Density functional theory study on the initial reactions of d-Xylose and d-Xylulose dehydration to furfural

Xiaowei Fang; Martin P Andersson; Ze Wang; Wenli Song; Songgeng Li

doi:10.1016/j.carres.2021.108463

Density functional theory study on the initial reactions of d-Xylose and d-Xylulose dehydration to furfural

Carbohydr Res. 2022 Jan:511:108463. doi: 10.1016/j.carres.2021.108463. Epub 2021 Oct 29.

Authors

Xiaowei Fang¹, Martin P Andersson², Ze Wang³, Wenli Song⁴, Songgeng Li⁴

Affiliations

¹ Xi'an Thermal Power Research Institute Co, LTD, China; State Key Laboratory of Multi-Phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Sino-Danish College, University of Chinese Academy of Sciences, Sino-Danish Center for Education and Research, Beijing, 100190, China.
² Department of Chemical and Biochemical Engineering, Technical University of Denmark, 2800, Lyngby, Kgs, Denmark. Electronic address: martan@kt.dtu.dk.
³ State Key Laboratory of Multi-Phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Sino-Danish College, University of Chinese Academy of Sciences, Sino-Danish Center for Education and Research, Beijing, 100190, China. Electronic address: wangze@ipe.ac.cn.
⁴ State Key Laboratory of Multi-Phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Sino-Danish College, University of Chinese Academy of Sciences, Sino-Danish Center for Education and Research, Beijing, 100190, China.

PMID: 34741878
DOI: 10.1016/j.carres.2021.108463

Abstract

The mechanism of the initial reactions in the acid-catalytic conversion of d-xylose/d-xylulose to furfural was studied with density functional theory. The reactions included mutual transformations among d-xylose, d-xylulose and the intermediate of 1,2-enediol. The catalytic performances of several acids including H₂SO₄, HNO₃, HCl, HBr and HI, and the solvent effects of water and THF (tetrahydrofuran) were studied. A simplified kinetic model of the d-xylose/d-xylulose-to-furfural conversion in water solvent was built, with the assumption that the conversion from 1,2-enediol to furfural was the rate-limiting step and could be treated as one-step reaction. The simulation can well fit the experimental regulation, which verifies the rationality of the model simplification. The dominant reaction pathways from d-xylose/d-xylulose to furfural were deduced based on the calculated energy barriers and corresponding reaction rate constants, with different acid catalysis and reaction mediums.

Keywords: Dominant reaction pathway; Energy barriers; Kinetic model; Rate-limiting step; Reaction mechanisms.

MeSH terms

Catalysis
Dehydration
Density Functional Theory
Furaldehyde*
Humans
Xylose
Xylulose*

Substances

Xylulose
Xylose
Furaldehyde