Research proposal for Contrats Doctoraux 2014 Ecole Doctorale Chimie, Universit Claude Bernard

Lyon1.

Thesis Title: Catalytic hydrogenolysis of polyols from renewable feedstocks in aqueous phase.
Introduction
Conversion of abundant renewable carbon resources available from biomass to high added-value
chemicals has immense potential. In particular, hydrogenolysis of biomass-derived C3-C6 polyols may
produce propanediols (1,2- or 1,3-PDO), ethylene glycol (EG); lactic acid (LA) can also be produced.
These compounds are important industrial intermediates. The use of a catalyst under appropriate
conditions may shift the selectivity to the desired product in the mixture.

Although hydrogenolysis of glycerol (C3 polyol) to EG and 1,2-PDO has been extensively studied
during the past decade, in contrast, limited information exists on hydrogenolysis of erythritol (C4
polyol), xylitol (C5 polyol) and sorbitol (C6 polyol). Unlike glycerol conversion, which is dominated by
C-O cleavage in the presence of metal catalysts, longer chain sugar alcohols conversions involve
even more complex parallel and consecutive C-O and C-C cleavages as competing reactions
(dehydrogenation-retroaldol pathway), posing significant challenges [1]. Conditions have usually
involved a supported metallic catalyst and a base to promote C-C cleavage via retroaldol
condensation.
It has also been shown that conversion of glycerol may give lactic acid (LA), using Ir or Pt-based
catalysts in strong alkaline medium under inert atmosphere [2]. Conversion of other sugar-derived C5C6 polyols to lactic acid has not been studied and would represent new promising reactions.
Further, interestingly, the presence of an oxophilic additive (ReOx, MoOx) in contact with the highly
reducible supported metal has been shown to promote the activity of the catalyst and to shift the
selectivity to produce 1,3-propanediol from glycerol or the corresponding linear diols from cyclic ethers
by a bifunctional catalysis [3]. This would be a way of synthesis of a,w-diols, used as monomers for
the production of polyesters and polyurethanes.
Scientific project
This work will be focused on the aqueous phase transformation of biomass-derived C3-C6 polyols to
the various value-added chemicals such as glycols and lactic acid. Significant undesired by-products
may also be formed (butanediols, monoalcohols, gaseous compounds such as methane ) which will
be thoroughly analyzed.
All these reactions will be typically conducted in the aqueous phase. The important factors influencing
the activity and selectivity will be investigated, such as the nature of the metallic catalyst (mono or
bimetallic catalyst), the type of the support (e.g. acid-base properties and its texture), the metallic
dispersion, the effect of the reaction conditions (temperature, gaseous atmosphere- H2 or N2, the type
of alkali promoters-NaOH, KOH vs. Ca(OH)2, Ba(OH)2, the possibility of working in base free
conditions,). These studies will be the basis for gaining insight into the reaction pathways to the
different products and for a deeper understanding of the reaction mechanisms, to develop systems
with improved selectivity.
This study will be performed in the group Valorisation of bioressources and green chemistry at
IRCELYON, equipped with the reactors (batch and continuous) and the analytical tools necessary for

the reaction [1,2,4,5]. All techniques of characterization of prepared catalysts are available in the
different scientific services.
Contact: Michle BESSON, Directeur de recherches CNRS, tl: +33(0)4 72 44 53 58, E-mail:
michele.besson @ircelyon.univ-lyon1.fr
References
[1] F. Auneau et al, Exploring the reaction conditions for Ru/C catalyzed selective hydrogenolysis of
xylitol alkaline aqueous solutions to glycols in a trickle-bed reactor, Catal. Today, 2014, in press.
[2] F. Auneau et al, On the role of the atmosphere in the catalytic glycerol transformation over Ir-based
catalysts, Catal. Commun. 16 (2011) 144-149.
[3] M. Chia et al, JACS133 (2011) 12675-12689.
[4] L. Corbel-Demailly et al, Heterogeneous catalytic hydrogenation of biobased levulinic and succinic
acids in aqueous solution, ChemSusChem. 62(2013) 2201-2213, 2388-2395.
[5] B.K. Ly et al, Effect of addition mode of Re in bimetallic Pd-Re/TiO2 catalysts upon the selective
aqueous-phase hydrogenation of succinic acid to 1,4-butanediol, Topics in Catal., 55 (2012) 466-473.
Ce sujet est soutenu par lIFPen, IFP Energies nouvelles