and Fuels Changzhi Li,† Xiaochen Zhao,† Aiqin Wang,† George W. Huber,†,‡ and Tao Zhang*,† †State Key Laborotary of Catalysis, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China ‡Department of Chemical and Biological Engineering, University of WisconsinMadison, Madison, Wisconsin 53706, United States

Catalytic Transformation of Lignin for the Production of Chemicals and Fuels

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.

https://pubs.rsc.org/en/Content/ArticlePDF/2013/GC/C2GC36364J

Deconstruction of lignocellulosic biomass with ionic liquids

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

Ionic liquid pretreatment of lignocellulosic biomass with ionic liquid–water mixtures

Fractionation of lignocellulosic biomass with the ionic liquid 1-butylimidazolium hydrogen sulfate

A compositional analysis was performed on Buddleja davidii to determine its general biomass characteristics and provide detailed analysis of the chemical structures of its cellulose and lignin using NMR. B. davidii is a new potential lignocellulosic bioresource for producing bioethanol because it has several attractive agroenergy features. The biomass composition of B. davidii is 30% lignin, 35% cellulose, and 34% hemicellulose. Solid-state CP/MAS C-13 NMR showed that 33% of the cellulose is para-crystalline and 41% is at inaccessible surfaces. Both quantitative C-13 and P-31 NMR were used to examine the structure of lignin. The lignin was determined to be guaiacyl and syringyl with an h:g:s ratio of 0:81:19.

Biomass characterization of Buddleja davidii: a potential feedstock for biofuel production.

Ethanol organosolv pretreatment was performed on Buddleja davidii to evaluate this bioresource as a potential feedstock for bioethanol production. B. davidii was pretreated and delignified, while 85% of the glucose content of the untreated material was retained in the pretreated solid fraction. The enzymatic hydrolysis showed that organosolv pretreatment produced solid substrates that were readily digestible by cellulases. Gel-permeation chromatography was used to determine the degree of polymerization (DP) of cellulose, and solid-state cross polarization/magic angle spinning 13C NMR experiments were conducted to study the changes in crystallinity and ultrastructure of cellulose. The results showed a decrease in DP along with an increase in the relative proportions of para-crystalline and amorphous cellulose and a decrease in cellulose Ia and Ib. Removal of lignin and hemicellulose, reduction in DP, and decrease in the crystalline allomorphs (Ia and Ib) increased the amenability of the biomass to enzymatic degradation.

Effect of Ethanol Organosolv Pretreatment on Enzymatic Hydrolysis of Buddleja davidii Stem Biomass

A current barrier to the large-scale production of lignocellulosic biofuels is the cost associated with the energy and chemical inputs required for feedstock pretreatment and hydrolysis. The use of controlled partial biological degradation to replace elements of the current pretreatment technologies would offer tangible energy and cost benefits to the whole biofuel process. It has been known for some time from studies of wood decay that, in the early stages of growth in wood, brown rot fungi utilise a mechanism that causes rapid and extensive depolymerisation of the carbohydrate polymers of the wood cell wall. The brown rot hyphae act as delivery vectors to the plant cell wall for what is thought to be a combination of a localised acid pretreatment and a hydroxyl radical based depolymerisation of the cell wall carbohydrate polymers. It is this quality that we have exploited in the present work to enhance the saccharification potential of softwood forest residues for biofuel production. Here we show that after restricted exposure of pine sapwood to brown rot fungi, glucose yields following enzymatic saccharification are significantly increased. Our results demonstrate the potential of using brown rot fungi as a biological pretreatment for biofuel production. © 2010 Elsevier Ltd.

Michael J. Ray

Papers

Ionic liquid pretreatment of lignocellulosic biomass with ionic liquid–water mixtures

Fractionation of lignocellulosic biomass with the ionic liquid 1-butylimidazolium hydrogen sulfate

Biomass characterization of Buddleja davidii: a potential feedstock for biofuel production.

Effect of Ethanol Organosolv Pretreatment on Enzymatic Hydrolysis of Buddleja davidii Stem Biomass

Brown rot fungal early stage decay mechanism as a biological pretreatment for softwood biomass in biofuel production