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Review Article
Design of new solid catalysts for the selective conversion of
glycerol
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
4 Monoglycerides from glycerol esterification Moreover, over the last catalyst, it appears that the selectivity
over acidic catalysts improvement is the result of both hydrophilicity and shape
selectivity, since the monoester is not further transformed into
Silica-immobilized molecular catalysts (SIMC) have become the di - and triester (cf. evolution of the monoester yield be-
very promising tools for catalysis since recent studies have tween 8 and 16 h of reaction in Fig. 3).
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 – 5 Glycerol etherification
especially the reaction rate – were lower than that of the cor-
responding homogeneous catalysts. It was suggested that 5.1 Polyglycerols
some specific surface properties (poor accessibility, high
hydrophilicity) of these materials could explain this lower These compounds are used in the manufacture of new prod-
catalytic activity. ucts for cosmetics, food additives, surfactants, lubricants, etc.,
Nevertheless, on account of the results obtained in the because of the possibility to control their hydrophilic-lipo-
glycerol transesterification presented above, the properties of philic balance (HLB). But in order to get well-defined deri-
mesoporous SIMC – especially mesoporous silica-supported vatives, the glycerol etherification step, which looks like a po-
sulfonic groups – with different pore sizes were investigated. lymerization, must be controlled.
The esterification of glycerol with 16-hydroxy- In previous works, the etherification of glycerol in the pres-
hexadecanoic acid (juniperic acid) was studied in the presence ence of the usual homogeneous acid (i.e. benzene sulfonic acid)
of p-toluene sulfonic acid (PTSA) as reference homogeneous or base (potassium carbonate) catalysts was shown to give a
catalyst. As expected, using PTSA, the resulting amphiphilic mixture of polyglycerols containing linear isomers coming from
monomer was obtained with a yield lower than 35% because of the reaction of primary hydroxyls, branched isomers formed
a rapid polymerization of reactants (Fig. 3). Then, sulfonic from secondary hydroxyls and cyclic isomers resulting from
groups were immobilized over three different mesoporous intramolecular condensation of the previous ones (Fig. 1).
silicas [30, 31] well known for their strong hydrophilicity. Over As an example, at the end of the reaction over sodium
such solids, interactions between the silica framework and carbonate [32] and after analysis of some of the isomers (the
glycerol are expected to favor a rapid desorption of the synthesis of each isomer was performed via chemical routes
amphiphilic monomer. [33, 34]), glycerol was completely transformed into diglycer-
The results presented in Fig. 3 show, as expected, that ols (31%), triglycerols (28%), tetraglycerols (17%) and others
mesoporous SBA-SO3H and HMS1-SO3H materials with (penta- to decaglycerols, 24%). Moreover, several solid and
pore diameters of 3.5 and 2.8 nm are much more selective basic catalysts (bulk alkaline and alkaline earth oxides) have
than homogeneous PTSA since a yield of 80% is obtained for been tested in this reaction, and most of the results have shown
the desired monoester. If the pore size of the catalyst was that neither the selectivity nor the reaction rate was improved
decreased (HMS2-SO3H, 2.3 nm), the reaction rate decreased since part of the catalyst was often solubilized during the
but the monoester yield was increased above 90% (Fig. 3). reaction [2, 35].
In recent years, mesoporous materials impregnated or then discovered that the (SiO2-SO3H) [30, 31] mentioned
exchanged with different bases (Li, Na, Cs, La) were used in above for glycerol esterification could also be used for the
glycerol etherification [36]. Among these catalysts, MCM-41- direct etherification of glycerol with 1-phenyl-1-propanol.
type materials with the specific surface area ranging from 400 Indeed, when an equimolar mixture of glycerol and 1-phenyl-
to 1200 m2/g and a pore size of 3–4 nm were the more effi- 1-propanol was heated at 80 7C in the presence of sulfonic
cient catalysts for the direct and selective transformation of catalyst grafted over silica (1.7 mol-%), the resulting MAGE
glycerol into di- and triglycerols, with a yield of about 80% were obtained in a 73% yield [40]. It is noteworthy that, in all
instead of 55% with homogeneous carbonate [35]. Moreover, cases, the desired a-monoalkyl glyceryl ether (1c) was always
using mesoporous catalysts, there is an important formation of obtained in more than 88% of regioselectivity (Fig. 4).
a,b- and a,b-diglycerols, which could confirm that the reac- Under similar conditions, many benzyl alcohols including
tion occurred inside the pores of a shape-selective material. 1-phenyl-1-ethanol, 1-tolyl-1-ethanol, 1-(4-chlorophenyl)-1-
ethanol, 1-phenyl-1-pentanol, benzhydrol and benzyl alcohol
5.2 Polyglycerols esters (Fig. 5) were successfully converted into their corresponding
MAGE, with yields ranging from 85 to 95%.
These compounds were often obtained in a two-step proce- As for 1-phenyl-1-propanol, the a-monoalkyl glyceryl
dure: (i) the preparation of a polyglycerol (PG) fraction and ether (2a) was mainly obtained, with the ratio 2a/2b varying
(ii) esterification or transesterification of the PG with different from 6 to 16.
acids or esters [2] – with most of these processes being per- Moreover, glycerol was also reacted with norbornylene,
formed in the presence of homogeneous catalysts [2]. dicyclopentadiene or dibenzyl ethers to form the correspond-
Recently, Barrault et al. reported that some mesoporous ing MAGE and produce a-regioisomers in 80% yield.
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 6 Conclusion
glycerol and methyl esters [36]. Over these solids, a mixture of
esters containing mainly diesters and triesters of diglycerols In the present short review on glycerol functionalization, some
(more than 60%) was obtained, representing a very promising recent results clearly evidenced that it is possible to find new
result for the development of new and green processes. reactions and new products starting from glycerol via the use
of optimized solid catalysts. All reactions are performed in
5.3 Alkyl glyceryl ethers green conditions at low temperature, without solvent (or with
green solvents) and with recyclable catalysts (reaction condi-
Monoalkyl glyceryl ethers (MAGE) exhibit a wide spectrum tions prevent the deactivation of catalysts). Moreover, the high
of biological activities and are also important precursors for selectivity of the catalysts as well as their high stability
the preparation of 1,3-dioxolan-2-ones [37, 38] and bis(so- (absence of leaching of active phases during the reaction)
dium sulfonate ester)-type cleavable surfactants [39]. avoids the formation of co-products and salts so that the pu-
The catalytic etherification of glycerol with alkyl alcohols rification and separation steps of the main products are greatly
was first investigated [40]. Since alkyl chlorides were generally facilitated. These researches open a new and broad field of
used for etherification with an important formation of salts, investigation for glycerol as well as for other polyols, sugars
the search for new catalytic pathways was necessary. It was and other saccharides.
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and cyclic polyglycerols. Polyglyceryled surfactants: Synthesis of 1,3-dioxolan-2-one derivative. Jpn Kokai Tokyo Koho, JP
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[34] S. Cassel, C. Debaig, T. Benvegnu, P. Chaimbault, M. [38] M. Okutsu, T. Kitsuki: Method for manufacturing cyclic car-
Lafosse, D. Plusquellec, P. Rollin: Original synthesis of linear, bonate.Jpn Kokai Tokyo Koho, JP 2004168674, 2004.
branched and cyclic oligoglycerol standards. Eur J Org Chem. [39] D. Ono, S. Yamamura, M. Magamura, T. Takeda: Synthesis
2001, 2001, 875–896. and properties of bis(sodium sulfonated ester) types of clea-
[35] J. Barrault, F. Jerome, Y. Pouilloux: Polyglycerols and their vable surfactants derived from 1-O-alkylglycerols. J Surfac-
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[36] J. Barrault, J. M. Clacens, Y. Pouilloux: Selective oligomeriza- erogeneously catalyzed etherification of glycerol. New path-
tion of glycerol over mesoporous catalysts. Top Catal. 2004, ways for transformation of glycerol to more valuable chemi-
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