Altmetric

From lignin to chemicals: Hydrogenation of lignin models and mechanistic insights into hydrodeoxygenation via low-temperature C-O bond cleavage

File Description SizeFormat 
ACSCatBri0718REV2.docxFile embargoed until 25 January 2020575.08 kBMicrosoft Word    Request a copy
Title: From lignin to chemicals: Hydrogenation of lignin models and mechanistic insights into hydrodeoxygenation via low-temperature C-O bond cleavage
Authors: Vriamont, CEJJ
Chen, T
Romain, C
Corbett, P
Manageracharath, P
Peet, J
Conifer, CM
Hallett, JP
Britovsek, GJP
Item Type: Journal Article
Abstract: The catalytic hydrogenation of a series of lignin model compounds, including anisole, guaiacol, 1,2-dimethoxybenzene, 4-propyl-2-methoxyphenol, and syringol, has been investigated in detail, using a Ru/C catalyst in acetic acid as the solvent. Both hydrogenation of the aromatic unit and C–O bond cleavage are observed, resulting in a mixture of cyclohexanes and cyclohexanols, together with cyclohexyl acetates due to esterification with the solvent. The effect on product composition of the reaction parameters temperature (80–140 °C), pressure (10–40 bar), and reaction time (0.5–4 h) has been evaluated in detail. The lignin model compound 4-propyl-2-methoxyphenol was converted to 4-propylcyclohexanol in 4 h at 140 °C and 30 bar of H2 pressure with 84% conversion and 63% selectivity. Mechanistic studies on the reactivity of reaction intermediates have shown that C–O bond cleavage under these relatively mild conditions does not involve a C–O bond hydrogenolysis reaction but is due to elimination and hydrolysis reactions (or acetolysis in acetic acid solvent) of highly reactive cyclohexadiene- and cyclohexene-based enols, enol ethers, and allyl ethers.
Issue Date: 1-Mar-2019
Date of Acceptance: 1-Jan-2019
URI: http://hdl.handle.net/10044/1/69605
DOI: https://dx.doi.org/10.1021/acscatal.8b04714
ISSN: 2155-5435
Publisher: American Chemical Society
Start Page: 2345
End Page: 2354
Journal / Book Title: ACS Catalysis
Volume: 9
Issue: 3
Copyright Statement: © 2019 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, after peer review and technical editing by the publisher. To access the final edited and published work see https://dx.doi.org/10.1021/acscatal.8b04714
Sponsor/Funder: Engineering & Physical Science Research Council (EPSRC)
The Coca-Cola Company
Funder's Grant Number: EP/K014676/1
4504238214
Keywords: Science & Technology
Physical Sciences
Chemistry, Physical
Chemistry
lignin
hydrogenation
hydrogenolysis
ruthenium
biomass
hydrodemethoxylation
AQUEOUS-PHASE HYDROGENATION
TEREPHTHALIC ACID
ACETIC-ACID
BIO-OIL
SELECTIVE HYDROGENATION
HETEROGENEOUS CATALYSTS
RU-H2O SYSTEM
VINYL ETHERS
PH DIAGRAM
BIOMASS
Publication Status: Published
Embargo Date: 2020-01-25
Online Publication Date: 2019-01-25
Appears in Collections:Chemistry
Catalysis and Advanced Materials
Chemical Engineering
Faculty of Natural Sciences



Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

Creative Commonsx