Kinetics of Levoglucosenone Isomerization. Issue 1 (13th December 2016)

• Record Type: Journal Article
• Authors: Krishna, Siddarth H.; Walker, Theodore W.; Dumesic, James A.; Huber, George W.
• Is Part Of: ChemSusChem. Volume 10:Issue 1(2017)
• Page Start: 129
• Page End: 138
• Publication Date: 2016-12-13
• Subjects: 5-hydroxymethylfurfural -- biomass -- isomerization -- kinetics -- levoglucosenone; Green chemistry -- Periodicals; Sustainable engineering -- Periodicals; Chemistry -- Periodicals; Chemical engineering -- Periodicals; 660
• DOI: 10.1002/cssc.201601308
• Languages: English
• ISSNs: 1864-5631

Abstract

Abstract: We studied the acid‐catalyzed isomerization of levoglucosenone (LGO) to 5‐hydroxymethylfurfural (HMF) and developed a reaction kinetics model that describes the experimental data across a range of conditions (100–150 °C, 50–100 mm H2 SO4, 50–150 mm LGO). LGO and its hydrated derivative exist in equilibrium under these reaction conditions. Thermal and catalytic degradation of HMF are the major sources of carbon loss. Within the range of conditions studied, higher temperatures and shorter reaction times favor the production of HMF. The yields of HMF and levulinic acid decrease monotonically as tetrahydrofuran is added to the aqueous solvent system, indicating that water plays a role in the LGO isomerization reaction. Initial‐rate analyses show that HMF is produced solely from LGO rather than from the hydrated derivative of LGO. The results of this study are consistent with a mechanism for LGO isomerization that proceeds through hydration of the anhydro bridge, followed by ring rearrangement analogous to the isomerization of glucose to fructose. Abstract : Finding the path : Levoglucosenone is a promising biomass‐derived platform molecule for the production of renewable chemicals. In the presence of water and a Brønsted acid catalyst, levoglucosenone undergoes isomerization to form 5‐hydroxymethylfurfural, which is further converted to levulinic acid and formic acid. The reaction network, mechanism, and kinetics of levoglucosenone isomerization are explored herein.