Rosaria Ciriminna and Mario Pagliaro in Lille University Doctoral Examination Committee

Doctoral Examination Committee meeting in Lille for Cyrille Guillon PhD defence, 25 February 2014

Lille, 25-Feb-2014 - Cyrille Guillon has been promoted Docteur en Chimie, Molécules et Matière condenseée, Université Lille 1 Sciences et Technologie, by the international Examination Committee presided by Axel Lofberg (CNRS) including Rosaria Ciriminna (CNR), Pedro Maireles Torres (University of Malaga), and Mario Pagliaro (CNR).

Dr Guillon brightly discussed a Thesis entitled “Ammoxidation du Glycerol en Phase Gaz” describing work carried out in the context of the EU 7th Framework Program “EuroBioRef” project, aimed at establishing a direct route for the ammoxidation of glycerol in gas phase to acryolonitrile in a single fixed-bed reactor over FeSbO4 mixed phase catalyst.

Currently produced by propene (and, to a lesser extent, by propane) ammoxidation on a > 5.5 million t scale, acrylonitrile is widely employed for the production of acrylic fibers as well as of nylon. The objective of the doctoral work was therefore to develop a suitable biomass-based route alternative to the petrochemical process affording acrylonitrile.

Glycerol is already the main platform biochemical of the chemical industry, and is abundantly available being obtained in huge (>2 million t/y) amount from global biodiesel and fatty acids and alcohols manufacturing.

The direct route from glycerol to acrylonitrile turned out to be impossible due to the high reactivity of glycerol towards oxygen at 400 °C, the typical reaction temperature for the antimony-iron catalyst.
Hence, the Dr Guillon -- mentored by Professors Franck Dumeignil and Sebastién Paul -- turned his attention to the conversion of eight glycerol direct derivatives, two of which (acrolein and allyl alcohol) gave noticeable results.

The selectivity of the allly alcohol conversion (55%) was higher than that of acrolein (44%). Futhermore, 23% of allyl alcohol is converted to acrolein, in itself a useful chemical.

Dr Guillon then developed the optimal conditions for allyl alcohol conversion. Following an elegant plan d’expérience using the ANOVA algorithm the selectivity to acrylonitrile could be increased from 55% to 83%, and conversion from 99% to 100%.

The work was published in the Green Chemistry 2013 themed collection “Renewable carbon and eco-efficient processes”.