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Mild organosolv lignin extraction with alcohols: the importance of benzylic alkoxylation

Research output: Contribution to journalArticlepeer-review

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Mild organosolv lignin extraction with alcohols : the importance of benzylic alkoxylation. / Zijlstra, Douwe S.; Lahive, Ciaran; Analbers, Coen A.; Figueiredo, Monique Bernardes; Wang, Zhiwen; Lancefield, Chris; Deuss, Peter J.

In: ACS Sustainable Chemistry & Engineering , Vol. 8, No. 13, 06.04.2020, p. 5119-5131.

Research output: Contribution to journalArticlepeer-review

Harvard

Zijlstra, DS, Lahive, C, Analbers, CA, Figueiredo, MB, Wang, Z, Lancefield, C & Deuss, PJ 2020, 'Mild organosolv lignin extraction with alcohols: the importance of benzylic alkoxylation', ACS Sustainable Chemistry & Engineering , vol. 8, no. 13, pp. 5119-5131. https://doi.org/10.1021/acssuschemeng.9b07222

APA

Zijlstra, D. S., Lahive, C., Analbers, C. A., Figueiredo, M. B., Wang, Z., Lancefield, C., & Deuss, P. J. (2020). Mild organosolv lignin extraction with alcohols: the importance of benzylic alkoxylation. ACS Sustainable Chemistry & Engineering , 8(13), 5119-5131. https://doi.org/10.1021/acssuschemeng.9b07222

Vancouver

Zijlstra DS, Lahive C, Analbers CA, Figueiredo MB, Wang Z, Lancefield C et al. Mild organosolv lignin extraction with alcohols: the importance of benzylic alkoxylation. ACS Sustainable Chemistry & Engineering . 2020 Apr 6;8(13):5119-5131. https://doi.org/10.1021/acssuschemeng.9b07222

Author

Zijlstra, Douwe S. ; Lahive, Ciaran ; Analbers, Coen A. ; Figueiredo, Monique Bernardes ; Wang, Zhiwen ; Lancefield, Chris ; Deuss, Peter J. / Mild organosolv lignin extraction with alcohols : the importance of benzylic alkoxylation. In: ACS Sustainable Chemistry & Engineering . 2020 ; Vol. 8, No. 13. pp. 5119-5131.

Bibtex - Download

@article{27558ec8bf9143c0b1affe31d17549b7,
title = "Mild organosolv lignin extraction with alcohols: the importance of benzylic alkoxylation",
abstract = "Lignin holds the key for maximizing value extraction from lignocellulosic biomass. This is currently hindered by the application of fractionation methods that significantly alter the lignin structure to give highly recalcitrant materials. For this reason, it can be highly beneficial to use less-severe fractionation conditions that allow for efficient extraction of lignin with retention of the β-aryl ether (β-O-4) content. Here, we present a detailed study on mild alcohol-based organosolv fractionation with the aim of understanding how to achieve a balance between efficiency of lignin extraction and the structure of the resulting lignin polymers, using walnut shells as model biomass. Monitoring different extraction conditions reveals how the structure of the extracted lignin changes depending on the extraction conditions in terms of molecular weight, alcohol incorporation, and H/G/S ratios. Moving from ethanol to n-pentanol, it was revealed that, in particular, alcohol incorporation at the benzylic α-position of β-aryl ether units not only plays a key role in protecting the β-O-4 linking motif but more importantly increases the solubility of larger lignin fragments under extraction conditions. This study shows that α-substitution already occurs prior to extraction and is essential for reaching improved extraction efficiencies. Furthermore, α-substitution with not only bulky secondary alcohols and tertiary alcohols but also chloride was revealed for the first time and the latter could be involved in facilitating α-alkoxylation. Overall, this study demonstrates how by tuning the fractionation setup and conditions, the resulting lignin characteristics can be influenced and potentially tailored to suit downstream demands.",
keywords = "Lignin, Mild organosolv extraction, Benzvlic alkoxvlation, β-O-4 retention, Solvent effects",
author = "Zijlstra, {Douwe S.} and Ciaran Lahive and Analbers, {Coen A.} and Figueiredo, {Monique Bernardes} and Zhiwen Wang and Chris Lancefield and Deuss, {Peter J.}",
note = "C.S.L. thanks the Leverhulme Trust Early Career Fellowship (ECF-2018-480). Z.W. acknowledges the China Scholarship Council for funding (grant number 201706300138).",
year = "2020",
month = apr,
day = "6",
doi = "10.1021/acssuschemeng.9b07222",
language = "English",
volume = "8",
pages = "5119--5131",
journal = "ACS Sustainable Chemistry & Engineering ",
issn = "2168-0485",
publisher = "American Chemical Society",
number = "13",

}

RIS (suitable for import to EndNote) - Download

TY - JOUR

T1 - Mild organosolv lignin extraction with alcohols

T2 - the importance of benzylic alkoxylation

AU - Zijlstra, Douwe S.

AU - Lahive, Ciaran

AU - Analbers, Coen A.

AU - Figueiredo, Monique Bernardes

AU - Wang, Zhiwen

AU - Lancefield, Chris

AU - Deuss, Peter J.

N1 - C.S.L. thanks the Leverhulme Trust Early Career Fellowship (ECF-2018-480). Z.W. acknowledges the China Scholarship Council for funding (grant number 201706300138).

PY - 2020/4/6

Y1 - 2020/4/6

N2 - Lignin holds the key for maximizing value extraction from lignocellulosic biomass. This is currently hindered by the application of fractionation methods that significantly alter the lignin structure to give highly recalcitrant materials. For this reason, it can be highly beneficial to use less-severe fractionation conditions that allow for efficient extraction of lignin with retention of the β-aryl ether (β-O-4) content. Here, we present a detailed study on mild alcohol-based organosolv fractionation with the aim of understanding how to achieve a balance between efficiency of lignin extraction and the structure of the resulting lignin polymers, using walnut shells as model biomass. Monitoring different extraction conditions reveals how the structure of the extracted lignin changes depending on the extraction conditions in terms of molecular weight, alcohol incorporation, and H/G/S ratios. Moving from ethanol to n-pentanol, it was revealed that, in particular, alcohol incorporation at the benzylic α-position of β-aryl ether units not only plays a key role in protecting the β-O-4 linking motif but more importantly increases the solubility of larger lignin fragments under extraction conditions. This study shows that α-substitution already occurs prior to extraction and is essential for reaching improved extraction efficiencies. Furthermore, α-substitution with not only bulky secondary alcohols and tertiary alcohols but also chloride was revealed for the first time and the latter could be involved in facilitating α-alkoxylation. Overall, this study demonstrates how by tuning the fractionation setup and conditions, the resulting lignin characteristics can be influenced and potentially tailored to suit downstream demands.

AB - Lignin holds the key for maximizing value extraction from lignocellulosic biomass. This is currently hindered by the application of fractionation methods that significantly alter the lignin structure to give highly recalcitrant materials. For this reason, it can be highly beneficial to use less-severe fractionation conditions that allow for efficient extraction of lignin with retention of the β-aryl ether (β-O-4) content. Here, we present a detailed study on mild alcohol-based organosolv fractionation with the aim of understanding how to achieve a balance between efficiency of lignin extraction and the structure of the resulting lignin polymers, using walnut shells as model biomass. Monitoring different extraction conditions reveals how the structure of the extracted lignin changes depending on the extraction conditions in terms of molecular weight, alcohol incorporation, and H/G/S ratios. Moving from ethanol to n-pentanol, it was revealed that, in particular, alcohol incorporation at the benzylic α-position of β-aryl ether units not only plays a key role in protecting the β-O-4 linking motif but more importantly increases the solubility of larger lignin fragments under extraction conditions. This study shows that α-substitution already occurs prior to extraction and is essential for reaching improved extraction efficiencies. Furthermore, α-substitution with not only bulky secondary alcohols and tertiary alcohols but also chloride was revealed for the first time and the latter could be involved in facilitating α-alkoxylation. Overall, this study demonstrates how by tuning the fractionation setup and conditions, the resulting lignin characteristics can be influenced and potentially tailored to suit downstream demands.

KW - Lignin

KW - Mild organosolv extraction

KW - Benzvlic alkoxvlation

KW - β-O-4 retention

KW - Solvent effects

U2 - 10.1021/acssuschemeng.9b07222

DO - 10.1021/acssuschemeng.9b07222

M3 - Article

VL - 8

SP - 5119

EP - 5131

JO - ACS Sustainable Chemistry & Engineering

JF - ACS Sustainable Chemistry & Engineering

SN - 2168-0485

IS - 13

ER -

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