Publication Date

10-5-2020

Department

Mechanical Engineering; Agricultural and Biosystems Engineering; Chemical and Biological Engineering; Bioeconomy Institute (BEI)

Campus Units

Mechanical Engineering, Chemical and Biological Engineering, Agricultural and Biosystems Engineering, Bioeconomy Institute (BEI)

OSTI ID+

1665904

Report Number

IS-J 10336

DOI

10.1039/D0GC02505D

Journal Title

Green Chemistry

Volume Number

22

Issue Number

19

First Page

6567

Last Page

6578

Abstract

We demonstrate for the first time non-catalytic, oxidative cracking with molecular oxygen (O2) to depolymerize native lignin into oxygenated phenolic monomers. Maximum monomer yield of 10.5 wt% was achieved at 250 °C after only 10 min of reaction and included vanillin, syringaldehyde, vanillic acid, and syringic acid. High rates of oxidation are attributed to the use of perfluorodecalin as solvent. Perfluorodecalin is a perfluorocarbon (PFC), characterized by their chemical stability and exceptionally high solubility for O2. Monomer yields were typically five-fold higher in perfluorodecalin compared to solvents more commonly employed in lignin conversion, such as methanol, butanol, acetonitrile, and ethyl acetate. Phenolic monomer production in perfluorodecalin favors high temperatures and short reaction times to prevent further oxidation of the produced monomers. Lignin oil obtained under oxidative conditions in perfluorodecalin showed lower molecular weight and smaller polydispersity compared to other solvents. Increasing the reaction time further decreased the molecular weight, while increasing reaction time in an inert atmosphere increased the molecular weight of the lignin oil. High concentrations of O2 in perfluorodecalin not only increased lignin depolymerization but suppressed undesirable condensation reactions. Depolymerization is likely initiated by thermally induced homolytic cleavage of ether linkages in lignin to form phenoxy and carbon-based radicals. These radicals bind with O2 as a radical scavenger and further react to form phenolic monomeric products rather than repolymerizing to large oligomers. The PFC process was scaled from 5 mL to 250 mL without any loss of yield. Because most organic compounds are not soluble in perfluorodecalin, recycling is easily achieved via liquid–liquid separation.

DOE Contract Number(s)

AC02-07CH11358

Language

en

Publisher

Iowa State University Digital Repository, Ames IA (United States)

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