Highly Selective Oxidation and Depolymerization of α,γ-Diol Protected Lignin

Lignin oxidation offers a potential sustainable pathway to oxygenated aromatic molecules. However, current methods that use real lignin tend to have low selectivity and a yield that is limited by lignin degradation during its extraction. We developed stoichiometric and catalytic oxidation methods using 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) as oxidant/catalyst to selectively deprotect the acetal and oxidize the α‐OH into a ketone. The oxidized lignin was then depolymerized using a formic acid/sodium formate system to produce aromatic monomers with a 36 mol % (in the case of stoichiometric oxidation) and 31 mol % (in the case of catalytic oxidation) yield (based on the original Klason lignin). The selectivity to a single product reached 80 % (syringyl propane dione, and 10–13 % to guaiacyl propane dione). These high yields of monomers and unprecedented selectivity are attributed to the preservation of the lignin structure by the acetal

Dual Valorization of Lignin as a Versatile and Renewable Matrix for Enzyme Immobilization and (Flow) Bioprocess Engineering

Lignin has emerged as an attractive alternative in the search for more eco-friendly and less costly materials for enzyme immobi- lization. In this work, the terephthalic aldehyde-stabilization of lignin is carried out during its extraction to develop a series of functionalized lignins with a range of reactive groups (epoxy, amine, aldehyde, metal chelates). This expands the immobiliza- tion to a pool of enzymes (carboxylase, dehydrogenase, trans- aminase) by different binding chemistries, affording immobiliza- tion yields of 64–100%. As a proof of concept, a ω- transaminase reversibly immobilized on polyethyleneimine- lignin is integrated in a packed-bed reactor. The stability of the immobilized biocatalyst is tested in continuous-flow deamina- tion reactions and maintains the same conversion for 100 cycles. These results outperform previous stability tests carried out with the enzyme covalently immobilized on methacrylic resins, with the advantage that the reversibility of the immobilized enzyme allows recycling and reuse of lignin beyond the enzyme inactivation. Additionally, an in-line system also based on lignin is added into the downstream process to separate the reaction products by catch-and-release. These results demonstrate a fully closed-loop sustainable flow- biocatalytic system based exclusively on lignin

Aldehyde-Assisted Fractionation Enhances Lignin Valorization in Endocarp Waste Biomass

Endocarp biomass, which forms much of the inedible portion of nuts and stone fruits, is a promising feedstock for aromatic chemical production due to its high lignin content and because it is a food industry waste. Here, we tested the nut shells and fruit kernels of seven species and report that their aromatic monomer yields can surpass those obtained using wood chips by up to 30% on a dry biomass basis due to their high lignin content. We also observed that acid-catalyzed aldehyde-assisted fractionation (AAF) facilitates lignin valorization when using industrially relevant particle sizes (3-5 mm) with monomers yields that are 80% to 170% higher than those obtained with reductive catalytic fractionation (RCF) for similarly sized particles. This difference was highly correlated with the feedstock surface area, demonstrating the importance of acidic pretreatment for substrates with low accessibility and/or large particles

Continuous hydrogenolysis of acetal-stabilized lignin in flow

Using acetal-stabilized lignin we performed a truly steady state continuous high-yielding lignin depolymerization (45% monophenolics using Ni/C), which offered a window into challenges and opportunities that will be faced when processing this feedstock. With an excess of catalyst present, we observed stable depolymerization yields for 125 h time on stream. However, using catalyst loadings that were just sufficient to achieve initial maximum hydrogenolysis monomer yields revealed rapid catalyst deactivation. High yields could be partially recovered with high temperature regeneration under a reducing environment. Characterization of spent catalysts revealed that sintering and carbonaceaous deposits rather than leaching were the main phenomena causing deactivation

Aldehyde-Assisted Lignocellulose Fractionation Provides Unique Lignin Oligomers for the Design of Tunable Polyurethane Bioresins

Thanks to chemical stabilization, aldehyde-assisted fractionation (AAF) of lignocellulosic biomass has recently emerged as a powerful tool for the production of largely uncondensed lignin. Depolymerization of AAF lignin via ether deavage provides aromatic monomers at near theoretical yields based on ether cleavage and an oligomeric fraction that remains largely unexploited despite its unique material properties. Here, we present an in-depth analytical characterization of AAF oligomers derived from hardwood and softwood in order to elucidate their molecular structures. These bioaromatic oligomers surpass technical Kraft lignin in terms of purity, solubility, and functionality and thus cannot even be compared to this common feedstock directly for material production. Instead, we performed comparative experiments with Kraft oligomers of similar molecular weight (Mn similar to 1000) obtained through solvent extraction. These oligomers were then formulated into polyurethane materials. Substantial differences in material properties were observed depending on the amount of lignin, the botanical origin, and the biorefining process (AAF vs Kraft), suggesting new design principles for lignin-derived biopolymers with tailored properties. These results highlight the surprising versatility of AAF oligomers towards the design of new biomaterials and further demonstrate that AAF can enable the conversion of all biomass fractions into value-added products

Carbon–carbon bond cleavage for a lignin refinery

Carbon–carbon bonds, ubiquitous in lignin, limit monomer yields from current depolymerization strategies, which mainly target C–O bonds. Selective cleavage of the inherently inert σ-type C–C bonds without pre-functionalization remains challenging. Here we report the breaking of C–C bonds in lignin obtained upon initial disruption of labile C–O bonds, achieving monocyclic hydrocarbon yields up to an order of magnitude higher than previously reported. The use of a Pt (de)hydrogenation function leads to olefinic groups close to recalcitrant C–C bonds, which can undergo β-scission over zeolitic Brønsted acid sites. After confirming that this approach can selectively cleave common C–C linkages (5–5′, β–1′, β–5′ and β–β′) in lignin skeletons, we demonstrate its utility in the valorization of various representative lignins. A techno-economic analysis shows the promise of our method for producing gasoline- and jet-range cycloalkanes and aromatics, while a life-cycle assessment confirms its potential for CO2-neutral fuel production

Carbon–carbon bond cleavage for a lignin refinery

Carbon–carbon bonds, ubiquitous in lignin, limit monomer yields from current depolymerization strategies, which mainly target C–O bonds. Selective cleavage of the inherently inert σ-type C–C bonds without pre-functionalization remains challenging. Here we report the breaking of C–C bonds in lignin obtained upon initial disruption of labile C–O bonds, achieving monocyclic hydrocarbon yields up to an order of magnitude higher than previously reported. The use of a Pt (de)hydrogenation function leads to olefinic groups close to recalcitrant C–C bonds, which can undergo β-scission over zeolitic Brønsted acid sites. After confirming that this approach can selectively cleave common C–C linkages (5–5′, β–1′, β–5′ and β–β′) in lignin skeletons, we demonstrate its utility in the valorization of various representative lignins. A techno-economic analysis shows the promise of our method for producing gasoline- and jet-range cycloalkanes and aromatics, while a life-cycle assessment confirms its potential for CO2-neutral fuel production