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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Methods for lignin depolymerization using thiols

The disclosure relates to a method for depolymerizing lignin. The method includes reacting a lignin compound with a thiol compound to depolymerize the lignin compound and to form a depolymerized lignin product having a reduced molecular weight relative to the lignin compound prior to reacting. The method can further include forming an oxidized thiol reaction product between two thiol groups from one or more thiol compounds, and then reducing the oxidized thiol reaction product to re-form or regenerate the thiol compound for further lignin depolymerization.

09 BIOMASS FUELS↗
DOE OSTI2022

Energy-resolved mass spectrometry as a tool for identification of lignin depolymerization products

Lignin is the largest source of bio-based aromatic compounds in nature, and its valorization is essential to the sustainability of lignocellulosic biorefining. Characterizing lignin-derived compounds remains challenging due to the heterogeneity of this biopolymer. Tandem mass spectrometry is a promising tool for lignin structural analytics, as fragmentation patterns of model compounds can be extrapolated to identify characteristic moieties in complex samples. This work extends previous resonance excitation type collision-induced dissociation (CID) methods that identified lignin oligomers containing β-Ο-4, β-5, and β-β bonds, to also identify characteristics of 5-5, β-1, and 4-Ο-5 dimers, enabled by quadrupole time-of-flight (QTOF) CID with energy-resolved mass spectrometry (ERMS). Overall, beam type ERMS offers in-depth structural information and could ultimately contribute to tools for high-throughput lignin dimer identification.

09 BIOMASS FUELS↗
DOE OSTI2025

Bioconversion of self-neutralized chemically depolymerized lignin streams into polyhydroxyalkanoates

Lignin is a chemically complex, diverse, and abundant plant polymer mainly composed of aromatic monomers. These aromatic monomers make lignin a potential source of aromatics and a viable substitute for petrochemically-derived aromatics. However, the structural recalcitrance of lignin requires harsh reagents from the chemical process and expensive catalysts for effective depolymerization. This chemical process often results in poor yields of chemical intermediate mixtures of varying bioavailability and/or toxicity. Furthermore, the cost of additional reagents required to separate or detoxify these intermediates makes processing lignin impractical. We report progress towards the use of such chemically depolymerized lignin streams by employing bacterial strains to produce polyhydroxyalkanoates (PHA). PHAs are a group of biodegradable microbial polyesters that have potential as a replacement for petroleum-based plastics. In this study we utilized two distinct lignin streams obtained after chemical depolymerization of lignin under alkaline and acidic pH in the presence of catalysts. We mixed the alkali-treated depolymerized stream with the acid-treated depolymerized stream to create a solution of neutral-pH chemically depolymerized lignin (CDL). We found moderate to substantial growth of both native and non-native PHA producers on the mixture of CDL as well as its aliphatic and aromatic components. PHA was detected by Sudan Black B staining in C. necator H16, P. putida KT2440, and E. coli LSBJ STQKAB grown on mixed CDL as the sole carbon source. For C. necator H16 and E. coli LSBJ STQKAB we found that PHA content was greater when grown on mixed CDL when compared to their preferred carbon source by GC-FID quantification. Our study provided progress towards a cost-competitive, sustainable, and industrially relevant use for lignin.

Winkler, Gordon L. W. [Univ. of Wisconsin, Madison↗
DOE OSTI2024

Reductive Depolymerization of Lignin to Aromatic Compounds over Promoted Nickel Catalysts in Sub– and Supercritical Methanol

The use of γ-Al 2 O 3 -supported Ni catalysts promoted with either Cu or Fe was investigated for the reductive catalytic fractionation (RCF) of hybrid poplar in methanol at 200 and 250 °C. The effectiveness of lignin depolymerization was quantified in terms of the lignin oil production, the quantity and distribution of identifiable monomers present in the lignin oil, and the yield of residual solids. All of the Ni-based catalysts tested provided improved yields of lignin oil and monomers, along with reduced char formation, relative to blank (sans catalyst) runs. The highest monomer yield of 51 % was obtained at 250 °C over a 20 wt.% Ni-5 wt.% Cu/Al 2 O 3 catalyst, the improved performance obtained through Cu promotion being attributed to the ability of Cu to facilitate NiO reduction, resulting in an increased amount of Ni 0 on the catalyst surface and, consequently, improved hydrogenation activity. Finally, the main monomers formed were propanol-, propyl- and propenyl-substituted guaiacol and syringol, the S/G ratio of the products corresponding closely to that in the native lignin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Mild, Electroreductive Lignin Cleavage: Optimizing the Depolymerization of Authentic Lignins

Among candidate strategies to depolymerize lignin, electroreduction has promise as a mild, environmentally friendly, low-cost method to cleave lignin’s most common linkage, the β-O-4 bond. Much of the prior work on lignin electrolysis has focused on anodic (oxidative) approaches, while most available electroreduction studies have studied lignin model compounds rather than authentic lignin. Here, after optimizing with a model system, we investigated the room-temperature electroreductive cleavage of four common lignin samples from different pretreatment approaches, including Kraft, Soda, GVL, and Cu-AHP lignin. This mild electrolysis process resulted in the solubilization of 45% of the GVL lignin and 60% of the Cu-AHP lignin, affording approximately 17.6 and 19.4 wt % of monomeric materials, respectively. Furthermore, the present work is an encouraging first step toward an electroreductive strategy for lignin depolymerization and upgrading.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Depolymerization of lignin for biological conversion through sulfonation and a chelator-mediated Fenton reaction

The generating value from lignin through depolymerization and biological conversion to valuable fuels, chemicals, or intermediates has great promise but is limited by several factors including lack of cost-effective depolymerization methods, toxicity within the breakdown products, and low bioconversion of the breakdown products. High yield depolymerization of natural lignins requires cleaving carbon-carbon bonds in addition to ether bonds. To address that need, we report that a chelator-mediated Fenton reaction can efficiently cleave C-C bonds in sulfonated polymers at or near room temperature, and that unwanted repolymerization can be minimized through optimizing reaction conditions. This method was used to depolymerize lignosulfonate from M w = 28,000 g/mol to M w = 800 g/mol. The breakdown products were characterized by SEC, FTIR and NMR and evaluated for bioavailability. The breakdown products are rich in acid, aldehyde, and alcohol functionalities but are largely devoid of aromatics and aliphatic dienes. A panel of nine organisms were tested for the ability to grow on the breakdown products. Growth at a low level was observed for several monocultures on the depolymerized LS in absence of glucose. Much stronger growth was observed in the presence of 0.2% glucose and for one organism we demonstrate doubling of melanin production in the presence of depolymerized LS. The results suggest that this chelator-mediated Fenton method is a promising new approach for biological conversion of lignin into higher value chemicals or intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Reversibly soluble bases for lignin oxidative depolymerization

Disclosed herein are lignin valorization strategies that integrate thermochemical pretreatment strategies. Using methods disclosed herein, yields of greater than 40% of usable monomers are obtained from lignin in biomass. The monomers can be assimilated by strains of Pseudomonas putida.

Kruger, Jacob S.↗
DOE OSTI2022

Synthesis of bioproducts from lignin-derived aromatics by genetically modified microorganisms

The present invention provides for a method of converting a depolymerized lignin aromatic compound into a bioproduct, comprising: (a) providing a composition comprising a depolymerized lignin aromatic compound, optionally a depolymerized cellulose, and optionally a depolymerized hemicellulose, and (b) introducing a genetically modified microorganism to the composition, wherein the genetically modified microorganism is capable of converting the depolymerized lignin aromatic compound into a bioproduct; such that the depolymerized lignin aromatic compound is converted into a bioproduct.

Gladden, John M.↗
DOE OSTI2023

2.3.4.100 - Lignin Utilization

Lignin depolymerization to aromatic monomers is a primary route for myriad lignin valorization strategies. To date, there are many strategies able to cleave aryl-ether linkages in lignin, but the lignin polymer, in both its native and processed forms, contains a substantial fraction of refractory carbon-carbon linkages between aromatic units, which typically limits aromatic monomer yields to -30-40 wt% or lower, depending on the feedstock. To that end, the Lignin Utilization (LigU) project addresses the critical challenge of lignin depolymerization catalysis with emphasis on C-C bond cleavage. Being able to achieve cost-effective C-C bond catalysis in lignin depolymerization would enable a substantial increase in accessible aromatic monomer yields from lignin. Among the catalysis strategies that have been investigated in the LigU project, we have made substantial progress in the use of autoxidation catalysis, inspired by the industrial conversion of p-xylene to terephthalic acid, for C-C bond cleavage in lignin. Using multiple substrates, we have demonstrated that autoxidation catalysis can produce mixtures of bio-available aromatic monomers for conversion to exemplary bioproducts, such as cis,cis-muconic acid, in collaboration with the Biological Lignin Valorization project. Prior to FY23, the LigU project also included lignin analytical chemistry method development, lignin analytics for BETO-funded projects, and model compound syntheses, which will also be presented.

BIOMASS FUELS↗
DOE OSTI2024

Perspective on Lignin Conversion Strategies That Enable Next Generation Biorefineries

The valorization of lignin, a currently underutilized component of lignocellulosic biomass, has attracted attention to promote a stable and circular bioeconomy. Successful approaches including thermochemical, biological, and catalytic lignin depolymerization have been demonstrated, enabling opportunities for lignino-refineries and lignocellulosic biorefineries. Although significant progress in lignin valorization has been made, this review describes unexplored opportunities in chemical and biological routes for lignin depolymerization and thereby contributes to economically and environmentally sustainable lignin-utilizing biorefineries. This review also highlights the integration of chemical and biological lignin depolymerization and identifies research gaps while also recommending future directions for scaling processes to establish a lignino-chemical industry.

09 BIOMASS FUELS↗
DOE OSTI2024

Catalytic carbon–carbon bond cleavage in lignin via manganese–zirconium-mediated autoxidation

Abstract Efforts to produce aromatic monomers through catalytic lignin depolymerization have historically focused on aryl–ether bond cleavage. A large fraction of aromatic monomers in lignin, however, are linked by various carbon–carbon (C–C) bonds that are more challenging to cleave and limit the yields of aromatic monomers from lignin depolymerization. Here, we report a catalytic autoxidation method to cleave C–C bonds in lignin-derived dimers and oligomers from pine and poplar. The method uses manganese and zirconium salts as catalysts in acetic acid and produces aromatic carboxylic acids as primary products. The mixtures of the oxygenated monomers are efficiently converted to cis,cis -muconic acid in an engineered strain of Pseudomonas putida KT2440 that conducts aromatic O -demethylation reactions at the 4-position. This work demonstrates that autoxidation of lignin with Mn and Zr offers a catalytic strategy to increase the yield of valuable aromatic monomers from lignin.

09 BIOMASS FUELS↗
DOE OSTI2023

Molecular insights into the evolution of woody plant decay in the gut of termites

Plant cell walls represent the most abundant pool of organic carbon in terrestrial ecosystems but are highly recalcitrant to utilization by microbes and herbivores owing to the physical and chemical barrier provided by lignin biopolymers. Termites are a paradigmatic example of an organism’s having evolved the ability to substantially degrade lignified woody plants, yet atomic-scale characterization of lignin depolymerization by termites remains elusive. We report that the phylogenetically derived termite Nasutitermes sp. efficiently degrades lignin via substantial depletion of major interunit linkages and methoxyls by combining isotope-labeled feeding experiments and solution-state and solid-state nuclear magnetic resonance spectroscopy. Exploring the evolutionary origin of lignin depolymerization in termites, we reveal that the early-diverging woodroach Cryptocercus darwini has limited capability in degrading lignocellulose, leaving most polysaccharides intact. Conversely, the phylogenetically basal lineages of “lower” termites are able to disrupt the lignin-polysaccharide inter- and intramolecular bonding while leaving lignin largely intact. These findings advance knowledge on the elusive but efficient delignification in natural systems with implications for next-generation ligninolytic agents.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Accessing monomers from lignin through carbon–carbon bond cleavage

Lignin, the heterogeneous aromatic macromolecule found in the cell walls of vascular plants, is an abundant feedstock for the production of biochemicals and biofuels. Here, many valorization schemes rely on lignin depolymerization, with decades of research focused on accessing monomers through C–O bond cleavage, given the abundance of β–O–4 bonds in lignin and the large number of available C–O bond cleavage strategies. Monomer yields are, however, invariably lower than desired, owing to the presence of recalcitrant C–C bonds whose selective cleavage remains a major challenge in catalysis. In this Review, we highlight lignin C–C cleavage reactions, including those of linkages arising from biosynthesis (β–1, β–5, β–β and 5–5) and industrial processing (5–CH 2 –5 and α–5). We examine multiple approaches to C–C cleavage, including homogeneous and heterogeneous catalysis, photocatalysis and biocatalysis, to identify promising strategies for further research and provide guidelines for definitive measurements of lignin C–C bond cleavage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Integrating catalytic fractionation and microbial funneling to produce 2-pyrone-4,6-dicarboxylic acid and ethanol

Replacing biorefinery designs that use stepwise fractionation, depolymerization, and conversion processes with designed tandem process steps can greatly reduce a biorefinery's operating costs and environmental impact. Reductive Catalytic Fractionation (RCF) is a highly efficient lignin-first approach that combines biomass fractionation and lignin depolymerization to generate a hydrogenolysis oil and pulp. The oil is composed of a complex mixture of phenolic monomers, dimers, and oligomers. Intergrating this chemical deconstruction process with microbial funneling of phenolics can simplify the product mixture and make high-value products. We applied RCF to poplar biomass in a biomass-to-bioproduct processing chain in which the phenolics were funneled to 2-pyrone-4,6-dicarboxylic acid (PDC) by an engineered strain of Novosphingobium aromaticivorans DSM12444. The pulp was enzymatically digested and the glucose and xylose was funneled to ethanol by an engineered strain of Saccharomyces cerevisiae GLBRCY945. By combining biomass fractionation and lignin depolymerization we removed a costly processing step that directly translated into a 29% reduction in the minimum selling price of PDC. This work combines experimentation with process modeling of an integrated biorefinery design to show how utilizing tandem process steps can significantly reduce operating expenses and environmental impact of upgrading lignocellulosic biomass to a portfolio of high value products.

Sener, Canan [Great Lakes Bioenergy Research Cente↗