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Lignin is the most abundant source of renewable aromatics on Earth, yet its enormous potential remains underexploited in current biorefinery and pulping processes. The extensive degree of condensation of the lignin fractions produced via the most widely adopted biomass pretreatments (i.e. “technical lignin”) poses a prominent limitation to their subsequent conversion toward valuable products. In this work, a broad range of methods for biomass pretreatment are reviewed, illustrating the impact of each strategy on the properties of the isolated lignin and carbohydrate fractions. The main pathways for the valorization of the obtained lignin streams (i.e. toward polymeric materials or chemicals) are critically discussed, and the relationship existing between (i) native lignin structure, (ii) pretreatment conditions, and (iii) lignin processability is rationalized. A key aspect for producing lignin streams amenable to further upgrading is the prevention of condensation reactions between lignin fragments during biomass fractionation. In this respect, a class of so-called “lignin-first” pretreatments, targeting the prompt stabilization of reactive lignin intermediates to minimize lignin condensation, has recently gained momentum. Herein, lignin-first approaches are reviewed, discussing in detail the fate of lignin, cellulose, and hemicellulose for each strategy. The potential of lignin-first biorefineries to realize a more complete valorization of lignocellulose and the current limitations of each method are highlighted. Overall, this work provides a comprehensive overview of the technologies that are available or currently emerging for lignin isolation and subsequent valorization., SCOPUS: re.j, info:eu-repo/semantics/published

The development of biomass pretreatment approaches that, next to (hemi)cellulose valorization, aim at the conversion of lignin to chemicals is essential for the long-term success of a biorefinery. Herein, we discuss a dithionite-assisted organosolv fractionation (DAOF) of lignocellulose in n-butanol and water to produce cellulosic pulp and mono-/oligo-aromatics. The present study frames the technicalities of this biorefinery process and relates them to the features of the obtained product streams. Via the extensive characterization of the solid pulp (by acid hydrolysis-HPLC, ATR-FTIR, XRD, SEM and enzymatic hydrolysis-HPLC), of lignin derivatives (by GPC, GC-MS/FID, 1H-13C HSQC NMR, and ICP-AES) and of carbohydrate derivatives (by HPLC) we comprehensively identify and quantify the different products of interest. These results were used for inspecting the economic feasibility of DAOF. The adoption of a dithionite loading of 16.7% w/wbiomass and of an equivolumetric mixture of n-butanol and water, which led to a high yield of monophenolics (~20%, based on acid insoluble lignin, for the treatment of birch sawdust), was identified as the most profitable process configuration. Furthermore, the treatment of various lignocellulosic feedstocks was explored, which showed that DAOF is particularly effective for processing hardwood and herbaceous biomass. Overall, this study provides a comprehensive view of the development of an effective dithionite-assisted organosolv fractionation method for the sustainable upgrading of lignocellulosic biomass.

Lignin is the most abundant source of renewable aromatics on Earth, but its tendency to undergo irreversible condensation reactions during lignocellulose pretreatment hampers its valorization in current biorefinery schemes. A strategy for circumventing this issue is the so-called reductive catalytic fractionation (RCF), which relies on the use of redox catalysts and hydrogen gas to promote the reductive cleavage of lignin and to prevent lignin condensation, ultimately yielding low-molecular weight phenolics, along with a delignified (hemi)cellulose fraction. Some limitations must be overcome to improve the potential of RCF. The treatment of biomass feedstocks alternative to the widely explored virgin wood is important for extending the range of applications of this method. In addition, the recurrent adoption of high pressures of hydrogen gas poses safety and equipment constraints. This dissertation reports on research undertaken to investigate the RCF of wheat straw, an inexpensive and abundantly available agricultural residue, with a focus on the study of hydrogen-free process configurations. Moreover, an innovative dithionite-assisted organosolv fractionation (DAOF) method for the reductive depolymerization of lignin within biomass pretreatment is developed, based on the use of sodium dithionite as a reducing agent, instead of hydrogen gas and redox catalysts. Overall, this dissertation shows that RCF and DAOF represent promising approaches for the sustainable production of light aromatics via the reductive depolymerization of lignin., (AGRO - Sciences agronomiques et ingénierie biologique) -- UCL, 2022

The development of biomass pretreatment approaches that, next to (hemi)cellulose valorization, aim at the conversion of lignin to chemicals is essential for the long-term success of a biorefinery. Herein, we discuss a dithionite-assisted organosolv fractionation (DAOF) of lignocellulose in n-butanol and water to produce cellulosic pulp and mono-/oligo-aromatics. The study frames the technicalities of this biorefinery process and relates them to the features of the obtained product streams. We comprehensively identify and quantify all products of interest: solid pulp (acid hydrolysis-HPLC, ATR-FTIR, XRD, SEM, enzymatic hydrolysis-HPLC), lignin derivatives (GPC, GC–MS/FID, 1H–13C HSQC NMR, ICP-AES), and carbohydrate derivatives (HPLC). These results were used for inspecting the economic feasibility of DAOF. In the best process configuration, a high yield of monophenolics was reached (∼20 wt%, based on acid insoluble lignin in birch sawdust). Various other lignocellulosic feedstocks were also explored, showing that DAOF is particularly effective on hardwood and herbaceous biomass. Overall, this study demonstrates that DAOF is a viable fractionation method for the sustainable upgrading of lignocellulosic biomass.

The reductive catalytic fractionation (RCF) is a promising method for the development of “lignin-first” biorefineries. Apart from the widely investigated virgin woody biomass, it is essential to explore the potential of waste biomass feedstocks. Herein, the RCF of wheat straw is examined to produce lignin mono-/oligomers along with a processable carbohydrate pulp. The use of different catalysts (Ru/C and Ru/Al2O3) and catalyst loadings (0–20% w/wbiomass) revealed the superior performance of Ru/C, which resulted in the largest yield of phenolic monomers (up to ∼25 wt % of initial acid-insoluble lignin) and in the lowest formation of high-molecular-weight fragments in the extracted lignin oil. Furthermore, the operating temperature was shown to substantially affect both lignin extraction–depolymerization and polysaccharides preservation–processability. For a reaction time of 3 h, an increase of the temperature from 200 to 250 °C resulted in a >2-fold boost of the yields of lignin oil and monophenolics, while the recovery of polysaccharides decreased by about 30 wt % (with ∼20% lower enzymatic digestibility). An economic assessment highlighted that the high-temperature treatment becomes the most profitable configuration as the market price of lignin products increases. Overall, this work provides insight into the adoption of the RCF for the upgrading of lignocellulose from inexpensive and widely available wheat straw biomass.