Mechanism for the formation of hydroxyacetaldehyde by the pyrolysis of xylopyranose and <em>O</em>-acetyl-xylopyranose

TIAN Hui-yun; HU Bin; ZHANG Yang; LU Qiang; DONG Chang-qing; YANG Yong-ping

Volume 43 Issue 02

Feb. 2015

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Article Navigation > Journal of Fuel Chemistry and Technology > 2015 > 43(02): 185-194

TIAN Hui-yun, HU Bin, ZHANG Yang, LU Qiang, DONG Chang-qing, YANG Yong-ping. Mechanism for the formation of hydroxyacetaldehyde by the pyrolysis of xylopyranose and O-acetyl-xylopyranose[J]. Journal of Fuel Chemistry and Technology, 2015, 43(02): 185-194.

Citation:

TIAN Hui-yun, HU Bin, ZHANG Yang, LU Qiang, DONG Chang-qing, YANG Yong-ping. Mechanism for the formation of hydroxyacetaldehyde by the pyrolysis of xylopyranose and O-acetyl-xylopyranose[J]. Journal of Fuel Chemistry and Technology, 2015, 43(02): 185-194.

Citation:

TIAN Hui-yun, HU Bin, ZHANG Yang, LU Qiang, DONG Chang-qing, YANG Yong-ping. Mechanism for the formation of hydroxyacetaldehyde by the pyrolysis of xylopyranose and O-acetyl-xylopyranose[J]. Journal of Fuel Chemistry and Technology, 2015, 43(02): 185-194.

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Mechanism for the formation of hydroxyacetaldehyde by the pyrolysis of xylopyranose and O-acetyl-xylopyranose

National Engineering Laboratory for Biomass Power Generation Equipment, North China Electric Power University, Beijing 102206, China

Received Date: 2014-08-09
Rev Recd Date: 2014-10-09
Publish Date: 2015-02-28

Abstract

Abstract

Xylopyranose and O-acetyl-xylopyranose, the two monomers of xylan, were employed as the model compounds to study the mechanism for the formation of hydroxyacetaldehyde (HAA) from xylan by pyrolysis. Six possible pathways from xylopyranose and three from O-acetyl-xylopyranose were proposed by employing the density functional theory (DFT) at B3LYP/6-31+G(d,p) level; the energetically favored pathways for HAA formation were revealed. Xylopyranose may undergo ring-opening, dehydration, rearrangement and retro-aldol reactions sequentially, to form HAA that contains C4/C5; the rate-determining step is the dehydration reaction, with an energy barrier of 253.3 kJ/mol. From O-acetyl-xylopyranose, the side chain is cleaved in the first place, forming acetic acid (AA) and a cyclic intermediate; the ring-opening and H-shift reactions happen afterwards from the cyclic intermediate to generate HAA containing C4/C5; the rate-determining step is the H-shif reaction, with an energy barrier of 317.6 kJ/mol.
- xylopyranose,
- O-acetyl,
- pyrolysis,
- hydroxyacetaldehyde,
- density functional theory

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References

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