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Furan Distribution as a Severity Indicator upon Organosolv Fractionation of Hardwood Sawdust through a Novel Ternary Solvent System
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Chemical Engineering.ORCID iD: 0000-0001-6011-6767
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Chemical Engineering.
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Chemical Engineering. Department of Earth and Environmental Sciences, University of Milano-Bicocca, Piazza della Scienza 1, 20126 Milan, Italy; NBFC − National Biodiversity Future Center, 90133 Palermo, Italy.ORCID iD: 0000-0003-3845-7017
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Chemical Engineering.ORCID iD: 0000-0001-7500-2367
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2024 (English)In: ACS Sustainable Chemistry and Engineering, E-ISSN 2168-0485, Vol. 12, no 4, p. 1666-1680Article in journal (Refereed) Published
Abstract [en]

Beech sawdust was treated with a ternary solvent system based on binary aqueous ethanol with partial substitution of ethanol by acetone at four different water contents (60, 50, 40, and 30%v/v). In addition to standard, i.e., noncatalyzed treatments, the application of inorganic acid in the form of 20 mm H2SO4 was evaluated. The various solvent systems were applied at 180 °C for 60 min. The obtained biomass fractions were characterized by standard biomass compositional methods, i.e., sugar monomer and oligomer contents, dehydration product contents of the aqueous product, and lignin, cellulose, and hemicellulose contents in isolated solid fractions. More advanced analyses were performed on the lignin fractions, including quantitative 13C NMR analyses, 1H–13C HSQC analysis, size exclusion chromatography, and pyrolysis-GC/MS, and the aqueous product, in the form of size exclusion chromatography and determination of total phenol contents. The picture emerging from the thorough analytical investigation performed on the lignin fractions is consistent with that resulting from the characterization of the other fractions: results point toward greater deconstruction of the lignocellulosic recalcitrance upon higher organic solvent content, replacing ethanol with acetone during the extraction, and upon addition of mineral acid. A pulp with cellulose content of 94.23 wt % and 95% delignification was obtained for the treatment employing a 55/30/15 EtOH/water/acetone mixture alongside 20 mm H2SO4. Furthermore, the results indicate the formation of two types of organosolv furan families during treatment, which differ in the substitution of their C1 and C5. While the traditional lignin aryl–ether linkages present themselves as indicators for process severity for the nonacid catalyzed systems, the distribution of these furan types can be applied as a severity indicator upon employment of H2SO4, including their presence in the isolated lignin fractions.

Place, publisher, year, edition, pages
American Chemical Society , 2024. Vol. 12, no 4, p. 1666-1680
Keywords [en]
fractionation, lignin, lignocellulose, organosolv, ternary solvent
National Category
Bioprocess Technology Analytical Chemistry
Research subject
Biochemical Process Engineering
Identifiers
URN: urn:nbn:se:ltu:diva-103975DOI: 10.1021/acssuschemeng.3c07236ISI: 001153822400001Scopus ID: 2-s2.0-85182564522OAI: oai:DiVA.org:ltu-103975DiVA, id: diva2:1832279
Funder
EU, Horizon 2020, 101007130
Note

Validerad;2024;Nivå 2;2024-01-29 (joosat);

Full text license: CC BY

Available from: 2024-01-29 Created: 2024-01-29 Last updated: 2024-05-02Bibliographically approved
In thesis
1. Structure and property oriented organosolv lignin extraction
Open this publication in new window or tab >>Structure and property oriented organosolv lignin extraction
2024 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In this Thesis, organosolv fractionation of softwood (spruce), hardwood (birch and beech), and herbaceous crops (wheat straw) was performed by applying various organosolv process conditions. Among these were a novel steam-explosion/organosolv hybrid mode, and two ternary solvent systems utilizing water/ethanol/acetone, and water/acetone/acetic acid. In addition, the effect of using inorganic acidic catalyst (H2SO4) was investigated for all raw material classes. Also, alkaline catalyst (NaOH) was investigated for wheat straw due to its reported high content of inorganics which presence adds additional structural complexity to the lignocellulosic recalcitrance. Following the organosolv fractionation, structural characterization was performed (content of cellulose, hemicellulose, lignin) in the isolated product fractions. Additionally, in-depth characterization of the isolated lignins was performed by combining Pyrolysis-Gas Chromatography Mass Spectroscopy (Pyr-GC/MS), Gel Permeation Chromatography (GPC), and different modes of Nuclear Magnetic Resonance (NMR; 13C, 1H-13C, 31P). Complementary analytics, such as content of monomeric/oligomeric sugars, dehydration products, total phenolics, and Size-Exclusion Chromatography (SEC) of the isolated product liquor, were performed to provide a comprehensive understanding of the process. Special attention was given the lignin structural changes occurring throughout the organosolv process. This was done as the use of lignin for higher-value application is considered crucial for the economic viability and development of a modern biorefinery. For this reason, significant focus was given to study how the lignin characteristics translate into physical properties such as solubility. The latter property was measured through solubility trials in binary aqueous acetone solutions, as well as solvent-based fractionation (acetone-water system). A coherent picture was aimed for, where structural motifs and lignin characteristics were correlated to reductions/enhancements in solubility at various water contents. To finally bridge this with a potential down-stream application, DPPH radical scavenging was performed in DMSO with and without intercalating Lithium Bromide (LiBr) for a selection of organosolv lignins, as well as their acetone/water fractionated lignins. This was complemented with a UV absorption study of the lignin solutions.The results provide a descriptive span of chemical characteristics related to organosolv lignins, where they range between highly native, to non-native. Whereas the former lignins are largely comprised of inter-unit motifs such as β-O-4’, β-β’ and β-5’, the non-native lignins are instead better characterized by a high content of oxidized sidechains, biaryls and bifurans, as well as showing strong indications of having quaternary cross-linkers originating from ketone functionalities. The ketones are also found to undergo aldol condensation with aldehydes formed throughout the process. Interestingly, these two extremes in lignin characteristics yield highly varying physical properties, where the predominantly native and non-native lignins for example display low and high solubility in pure acetone, respectively. Simultaneously, the latter is more prone towards water-induced precipitation, whereas the former instead require water to display complete (~100%) solubility at specific concentrations. These properties and findings are eventually consistent with recent literature where lignin aggregates also dominate their dissolved state, and the interunit motifs dictate the affinity on forming such aggregates which are important for both their dissolution, precipitation, but also their display of functionality such as antioxidant activity.                    

Place, publisher, year, edition, pages
Luleå: Luleå University of Technology, 2024
Series
Doctoral thesis / Luleå University of Technology 1 jan 1997 → …, ISSN 1402-1544
National Category
Chemical Process Engineering
Research subject
Biochemical Process Engineering
Identifiers
urn:nbn:se:ltu:diva-105316 (URN)978-91-8048-564-7 (ISBN)978-91-8048-565-4 (ISBN)
Public defence
2024-09-20, C305, Luleå University of Technology, Luleå, 12:00 (English)
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Supervisors
Available from: 2024-05-02 Created: 2024-05-02 Last updated: 2024-06-10Bibliographically approved

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Thoresen, Petter PaulsenDelgado Vellosillo, IreneLange, HeikoRova, UlrikaChristakopoulos, PaulMatsakas, Leonidas

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