycerides or a,a-diglycerides) was com-
plete since only these isomers precipitated. One may consider
this result quite important since different properties can be
observed depending on the position of the hydrocarbon chain.
The increase of the monoglyceride selectivity in the pres-
ence of solid catalysts was mentioned for the first time in using
mesoporous and basic materials [25]. Over an Mg-MCM-41
catalyst exhibiting a surface area of about 800 m2/g, glycerol
monododecanoate was obtained with a selectivity and a yield
of about 80% (with a glycerol/ester ratio of 2), showing that
such catalysts induced a shape selectivity. Indeed, it was also
demonstrated that, by changing the pore size of the catalyst or
the hydrocarbon chain length of the methyl ester, the effect of
shape selectivity was also modified. Moreover, as the reaction
was performed in a batch reactor, the catalyst recycling was
also investigated and the results showed no modification of the
catalytic properties during the reaction.
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Eur. J. Lipid Sci. Technol. 2008, 110, 825–830
4 Monoglycerides from glycerol esterification
over acidic catalysts
Silica-immobilized molecular catalysts (SIMC) have become
very promising tools for catalysis since recent studies have
shown a clear synergistic effect between the immobilized cat-
alytic entities and the siliceous support [26–29]. However, in
this case also, the catalytic performances of that SIMC –
especially the reaction rate – were lower than that of the cor-
responding homogeneous catalysts. It was suggested that
some specific surface properties (poor accessibility, high
hydrophilicity) of these materials could explain this lower
catalytic activity.
Nevertheless, on account of the results obtained in the
glycerol transesterification presented above, the properties of
mesoporous SIMC – especially mesoporous silica-supported
sulfonic groups – with different pore sizes were investigated.
The esterification of glycerol with 16-hydroxy-
hexadecanoic acid (juniperic acid) was studied in the presence
of p-toluene sulfonic acid (PTSA) as reference homogeneous
catalyst. As expected, using PTSA, the resulting amphiphilic
monomer was obtained with a yield lower than 35% because of
a rapid polymerization of reactants (Fig. 3). Then, sulfonic
groups were immobilized over three different mesoporous
silicas [30, 31] well known for their strong hydrophilicity. Over
such solids, interactions between the silica framework and
glycerol are expected to favor a rapid desorption of the
amphiphilic monomer.
The results presented in Fig. 3 show, as expected, that
mesoporous SBA-SO3H and HMS1-SO3H materials with
pore diameters of 3.5 and 2.8 nm are much more selective
than homogeneous PTSA since a yield of 80% is obtained for
the desired monoester. If the pore size of the catalyst was
decreased (HMS2-SO3H, 2.3 nm), the reaction rate decreased
but the monoester yield was increased above 90% (Fig. 3).
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
New catalysts for the selective conversion of glycerol 827
Moreover, over the last catalyst, it appears that the selectivity
improvement is the result of both hydrophilicity and shape
selectivity, since the monoester is not further transformed into
the di - and triester (cf. evolution of the monoester yield be-
tween 8 and 16 h of reaction in Fig. 3).
5 Glycerol etherification
5.1 Polyglycerols
These compounds are used in the manufacture of new prod-
ucts for cosmetics, food additives, surfactants, lubricants, etc.,
because of the possibility to control their hydrophilic-lipo-
philic balance (HLB). But in order to get well-defined deri-
vatives, the glycerol etherification step, which looks like a po-
lymerization, must be controlled.
In previous works, the etherification of glycerol in the pres-
ence of the usual homogeneous acid (i.e. benzene sulfonic acid)
or base (potassium carbonate) catalysts was shown to give a
mixture of polyglycerols containing linear isomers coming from
the reaction of primary hydroxyls, branched isomers formed
from secondary hydroxyls and cyclic isomers resulting from
intramolecular condensation of the previous ones (Fig. 1).
As an example, at the end of the reaction over sodium
carbonate [32] and after analysis of some of the isomers (the
synthesis of each isomer was performed via chemical routes
[33, 34]), glycerol was completely transformed into diglycer-
ols (31%), triglycerols (28%), tetraglycerols (17%) and others
(penta- to decaglycerols, 24%). Moreover, several solid and
basic catalysts (bulk alkaline and alkaline earth oxides) have
been tested in this reaction, and most of the results have shown
that neither the selectivity nor the reaction rate was improved
since part of the catalyst was often solubilized during the
reaction [2, 35].
Figure 3. Yield of glycerol monoester (juniperic
acid) over (n) SBA-15-SO3H (surface area/SA:
742 m2/g, pore diameter/PD: 3.5 nm, H1
exchange capacity/HEC: 0.44 mmol/g),
(m) HMS1-SO3H (SA: 1093 m2/g, PD: 2.8 nm,
HEC: 0.21 mmol/g), (n) HMS2-SO3H (SA:
1290 m2/g, PD: 2.3 nm, HEC: 0.24 mmol/g),
(6) PTSA and (n) blank (from ref. [30]). SBA and
HMS are abbreviations of respectively Santa Bar-
bara (place where the first synthesis of these
materials was done) and hexagonal mesoporous
silicas. Experimental conditions: temperature:
110 7C, 5 mol-% of p-toluene sulfonic acid (the
catalyst percentage is related to the acid content),
glycerol/acid: 6 (molar).
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828 J. Barrault et al.
In recent years, mesoporous materials impregnated or
exchanged with different bases (Li, Na, Cs, La) were used in
glycerol etherification [36]. Among these catalysts, MCM-41-
type materials with the specific surface area ranging from 400
to 1200 m2/g and a pore size of 3–4 nm were the more effi-
cient catalysts for the direct and selective transformation of
glycerol into di- and triglycerols, with a yield of about 80%
instead of 55% with homogeneous carbonate [35]. Moreover,
using mesoporous catalysts, there is an important formation of
a,b- and a,b-diglycerols, which could confirm that the reac-
tion occurred inside the pores of a shape-selective material.
5.2 Polyglycerols esters
These compounds were often obtained in a two-step proce-
dure: (i) the preparation of a polyglycerol (PG) fraction and
(ii) esterification or transesterification of the PG with different
acids or esters [2] – with most of these processes being per-
formed in the presence of homogeneous catalysts [2].
Recently, Barrault et al. reported that some mesoporous
materials similar to that used in the synthesis of PG (Cs/
MCM) could also represent selective catalysts for the forma-
tion of diglycerol esters either from diglycerol or directly from
glycerol and methyl esters [36]. Over these solids, a mixture of
esters containing mainly diesters and triesters of diglycerols
(more than 60%) was obtained, representing a very promising
result for the development of new and green processes.
5.3 Alkyl glyceryl ethers
Monoalkyl glyceryl ethers (MAGE) exhibit a wide spectrum
of biological activities and are also important precursors for
the preparation of 1,3-dioxolan-2-ones [37, 38] and bis(so-
dium sulfonate ester)-type cleavable surfactants [39].
The catalytic etherification of glycerol with alkyl alcohols
was first investigated [40]. Since alkyl chlorides were generally
used for etherification with an important formation of salts,
the search for new catalytic pathways was necessary. It was
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Lipid Sci. Technol. 2008, 110, 825–830
then discovered that the (SiO2-SO3H) [30, 31] mentioned
above for glycerol esterification could also be used for the
direct etherification of glycerol with 1-phenyl-1-propanol.
Indeed, when an equimolar mixture of glycerol and 1-phenyl-
1-propanol was heated at 80 7C in the presence of sulfonic
catalyst grafted over silica (1.7 mol-%), the resulting MAGE
were obtained in a 73% yield [40]. It is noteworthy that, in all
cases, the desired a-monoalkyl glyceryl ether (1c) was always
obtained in more than 88% of regioselectivity (Fig. 4).
Under similar conditions, many benzyl alcohols including
1-phenyl-1-ethanol, 1-tolyl-1-ethanol, 1-(4-chlorophenyl)-1-
ethanol, 1-phenyl-1-pentanol, benzhydrol and benzyl alcohol
(Fig. 5) were successfully converted into their corresponding
MAGE, with yields ranging from 85 to 95%.
As for 1-phenyl-1-propanol, the a-monoalkyl glyceryl
ether (2a) was mainly obtained, with the ratio 2a/2b varying
from 6 to 16.
Moreover, glycerol was also reacted with norbornylene,
dicyclopentadiene or dibenzyl ethers to form the correspond-
ing MAGE and produce a-regioisomers in 80% yield.
6 Conclusion
In the present short review on glycerol functionalization, some
recent results clearly evidenced that it is possible to find new
reactions and new products starting from glycerol via the use
of optimized solid catalysts. All reactions are performed in
green conditions at low temperature, without solvent (or with
green solvents) and with recyclable catalysts (reaction condi-
tions prevent the deactivation of catalysts). Moreover, the high
selectivity of the catalysts as well as their high stability
(absence of leaching of active phases during the reaction)
avoids the formation of co-products and salts so that the pu-
rification and separation steps of the main products are greatly
facilitated. These researches open a new and broad field of
investigation for glycerol as well as for other polyols, sugars
and other saccharides.
Figure 4. Etherification of glycerol with 1-
phenyl-1-propanol over (SiO2-SO3H) [30, 31].
Figure 5. Etherification of glycerol with alkyl alcohols over (HMS1-
SO3H) [30, 31].
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Eur. J. Lipid Sci. Technol. 2008, 110, 825–830
Conflict of interest statement
The authors have declared no conflict of interest.
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