Oxidative upgrade of lignin – Recent routes reviewed
TL;DR: In this article, a review of recent achievements in the field of oxidatively upgrading lignin is presented, focusing on organometal catalyses (MTO, salen complexes, POMs), biomimetic catalyses, and enzymatic catalyses.
About: This article is published in European Polymer Journal.The article was published on 2013-06-01 and is currently open access. It has received 398 citations till now.
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TL;DR: This paper presents a new state-of-the-art implementation of the iChEM (Collaborative Innovation Center of Chemistry for Energy Materials) Key Laborotary of Catalysis, which automates the very labor-intensive and therefore expensive and therefore time-heavy and expensive process ofalysis.
Abstract: 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 WisconsinMadison, Madison, Wisconsin 53706, United States
1,977 citations
TL;DR: 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.
Abstract: 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.
1,466 citations
TL;DR: This review provides a “beginning‐to‐end” analysis of the recent advances reported in lignin valorisation, with particular emphasis on the improved understanding of lign in's biosynthesis and structure.
Abstract: 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.
1,390 citations
TL;DR: This Review focuses on methods developed to synthesize polymers derived from lignin, monolignols, and lignIn-derived chemicals, such as vanillin.
Abstract: The majority of commodity plastics and materials are derived from petroleum-based chemicals, illustrating the strong dependence on products derived from non-renewable energy sources. As the most accessible, renewable form of carbon (in comparison to CO2), lignocellulosic biomass (defined as organic matter available on a renewable basis) has been acknowledged as the most logical carbon-based feedstock for a variety of materials such as biofuels and chemicals. This Review focuses on methods developed to synthesize polymers derived from lignin, monolignols, and lignin-derived chemicals. Major topics include the structure and processing of lignocellulosic biomass to lignin, polymers utilizing lignin as a macromonomer, synthesis of monomers and polymers from monolignols, and polymers from lignin-derived chemicals, such as vanillin.
1,008 citations
TL;DR: A review of the use of lignin in polymer applications can be found in this paper, where both the direct use of Lignin and the chemical modifications of it are discussed from a polymer chemistry perspective.
Abstract: Next to cellulose, lignin is the second most abundant biopolymer, and the main source of aromatic structures on earth. It is a phenolic macromolecule, with a complex structure which considerably varies depending on the plant species and the isolation process. Lignin has long been obtained as a by-product of cellulose in the paper pulp production, but had rather low added-value applications. Changes in the paper market have however stimulated the need to focus on other applications for lignins. In addition, the emergence of biorefinery projects to develop biofuels, bio-based materials and chemicals from carbohydrate polymers should also generate large amounts of lignin with the potential for value addition. These developments have brought about renewed interest in the last decade for lignin and its potential use in polymer materials. This review covers both the topics of the direct use of lignin in polymer applications, and of the chemical modifications of lignin, in a polymer chemistry perspective. The future trend toward micro- and nanostructured lignin-based materials is then addressed.
564 citations
References
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TL;DR: Simultaneous saccharification and fermentation effectively removes glucose, which is an inhibitor to cellulase activity, thus increasing the yield and rate of cellulose hydrolysis, thereby increasing the cost of ethanol production from lignocellulosic materials.
5,860 citations
"Oxidative upgrade of lignin – Recen..." refers background in this paper
...(thermolysis) [17–20], hydrolysis [21,22], reduction (hydrogenolysis) [23–25], or oxidation [26,27], to newer...
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TL;DR: A review of the recent developments in the wood pyrolysis and reports the characteristics of the resulting bio-oils, which are the main products of fast wood pyrotechnics, can be found in this paper.
Abstract: Fast pyrolysis utilizes biomass to produce a product that is used both as an energy source and a feedstock for chemical production. Considerable efforts have been made to convert wood biomass to liquid fuels and chemicals since the oil crisis in mid-1970s. This review focuses on the recent developments in the wood pyrolysis and reports the characteristics of the resulting bio-oils, which are the main products of fast wood pyrolysis. Virtually any form of biomass can be considered for fast pyrolysis. Most work has been performed on wood, because of its consistency and comparability between tests. However, nearly 100 types of biomass have been tested, ranging from agricultural wastes such as straw, olive pits, and nut shells to energy crops such as miscanthus and sorghum. Forestry wastes such as bark and thinnings and other solid wastes, including sewage sludge and leather wastes, have also been studied. In this review, the main (although not exclusive) emphasis has been given to wood. The literature on woo...
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TL;DR: Biomass is an important feedstock for the renewable production of fuels, chemicals, and energy, and it recently surpassed hydroelectric energy as the largest domestic source of renewable energy.
Abstract: Biomass is an important feedstock for the renewable production of fuels, chemicals, and energy. As of 2005, over 3% of the total energy consumption in the United States was supplied by biomass, and it recently surpassed hydroelectric energy as the largest domestic source of renewable energy. Similarly, the European Union received 66.1% of its renewable energy from biomass, which thus surpassed the total combined contribution from hydropower, wind power, geothermal energy, and solar power. In addition to energy, the production of chemicals from biomass is also essential; indeed, the only renewable source of liquid transportation fuels is currently obtained from biomass.
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TL;DR: In this paper, the authors identified twelve building block chemicals that can be produced from sugar via biological or chemical conversions, and the twelve building blocks can be subsequently converted to a number of high-value bio-based chemicals or materials.
Abstract: This report identifies twelve building block chemicals that can be produced from sugars via biological or chemical conversions. The twelve building blocks can be subsequently converted to a number of high-value bio-based chemicals or materials. Building block chemicals, as considered for this analysis, are molecules with multiple functional groups that possess the potential to be transformed into new families of useful molecules. The twelve sugar-based building blocks are 1,4-diacids (succinic, fumaric and malic), 2,5-furan dicarboxylic acid, 3-hydroxy propionic acid, aspartic acid, glucaric acid, glutamic acid, itaconic acid, levulinic acid, 3-hydroxybutyrolactone, glycerol, sorbitol, and xylitol/arabinitol.
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TL;DR: In this article, a solid substrate with a positively charged planar surface is immersed in a solution containing an anionic polyelectrolyte and a monolayer of the polyanion is adsorbed.
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