Background Lignin, nature’s dominant aromatic polymer, is found in most terrestrial plants in the approximate range of 15 to 40% dry weight and provides structural integrity. Traditionally, most large-scale industrial processes that use plant polysaccharides have burned lignin to generate the power needed to productively transform biomass. The advent of biorefineries that convert cellulosic biomass into liquid transportation fuels will generate substantially more lignin than necessary to power the operation, and therefore efforts are underway to transform it to value-added products. Production of biofuels from cellulosic biomass requires separation of large quantities of the aromatic polymer lignin. In planta genetic engineering, enhanced extraction methods, and a deeper understanding of the structure of lignin are yielding promising opportunities for efficient conversion of this renewable resource to carbon fibers, polymers, commodity chemicals, and fuels. [Credit: Oak Ridge National Laboratory, U.S. Department of Energy] Advances Bioengineering to modify lignin structure and/or incorporate atypical components has shown promise toward facilitating recovery and chemical transformation of lignin under biorefinery conditions. The flexibility in lignin monomer composition has proven useful for enhancing extraction efficiency. Both the mining of genetic variants in native populations of bioenergy crops and direct genetic manipulation of biosynthesis pathways have produced lignin feedstocks with unique properties for coproduct development. Advances in analytical chemistry and computational modeling detail the structure of the modified lignin and direct bioengineering strategies for targeted properties. Refinement of biomass pretreatment technologies has further facilitated lignin recovery and enables catalytic modifications for desired chemical and physical properties. Outlook Potential high-value products from isolated lignin include low-cost carbon fiber, engineering plastics and thermoplastic elastomers, polymeric foams and membranes, and a variety of fuels and chemicals all currently sourced from petroleum. These lignin coproducts must be low cost and perform as well as petroleum-derived counterparts. Each product stream has its own distinct challenges. Development of renewable lignin-based polymers requires improved processing technologies coupled to tailored bioenergy crops incorporating lignin with the desired chemical and physical properties. For fuels and chemicals, multiple strategies have emerged for lignin depolymerization and upgrading, including thermochemical treatments and homogeneous and heterogeneous catalysis. The multifunctional nature of lignin has historically yielded multiple product streams, which require extensive separation and purification procedures, but engineering plant feedstocks for greater structural homogeneity and tailored functionality reduces this challenge.

https://lifelong.unt.edu/sites/default/files/EmeritusCollege/Spring2015/Handouts/Lignin%20co-products.pdf

Lignin valorization: improving lignin processing in the biorefinery.

Lignocellulosic biomass pyrolysis mechanism: A state-of-the-art review

In pursuit of more sustainable and competitive biorefineries, the effective valorisation of lignin is key. An alluring opportunity is the exploitation of lignin as a resource for chemicals. Three technological biorefinery aspects will determine the realisation of a successful lignin-to-chemicals valorisation chain, namely (i) lignocellulose fractionation, (ii) lignin depolymerisation, and (iii) upgrading towards targeted chemicals. This review provides a summary and perspective of the extensive research that has been devoted to each of these three interconnected biorefinery aspects, ranging from industrially well-established techniques to the latest cutting edge innovations. To navigate the reader through the overwhelming collection of literature on each topic, distinct strategies/topics were delineated and summarised in comprehensive overview figures. Upon closer inspection, conceptual principles arise that rationalise the success of certain methodologies, and more importantly, can guide future research to further expand the portfolio of promising technologies. When targeting chemicals, a key objective during the fractionation and depolymerisation stage is to minimise lignin condensation (i.e. formation of resistive carbon–carbon linkages). During fractionation, this can be achieved by either (i) preserving the (native) lignin structure or (ii) by tolerating depolymerisation of the lignin polymer but preventing condensation through chemical quenching or physical removal of reactive intermediates. The latter strategy is also commonly applied in the lignin depolymerisation stage, while an alternative approach is to augment the relative rate of depolymerisation vs. condensation by enhancing the reactivity of the lignin structure towards depolymerisation. Finally, because depolymerised lignins often consist of a complex mixture of various compounds, upgrading of the raw product mixture through convergent transformations embodies a promising approach to decrease the complexity. This particular upgrading approach is termed funneling, and includes both chemocatalytic and biological strategies.

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Chemicals from lignin: an interplay of lignocellulose fractionation, depolymerisation, and upgrading

Lignin is an abundant biopolymer with a high carbon content and high aromaticity. Despite its potential as a raw material for the fuel and chemical industries, lignin remains the most poorly utilised of the lignocellulosic biopolymers. Effective valorisation of lignin requires careful fine-tuning of multiple "upstream" (i.e., lignin bioengineering, lignin isolation and "early-stage catalytic conversion of lignin") and "downstream" (i.e., lignin depolymerisation and upgrading) process stages, demanding input and understanding from a broad array of scientific disciplines. This review provides a "beginning-to-end" analysis of the recent advances reported in lignin valorisation. Particular emphasis is placed on the improved understanding of lignin's biosynthesis and structure, differences in structure and chemical bonding between native and technical lignins, emerging catalytic valorisation strategies, and the relationships between lignin structure and catalyst performance.

Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis.

Lignin, a major component of lignocellulose, is the largest source of aromatic building blocks on the planet and harbors great potential to serve as starting material for the production of biobased products. Despite the initial challenges associated with the robust and irregular structure of lignin, the valorization of this intriguing aromatic biopolymer has come a long way: recently, many creative strategies emerged that deliver defined products via catalytic or biocatalytic depolymerization in good yields. The purpose of this review is to provide insight into these novel approaches and the potential application of such emerging new structures for the synthesis of biobased polymers or pharmacologically active molecules. Existing strategies for functionalization or defunctionalization of lignin-based compounds are also summarized. Following the whole value chain from raw lignocellulose through depolymerization to application whenever possible, specific lignin-based compounds emerge that could be in the fu...

Bright Side of Lignin Depolymerization: Toward New Platform Chemicals

Background: In converting biomass to bioethanol, pretreatment is a key step intended to render cellulose more amenable and accessible to cellulase enzymes and thus increase glucose yields. In this study, four cellulose samples with different degrees of polymerization and crystallinity indexes were subjected to aqueous sodium hydroxide and anhydrous liquid ammonia treatments. The effects of the treatments on cellulose crystalline structure were studied, in addition to the effects on the digestibility of the celluloses by a cellulase complex. Results: From X-ray diffractograms and nuclear magnetic resonance spectra, it was revealed that treatment with liquid ammonia produced the cellulose IIII allomorph; however, crystallinity depended on treatment conditions. Treatment at a low temperature (25°C) resulted in a less crystalline product, whereas treatment at elevated temperatures (130°C or 140°C) gave a more crystalline product. Treatment of cellulose I with aqueous sodium hydroxide (16.5 percent by weight) resulted in formation of cellulose II, but also produced a much less crystalline cellulose. The relative digestibilities of the different cellulose allomorphs were tested by exposing the treated and untreated cellulose samples to a commercial enzyme mixture (Genencor-Danisco; GC 220). The digestibility results showed that the starting cellulose I samples were the least digestible (except for corn stover cellulose, which had a high amorphous content). Treatment with sodium hydroxide produced the most digestible cellulose, followed by treatment with liquid ammonia at a low temperature. Factor analysis indicated that initial rates of digestion (up to 24 hours) were most strongly correlated with amorphous content. Correlation of allomorph type with digestibility was weak, but was strongest with cellulose conversion at later times. The cellulose IIII samples produced at higher temperatures had comparable crystallinities to the initial cellulose I samples, but achieved higher levels of cellulose conversion, at longer digestion times. Conclusions: Earlier studies have focused on determining which cellulose allomorph is the most digestible. In this study we have found that the chemical treatments to produce different allomorphs also changed the crystallinity of the cellulose, and this had a significant effect on the digestibility of the substrate. When determining the relative digestibilities of different cellulose allomorphs it is essential to also consider the relative crystallinities of the celluloses being tested.

/pdf/effects-of-alkaline-or-liquid-ammonia-treatment-on-1vjbjwl5go.pdf

Effects of alkaline or liquid-ammonia treatment on crystalline cellulose: changes in crystalline structure and effects on enzymatic digestibility.

Reductive catalytic fractionation (RCF) has emerged as an effective biomass pretreatment strategy to depolymerize lignin into tractable fragments in high yields. We investigate the RCF of corn stover, a highly abundant herbaceous feedstock, using carbon-supported Ru and Ni catalysts at 200 and 250 °C in methanol and, in the presence or absence of an acid cocatalyst (H3PO4 or an acidified carbon support). Three key performance variables were studied: (1) the effectiveness of lignin extraction as measured by the yield of lignin oil, (2) the yield of monomers in the lignin oil, and (3) the carbohydrate retention in the residual solids after RCF. The monomers included methyl coumarate/ferulate, propyl guaiacol/syringol, and ethyl guaiacol/syringol. The Ru and Ni catalysts performed similarly in terms of product distribution and monomer yields. The monomer yields increased monotonically as a function of time for both temperatures. At 6 h, monomer yields of 27.2 and 28.3% were obtained at 250 and 200 °C, respec...

Reductive Catalytic Fractionation of Corn Stover Lignin

Flowthrough Reductive Catalytic Fractionation of Biomass

Lignocellulosic biorefineries will produce a substantial pool of lignin-enriched residues, which are currently slated to be burned for heat and power. Going forward, however, valorization strategies for residual solid lignin will be essential to the economic viability of modern biorefineries. To achieve these strategies, effective lignin depolymerization processes will be required that can convert specific lignin-enriched biorefinery substrates into products of sufficient value and market size. Base-catalyzed depolymerization (BCD) of lignin using sodium hydroxide and other basic media has been shown to be an effective depolymerization approach when using technical and isolated lignins relevant to the pulp and paper industry. To gain insights in the application of BCD to lignin-rich, biofuels-relevant residues, here we apply BCD with sodium hydroxide at two catalyst loadings and temperatures of 270, 300, and 330 °C for 40 min to residual biomass from typical and emerging biochemical conversion processes. ...

https://pubs.acs.org/doi/pdf/10.1021/acssuschemeng.5b01451

Rui Katahira

Papers

Effects of alkaline or liquid-ammonia treatment on crystalline cellulose: changes in crystalline structure and effects on enzymatic digestibility.

Reductive Catalytic Fractionation of Corn Stover Lignin

Flowthrough Reductive Catalytic Fractionation of Biomass

Base-Catalyzed Depolymerization of Biorefinery Lignins

Lignin depolymerisation by nickel supported layered-double hydroxide catalysts