Improved catalytic depolymerization of lignin waste using carbohydrate derivatives

doi:10.1016/j.envpol.2020.115674

Environmental Pollution

Volume 268, Part A, 1 January 2021, 115674

https://doi.org/10.1016/j.envpol.2020.115674 Get rights and content

Highlights

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Carbohydrate-derived additives were used in the depolymerization of lignin.
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The aromatic monomer yields from Kraft lignin and organosolv lignin increased.
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Mannitol and sucrose were found to most improve the aromatic monomer yields.
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Carbohydrates improved the lignin depolymerization of lignocellulose.
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The improved depolymerization was confirmed by GPC and NMR studies.

Abstract

Carbohydrate-

or sugar-derived compounds were used as environmentally friendly additives for the depolymerization of Kraft lignin waste and organosolv lignin prepared from Miscanthus giganteus. The yields of the aromatic monomers obtained from Kraft lignin increased from 5.1 to 49.2% with the addition of mannitol, while those obtained from organosolv lignin increased from 44.4 to 83.0% with the addition of sucrose. This improved lignin depolymerization was also confirmed by gel permeation chromatography and nuclear magnetic resonance spectroscopy. The above results clearly indicate the beneficial effects of carbohydrate derivatives on the lignin depolymersization process, more specifically, suggesting that the presence of carbohydrates improve the lignin depolymerization of lignocellulose, as observed for the raw lignocellulose feed.

Graphical abstract

Section snippets

Author statement

Sangseo Gu, Investigation, Writing – Original Darft. Jae-Wook Choi, Methodology, Formal analysis. Hyunjoo Lee, Methodology, Formal analysis. Dong Jin Suh, Conceptualization. Jungkyu Choi, Supervision, Writing - review & editing. Jeong-Myeong Ha, Supervision, Writing - review & editing.

Materials

The NH₃ form of zeolite β (NH₃-β, Si/Al = 25 (mol/mol) and BET surface area = 680 m²/g, as reported by the vendor) was purchased from Zeolyst (Conshohocken, Pennsylvania, USA). Arabinose (≥99.0%), alkali lignin (Kraft lignin, low sulfonate content), cellulose, D-(+)-cellobiose (≥98%), D-(+)-glucose (≥99%), D-mannitol, D-(+)-mannose, DL-glyceraldehyde (≥90.0%), L-(−)-arabitol, starch, ruthenium(III) chloride hydrate (RuCl₃·xH₂O), deuterated dimethyl sulfoxide (d₆-DMSO, 99.9%), pyridine

Catalytic depolymerization of the raw lignocellulose and the organosolv lignin

It has been reported that higher yields of the aromatic monomers were obtained from the depolymerization of raw biomass compared to extracted lignin (Renders et al., 2017; Son et al., 2019; Van den Bosch et al., 2017). Thus, we herein performed the catalytic depolymerization of the raw biomass of MG, its organosolv lignin (MGL), and commercially available Kraft lignin (AKL), whereby the highest aromatic monomer yield was obtained for MG (based on the measured fraction of lignin in MG) (Table 1).

Conclusion

We herein reported our investigation into the use of sugar-derived compounds as additives in the depolymerization of commercially available Kraft lignin (AKL) and organosolv lignin (MGL) prepared from M. giganteus (MG). The use of sugar derivatives prepared from biomass allowed the amount of added petroleum-based chemicals to be decreased, thus achieving a more environmentally friendly process. It was found that the depolymerization of MG exhibited the highest aromatic monomer yield compared to

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgement

This work was supported by the Korea Institute of Science and Technology (KIST) Institutional Program (2E30170).

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Roles of metal and acid sites in the reductive depolymerization of concentrated lignin over supported Pd catalysts
2023, Catalysis Today
Citation Excerpt :
Because of the poor solubility of lignin, several solvents including methanol [9,10], ethanol [10–12], 2-propanol [9], methylcylohexane [9], aqueous methanol [13–15], aqueous ethanol [10,11,13,16,17], tetrahydrofuran [10], amines [18], and others [19] were used for its dissolution. Lignin depolymerization is promoted by these organic solvents [9–13,18] and additives [14], and can be enhanced by improving the mobility of solvent-mixed lignin or providing a hydrogen supply through transfer hydrogenation. Although high-dilution conditions favor the formation of lignin oil and lignin-derived monomers, the associated need to handle large solvent quantities complicates the purification process and reduces economic feasibility.
Lignin is a natural polymer contained in lignocellulose and is a potential feedstock for the production of phenolics or small aromatic molecules. However, lignin depolymerization is typically performed using low lignin concentrations and insufficiently active catalysts, which hinders industrial applications. To address this issue, we herein investigated the depolymerization of concentrated kraft lignin and oak-extracted organosolv lignin promoted by supported bifunctional metal (palladium)-acid catalysts and elucidated the roles of acid and metal sites. In addition to acid sites, which are known to be critical for lignin degradation, metal sites were found to be required to initiate lignin depolymerization. Palladium atoms promoted depolymerization even in the absence of acid sites, while acid site–promoted depolymerization required the presence of surface palladium atoms. Catalysts with bulk palladium particles were much more active than those with highly dispersed palladium particles, which suggested that efficient depolymerization required the bulky lignin polymer to be adsorbed on the palladium surface in a multidentate fashion. Thus, our work provides valuable insights into the mechanism of catalytic lignin depolymerization and paves the way to the industrial-scale application of this process.
Metal/acid bifunctional catalysts for the reductive catalytic fractionation of lignocellulose into phenols and holocellulose
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Citation Excerpt :
Unsaturated fragments, such as G and S units, which are easily repolymerized, are produced in the initial solvolytic extraction [1,25]. The addition of organic chemicals, particularly sugar derivatives, also significantly improved the reductive depolymerization of lignin, achieving a yield of phenolic monomers as high as 83.0 % [38]. Finally, heterogeneous transition-metal catalysts (e.g., Ni, Ru, Rh, Pt, Pd, and Cu) can catalyze the depolymerization of lignin oligomers to generate stable monomers while hindering unwanted repolymerization [34,36,39–41].
Mongolian oak (MO), a lignocellulosic biomass feedstock comprising lignin, hemicellulose, and cellulose, was fractionated via reductive catalytic fractionation (RCF) into holocellulose-rich solid residue and lignin-derived phenol-rich liquid oil. To achieve an economically feasible RCF process, tungstate-zirconia (WZr)-supported metal catalysts, exhibiting bifunctionalities of hydrogen-adsorbing metal and acidic WZr, were used for depolymerizing and valorizing lignocellulose, and their catalytic activity was found to be highly dependent on the deposited metal. Ru/WZr exhibited excellent fractioning ability, achieving a maximum yield of 23.6 wt% of monomeric and dimeric compounds from MO and exhibiting the potential to be techno-economically viable. The superior activity of Ru/WZr can be attributed to the synergistic effects of metal and acid, which were studied by investigating the product distributions of aromatic small molecules depending on the properties of WZr-supported metal catalysts. The stabilization of reactive radical intermediates depending on the surface Brønsted acidity of acid catalysts and hydrogen-adsorbing ability of metals were also investigated. RCF reaction conditions were optimized for the maximum yield of monomeric compounds, which can be beneficial for the further development of industrial processes.
Visibly transparent UV protection and adjusted mechanical properties of films composed of lignin-derived wastes and poly[(R)-3-hydroxybutyric acid]
2023, Korean Journal of Chemical Engineering
Effects of the Preferential Oxidation of Phenolic Lignin Using Chlorine Dioxide on Pulp Bleaching Efficiency
2022, International Journal of Molecular Sciences
Wastewater as a Resource for Pest Control: An Overview
2021, BioResources

^☆: This paper has been recommended for acceptance by Jörg Rinklebe.

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Improved catalytic depolymerization of lignin waste using carbohydrate derivatives☆

Highlights

Abstract

Carbohydrate-

Graphical abstract

Section snippets

Author statement

Materials

Catalytic depolymerization of the raw lignocellulose and the organosolv lignin

Conclusion

Declaration of competing interest

Acknowledgement

Joule

Renew. Sustain. Energy Rev.

Bioresour. Technol.

Chem. Eng. J.

J. Ind. Eng. Chem.

Appl. Catal. Gen.

Environ. Pollut.

Methanol as hydrogen source: transfer hydrogenation of aromatic aldehydes with a rhodacycle

Chem. Commun.

Integrated conversion of hemicellulose and cellulose from lignocellulosic biomass

Energy Environ. Sci.

Evaluation of small organic acids present in fast pyrolysis bio-oil from lignocellulose as feedstocks for bacterial bioconversion

GCB Bioenergy

Catalytic biorefining of plant biomass to non-pyrolytic lignin bio-oil and carbohydrates through hydrogen transfer reactions

Angew. Chem. Int. Ed.

Selective route to 2-propenyl aryls directly from wood by a tandem organosolv and palladium-catalysed transfer hydrogenolysis

Chemsuschem

Valorization of lignin to simple phenolic compounds over tungsten carbide: impact of lignin structure

Chemsuschem

Role of Cu–Mg–Al mixed oxide catalysts in lignin depolymerization in supercritical ethanol

ACS Catal.

Catalytic depolymerization of lignin in supercritical ethanol

Chemsuschem

Effective release of lignin fragments from lignocellulose by Lewis acid metal triflates in the lignin-first approach

Chemsuschem

Conversion of lignin to phenol-rich oil fraction under supercritical alcohols in the presence of metal catalysts

Energy & Fuels

Recent efforts to prevent undesirable reactions from fractionation to depolymerization of lignin: toward maximizing the value from lignin

Frontiers in Energy Research

Lignin depolymerization over Ni/C catalyst in methanol, a continuation: effect of substrate and catalyst loading

Catalysis Science & Technology

Synthesis and utilisation of sugar compounds derived from lignocellulosic biomass

Green Chem.

Protection group effects during α,γ-diol lignin stabilization promote high-selectivity monomer production

Angew. Chem. Int. Ed.

Lignin-first depolymerization of native corn stover with an unsupported MoS2 catalyst

RSC Adv.

Mild redox-neutral depolymerization of lignin with a binuclear Rh complex in water

ACS Catal.

Rhodium-terpyridine catalyzed redox-neutral depolymerization of lignin in water

Green Chem.