(558bz) Catalytic Deoxydehydration of Glycerol to Allyl Alcohol with 2-Hexanol As H-Donor – Catalyst Development and Separation Process | AIChE

(558bz) Catalytic Deoxydehydration of Glycerol to Allyl Alcohol with 2-Hexanol As H-Donor – Catalyst Development and Separation Process

Authors 

Silva Vargas, K. - Presenter, Univ Lille, Centrale Lille, ENSCL, Univ Artois, UMR 8181 - UCCS- Unité de catalyse et chimie du solide
Katryniok, B., Univ Lille, Centrale Lille, ENSCL, Univ Artois, UMR 8181 - UCCS- Unité de catalyse et chimie du solide
Araque Marin, M., Univ Lille, Centrale Lille, ENSCL, Univ Artois, UMR 8181 - UCCS- Unité de catalyse et chimie du solide
Paul, S., Univ Lille, Centrale Lille, ENSCL, Univ Artois, UMR 8181 - UCCS- Unité de catalyse et chimie du solide
Dumeignil, F., Univ Lille, Centrale Lille, ENSCL, Univ Artois, UMR 8181 - UCCS- Unité de catalyse et chimie du solide
Ally alcohol is a very promising starting material for a variety of molecules such as acrylonitrile, acrolein, and acrylic acid – all, important intermediates for the chemical industry: the ammoxidation of allyl alcohol to acrylonitrile was reported with high yield (more than 80%) by Guillon et al.[i],[ii] . The selective oxidation of allyl alcohol to produce acrylic acid yields up to 85 % at rather low temperatures (300°C) over MoVOx catalyst was reported.[iii] However, the main bottleneck for these applications lies in the sourcing of allyl alcohol. Nowadays, allyl alcohol is produced by the selective catalytic hydrogenation of acrolein, which is obtained by the selective catalytic oxidation of propylene. Recently, we reported the synthesis of allyl alcohol in high yields (>86%) coming from deoxydehydration (DODH) of glycerol over heterogeneous rhenium based catalyst with 2-hexanol as sacrificial hydrogen-donor, at 175°C and 2.5h as reaction conditions. This catalyst maintained a catalytic performance stable several cycles and it did not pose issues of ageing. Furthermore, it showed a good catalytic performance (>80% yield) when other alcohols are used, mainly, secondary alcohols of long aliphatic chains (C5 to C8); it also maintained a good performance (> 80% Yield) when a glycerol purity in water was used up to 80%, and finally, did not present leaching problems, which makes it possible to perform its upscaling afterward.

Therefore, in order to approach a viable separation process, the distillation process of allyl alcohol was studied as the first stage of separation. Simulation process (via Aspen plus V9 software) was carried out using the binary coefficients of NRTL and WILSON thermodynamic models. The corresponding binary coefficients were obtained from the experimental equilibrium phase diagram liquid-vapor at atmospheric pressure as well as the corresponding activity coefficients. Binary mixtures such as 2-hexanol – allyl alcohol, 2-hexanol-2 hexanone, 2-hexanone-Allyl alcohol were studied. Finally, the simulation of a distillation column was performed using equilibrium thermodynamic data and Aspen HYSYS software.

[i] C. Liebig, S. Paul, B. Katryniok, C. Guillon, J-L. Coururier, J-L. Dubois, F. Dumeignil, W.F. Hoelderich, Appl. Catal. B: Env. 132-133 (2013) 170.

[ii] C. Guillon, C. Liebig, S. Paul, A-S. Mamede, W.F. Hoelderich, F. Dumeignil, B. Katryniok, Green Chem. 11 (2013) 3015.

[iii] T. Murayama, B. Katryniok, S. Heyte, M. Araque, S. Ishakawa, F. Dumeignil, S. Paul, W. Ueda, ChemCatChem 8 (2016) 1