Abstract

Biomass-derived solvents have been proposed as a novel pathway in biorefining for the realization of biofuels and bioproducts derived from lignocellulosic biomass. Cyrene derived from cellulose has recently been shown to have a high potential as a green organic solvent for pretreating poplar biomass. However, due to its high dynamic viscosity nature, high Cyrene concentration could cause negative effects on the sugar release of the pretreated biomass as well as driving up the operational cost of the lignin recovery. In this study, we combine experimental and computational approaches to examine the impact of Cyrene pretreatment with reduced Cyrene concentration under mild conditions on switchgrass lignin. Our experimental studies indicated correlation between pretreatment condition and recovery and structure modification of lignin. Switchgrass lignin extracted by Cyrene pretreatment possessed high preservation of β-O-4 ether inter-unit linkage, which could provide versatility in the integration of downstream lignin valorization into the modern biorefinery industries. Molecular modeling examining the solvation of switchgrass lignin polymer and the disaggregation of low-molecular weight lignin aggregates under pretreatment conditions indicated that a preferential interaction exists between Cyrene and lignin, which likely drives lignin release, and that the disruption of inter-lignin contacts can be modulated as a non-monotonic function ofmore » Cyrene : water ratio. Further, while Cyrene–lignin interactions permit the solubilization of lignin, simulations with proxy reactive-species reveal that changes to the diffusion of these reactive proxies and their localization near linkage sites under Cyrene conditions may inhibit chemical processes. In conclusion, the results indicated that loss of pretreatment efficacy caused by low Cyrene concentration could be compensated by prolonged pretreatment time and high catalyst dosage.« less

Authors:

Wang, Yun-Yan ^[1]; Wang, Yunxuan ^[1]; Liang, Luna ^[1]; Smith, Micholas Dean  ^[2];

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• Search DOE PAGES for ORCID "0000-0002-0777-7539"

Meng, Xianzhi  ^[1];

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• Search DOE PAGES for ORCID "0000-0003-4303-3403"

Pu, Yunqiao  ^[3];

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• Search DOE PAGES for ORCID "0000-0003-2554-1447"

Mazarei, Mitra ^[1]; Agarwal, Rupesh  ^[2];

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• Search DOE PAGES for ORCID "0000-0003-1029-2281"

Rukmani, Shalini J.  ^[3];

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• Search DOE PAGES for ORCID "0000-0001-8474-9403"

Davison, Brian H.  ^[3];

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• Search DOE PAGES for ORCID "0000-0002-7408-3609"

Ragauskas, Arthur J.  ^[2]

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• Search DOE PAGES for ORCID "0000-0002-3536-554X"

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+ Show Author Affiliations

1. University of Tennessee, Knoxville, TN (United States)
2. University of Tennessee, Knoxville, TN (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
3. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Publication Date:

Wed Oct 04 00:00:00 EDT 2023

Research Org.:

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR)

OSTI Identifier:

2267627

Alternate Identifier(s):

OSTI ID: 2202491

Grant/Contract Number:  

AC05-00OR22725; ERCAP0025417

Resource Type:

Accepted Manuscript

Journal Name:

Green Chemistry

Additional Journal Information:

Journal Volume: 26; Journal Issue: 6; Journal ID: ISSN 1463-9262

Publisher:

Royal Society of Chemistry

Country of Publication:

United States

Language:

English

Subject:

09 BIOMASS FUELS