Selective Fragmentation of Biorefinery Corncob Lignin into p‐Hydroxycinnamic Esters with a Supported Zinc Molybdate Catalyst

Lignin is the largest renewable resource of bioaromatics, and the catalytic fragmentation of lignin into phenolic monomers is increasingly recognized as an important starting point for lignin valorization. Herein, we report that ZnMoO4 supported on MCM‐41 can catalyze the fragmentation of biorefiner...

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Bibliographic Details
Published in:ChemSusChem 2018-07, Vol.11 (13), p.2114-2123
Main Authors: Wang, Shuizhong, Gao, Wa, Li, Helong, Xiao, Ling‐Ping, Sun, Run‐Cang, Song, Guoyong
Format: Article
Language:English
Subjects:
biomass
biorefinery
Catalysis
Catalysts
Catalytic activity
Deactivation
Esters
Fragmentation
Lignin
molybdenum
Monomers
Polyester resins
Refining
Selectivity
supported catalysts
Zinc
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Summary:Lignin is the largest renewable resource of bioaromatics, and the catalytic fragmentation of lignin into phenolic monomers is increasingly recognized as an important starting point for lignin valorization. Herein, we report that ZnMoO4 supported on MCM‐41 can catalyze the fragmentation of biorefinery technical lignin, enzymatic mild acidolysis lignin, and native lignin derived from corncob to yield lignin oily products that contain 15–37.8 wt % phenolic monomers, in which the high selectivities towards methyl coumarate (1) and methyl ferulate (2) were obtained (up to 78 %). The effects of some key parameters such as the influence of the solvent, reaction temperature, time, H2 pressure, and catalyst dosage were examined in view of activity and selectivity. The loss of Zn from the catalyst is discussed as the primary cause of deactivation, and the catalytic activity and selectivity can be well preserved in at least six runs by thermal calcination. The high selectivity to 1 and 2 leads to their easy separation and purification from lignin oily product to provide sustainable monomers for the preparation of functional polyether esters and polyesters. Breaking good: The catalytic fragmentation of biorefinery technical lignin, enzymatic mild acidolysis lignin, and native lignin derived from corncob with ZnMoO4/MCM‐41 can afford methyl coumarate and methyl ferulate selectively.
ISSN:1864-5631
1864-564X
DOI:10.1002/cssc.201800455