We explore a glycerol-to-olefins process in a reactor containing dehydration, hydrogenation, and upgrading stages in series. Glycerol, co-fed with H2 over HZSM-5 (1.0 g, Si/Al = 11.5, 400 C), was first dehydrated to yield a mixture of acetaldehyde, acrolein, and hydroxypropanone. Acrolein was hydrogenated to propanal over a Pd/α-Al2O 3 catalyst and the effluent was passed to a third stage which served to further upgrade propanal to olefins. Rapid third stage deactivation was observed, although, we obtained a maximum 70% yield of light olefins from a propanal stream reacted over HBEA (0.5 g, 500 C) with minimal CO production. A decrease in propanal conversion and C2-3 olefin yield was observed along with a corresponding increase in C4-5 olefin yield as time-on-stream increased to 150 min. We conclude that propanal condensed over Brønsted acid sites to form C4-5 olefins, which subsequently cracked at high conversion to form C2-3 olefins. Increasing the temperature from 400 to 500 C also decreased the C4-5 olefin yield from 13 to 9% while increasing C2-3 olefin yield from 4 to 15%. CC bond formation occurred during glycerol upgrading in a staged reactor configuration and negligible carbon is lost as CO.
Bibliographical noteFunding Information:
The authors acknowledge financial support from the National Science Foundation : Emerging Frontiers in Research and Innovation (EFRI) – Hydrocarbons from Biomass (award number: 0937706). SB acknowledges the National Science Foundation for a graduate research fellowship.
- Aldol condensation
- Glycerol upgrading