Ambient-pressure lignin valorization to high-performance polymers by intensified reductive catalytic deconstruction

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Abstract

Chemocatalytic lignin valorization strategies are critical for a sustainable bioeconomy, as lignin, especially technical lignin, is one of the most available and underutilized aromatic feedstocks. Here, we provide the first report of an intensified reactive distillation–reductive catalytic deconstruction (RD-RCD) process to concurrently deconstruct technical lignins from diverse sources and purify the aromatic products at ambient pressure. We demonstrate the utility of RD-RCD bio-oils in high-performance additive manufacturing via stereolithography 3D printing and highlight its economic advantages over a conventional reductive catalytic fractionation/RCD process. As an example, our RD-RCD reduces the cost of producing a biobased pressure-sensitive adhesive from softwood Kraft lignin by up to 60% in comparison to the high-pressure RCD approach. Last, a facile screening method was developed to predict deconstruction yields using easy-to-obtain thermal decomposition data. This work presents an integrated lignin valorization approach for upgrading existing lignin streams toward the realization of economically viable biorefineries.

Abstract

Process intensification was leveraged to develop a scalable route to upgrade lignin to high-performance materials and chemicals.

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Most cited references 76

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Chemicals from lignin: an interplay of lignocellulose fractionation, depolymerisation, and upgrading.

W. Schutyser, B Sels, G Beckham … (2018)

In pursuit of more sustainable and competitive biorefineries, the effective valorisation of lignin is key. An alluring opportunity is the exploitation of lignin as a resource for chemicals. Three technological biorefinery aspects will determine the realisation of a successful lignin-to-chemicals valorisation chain, namely (i) lignocellulose fractionation, (ii) lignin depolymerisation, and (iii) upgrading towards targeted chemicals. This review provides a summary and perspective of the extensive research that has been devoted to each of these three interconnected biorefinery aspects, ranging from industrially well-established techniques to the latest cutting edge innovations. To navigate the reader through the overwhelming collection of literature on each topic, distinct strategies/topics were delineated and summarised in comprehensive overview figures. Upon closer inspection, conceptual principles arise that rationalise the success of certain methodologies, and more importantly, can guide future research to further expand the portfolio of promising technologies. When targeting chemicals, a key objective during the fractionation and depolymerisation stage is to minimise lignin condensation (i.e. formation of resistive carbon-carbon linkages). During fractionation, this can be achieved by either (i) preserving the (native) lignin structure or (ii) by tolerating depolymerisation of the lignin polymer but preventing condensation through chemical quenching or physical removal of reactive intermediates. The latter strategy is also commonly applied in the lignin depolymerisation stage, while an alternative approach is to augment the relative rate of depolymerisation vs. condensation by enhancing the reactivity of the lignin structure towards depolymerisation. Finally, because depolymerised lignins often consist of a complex mixture of various compounds, upgrading of the raw product mixture through convergent transformations embodies a promising approach to decrease the complexity. This particular upgrading approach is termed funneling, and includes both chemocatalytic and biological strategies.

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Bright Side of Lignin Depolymerization: Toward New Platform Chemicals

Zhuohua Sun, Bálint Fridrich, Alessandra de Santi … (2018)

Lignin, a major component of lignocellulose, is the largest source of aromatic building blocks on the planet and harbors great potential to serve as starting material for the production of biobased products. Despite the initial challenges associated with the robust and irregular structure of lignin, the valorization of this intriguing aromatic biopolymer has come a long way: recently, many creative strategies emerged that deliver defined products via catalytic or biocatalytic depolymerization in good yields. The purpose of this review is to provide insight into these novel approaches and the potential application of such emerging new structures for the synthesis of biobased polymers or pharmacologically active molecules. Existing strategies for functionalization or defunctionalization of lignin-based compounds are also summarized. Following the whole value chain from raw lignocellulose through depolymerization to application whenever possible, specific lignin-based compounds emerge that could be in the future considered as potential lignin-derived platform chemicals.

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Formic-acid-induced depolymerization of oxidized lignin to aromatics.

Alireza Rahimi, Arne Ulbrich, Joshua Coon … (2014)

Lignin is a heterogeneous aromatic biopolymer that accounts for nearly 30% of the organic carbon on Earth and is one of the few renewable sources of aromatic chemicals. As the most recalcitrant of the three components of lignocellulosic biomass (cellulose, hemicellulose and lignin), lignin has been treated as a waste product in the pulp and paper industry, where it is burned to supply energy and recover pulping chemicals in the operation of paper mills. Extraction of higher value from lignin is increasingly recognized as being crucial to the economic viability of integrated biorefineries. Depolymerization is an important starting point for many lignin valorization strategies, because it could generate valuable aromatic chemicals and/or provide a source of low-molecular-mass feedstocks suitable for downstream processing. Commercial precedents show that certain types of lignin (lignosulphonates) may be converted into vanillin and other marketable products, but new technologies are needed to enhance the lignin value chain. The complex, irregular structure of lignin complicates chemical conversion efforts, and known depolymerization methods typically afford ill-defined products in low yields (that is, less than 10-20wt%). Here we describe a method for the depolymerization of oxidized lignin under mild conditions in aqueous formic acid that results in more than 60wt% yield of low-molecular-mass aromatics. We present the discovery of this facile C-O cleavage method, its application to aspen lignin depolymerization, and mechanistic insights into the reaction. The broader implications of these results for lignin conversion and biomass refining are also considered.

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Author and article information

Contributors

Robert M. O’Dea:

ORCID: https://orcid.org/0000-0002-7280-4687

Role: ConceptualizationRole: Formal analysisRole: InvestigationRole: MethodologyRole: ResourcesRole: ValidationRole: VisualizationRole: Writing - original draftRole: Writing - review & editing

Paula A. Pranda: Role: ConceptualizationRole: Data curationRole: Formal analysisRole: InvestigationRole: MethodologyRole: Project administrationRole: ResourcesRole: SoftwareRole: SupervisionRole: ValidationRole: VisualizationRole: Writing - original draftRole: Writing - review & editing

Yuqing Luo:

ORCID: https://orcid.org/0000-0002-4174-946X

Role: ConceptualizationRole: Formal analysisRole: MethodologyRole: ValidationRole: VisualizationRole: Writing - original draftRole: Writing - review & editing

Alice Amitrano: Role: ConceptualizationRole: Data curationRole: InvestigationRole: MethodologyRole: ResourcesRole: ValidationRole: VisualizationRole: Writing - original draftRole: Writing - review & editing

Elvis O. Ebikade:

ORCID: https://orcid.org/0000-0003-2350-0270

Role: Formal analysisRole: InvestigationRole: MethodologyRole: ValidationRole: Writing - review & editing

Eric R. Gottlieb:

ORCID: https://orcid.org/0000-0002-7948-8031

Role: ConceptualizationRole: Methodology

Olumoye Ajao:

ORCID: https://orcid.org/0000-0002-0816-8866

Role: ConceptualizationRole: InvestigationRole: MethodologyRole: Project administrationRole: ResourcesRole: SupervisionRole: ValidationRole: VisualizationRole: Writing - original draftRole: Writing - review & editing

Marzouk Benali:

ORCID: https://orcid.org/0000-0003-1920-7020

Role: ConceptualizationRole: Funding acquisitionRole: InvestigationRole: MethodologyRole: Project administrationRole: ResourcesRole: SupervisionRole: ValidationRole: VisualizationRole: Writing - original draftRole: Writing - review & editing

Dionisios G. Vlachos:

ORCID: https://orcid.org/0000-0002-6795-8403

Role: ConceptualizationRole: Data curationRole: Funding acquisitionRole: MethodologyRole: Project administrationRole: SupervisionRole: ValidationRole: Writing - original draftRole: Writing - review & editing

Marianthi Ierapetritou:

ORCID: https://orcid.org/0000-0002-1758-9777

Role: MethodologyRole: Project administrationRole: SupervisionRole: Writing - review & editing

Thomas H. Epps III:

ORCID: https://orcid.org/0000-0002-2513-0966

Role: ConceptualizationRole: Formal analysisRole: Funding acquisitionRole: MethodologyRole: Project administrationRole: SupervisionRole: ValidationRole: Writing - original draftRole: Writing - review & editing

Journal

Journal ID (nlm-ta): Sci Adv

Journal ID (iso-abbrev): Sci Adv

Journal ID (publisher-id): sciadv

Journal ID (hwp): advances

Title: Science Advances

Publisher: American Association for the Advancement of Science

ISSN (Electronic): 2375-2548

Publication date Collection: January 2022

Publication date (Electronic, pub): 19 January 2022

Volume: 8

Issue: 3

Electronic Location Identifier: eabj7523

Affiliations

[1 ]Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE 19716, USA.

[2 ]Catalysis Center for Energy Innovation, 221 Academy St., Newark, DE 19716, USA.

[3 ]Natural Resources Canada, CanmetENERGY, P.O. Box 4800, Varennes, Quebec J3X 1S6, Canada.

[4 ]Department of Materials Science and Engineering, University of Delaware, Newark, DE 19716, USA.

[5 ]Center for Research in Soft matter and Polymers (CRiSP), University of Delaware, Newark, DE 19716, USA.

Author notes

[†]

These authors contributed equally to this work.

[* ]Corresponding author. Email: thepps@ 123456udel.edu

Author information

Robert M. O’Dea https://orcid.org/0000-0002-7280-4687

Yuqing Luo https://orcid.org/0000-0002-4174-946X

Elvis O. Ebikade https://orcid.org/0000-0003-2350-0270

Eric R. Gottlieb https://orcid.org/0000-0002-7948-8031

Olumoye Ajao https://orcid.org/0000-0002-0816-8866

Marzouk Benali https://orcid.org/0000-0003-1920-7020

Dionisios G. Vlachos https://orcid.org/0000-0002-6795-8403

Marianthi Ierapetritou https://orcid.org/0000-0002-1758-9777

Thomas H. Epps III https://orcid.org/0000-0002-2513-0966

Article

Publisher ID: abj7523

DOI: 10.1126/sciadv.abj7523

PMC ID: 8769544

PubMed ID: 35044829

SO-VID: ffaa2d68-469f-459b-ac8e-32abaa1ab76a

Copyright © Copyright © 2022 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

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This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license, which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited.

History

Date received : 30 May 2021

Date accepted : 22 November 2021

Funding

Funded by: FundRef http://dx.doi.org/10.13039/100000001, National Science Foundation;

Award ID: NSF GCR CMMI 1934887

Funded by: FundRef http://dx.doi.org/10.13039/501100012394, Canadian Forest Service;

Award ID: Program on Energy Research and Development

Funded by: Delaware Bioscience Center for Advanced Technology;

Award ID: Entrepreneurial Proof of Concept Grant

Funded by: Canadian Forest Service at Natural Resources Canada;

Award ID: Forest Innovation Program

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Ambient-pressure lignin valorization to high-performance polymers by intensified reductive catalytic deconstruction

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Negative Pressure Wound Therapy

Most cited references 76

Chemicals from lignin: an interplay of lignocellulose fractionation, depolymerisation, and upgrading.

Bright Side of Lignin Depolymerization: Toward New Platform Chemicals

Formic-acid-induced depolymerization of oxidized lignin to aromatics.

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