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.

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

Research on lignin deconstruction has recently become the center of interest for scientists and companies worldwide, racing towards harvesting fossil-fuel like aromatic compounds which are so durably put together by plants as products of millions of years of evolution. The natural complexity and high stability of lignin bonds (also as an evolutionary adaptation by plants) makes lignin depolymerization a highly challenging task. Several efforts have been directed towards a more profound understanding of the structure and composition of lignin in order to devise pathways to break down the biopolymer into useful compounds. The present contribution aims to provide an overview of key advances in the field of lignin depolymerisation. Protocols and technologies will be discussed as well as critically evaluated in terms of possibilities and potential for further industrial implementation.

Lignin depolymerisation strategies: towards valuable chemicals and fuels

Valorization of native birch wood lignin into monomeric phenols over nickel-based catalysts has been studied. High chemoselectivity to aromatic products was achieved by using Ni-based catalysts and common alcohols as solvents. The results show that lignin can be selectively cleaved into propylguaiacol and propylsyringol with total selectivity >90% at a lignin conversion of about 50%. Alcohols, such as methanol, ethanol and ethylene glycol, are suitable solvents for lignin conversion. Analyses with MALDI-TOF and NMR show that birch lignin is first fragmented into smaller lignin species consisting of several benzene rings with a molecular weight of m/z ca. 1100 to ca. 1600 via alcoholysis reaction. The second step involves the hydrogenolysis of the fragments into phenols. The presence of gaseous H2 has no effect on lignin conversion, indicating that alcohols provide active hydrogen species, which is further confirmed by isotopic tracing experiments. Catalysts are recycled by magnetic separation and can be reused four times without losing activity. The mechanistic insights from this work could be helpful in understanding native lignin conversion and the formation of monomeric phenolics via reductive depolymerization.

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Lignin depolymerization (LDP) in alcohol over nickel-based catalysts via a fragmentation–hydrogenolysis process

Hydrogenolysis of lignosulfonate into phenols over heterogeneous nickel catalysts

The use of a heterogeneous Lewis acid catalyst, which is insoluble and easily separable during the reaction, is a promising option for hydrolysis reactions from both environmental and practical viewpoints. In this study, ceria showed excellent catalytic activity in the hydrolysis of 4-methyl-1,3-dioxane to 1,3-butanediol in 95% yield and in the one-pot synthesis of 1,3-butanediol from propylene and formaldehyde via Prins condensation and hydrolysis reactions in an overall yield of 60%. In-depth investigations revealed that ceria is a water-tolerant Lewis acid catalyst, which has seldom been reported previously. The ceria catalysts showed rather unusual high activity in hydrolysis, with a turnover number (TON) of 260, which is rather high for bulk oxide catalysts, whose TONs are usually less than 100. Our conclusion that ceria functions as a Lewis acid catalyst in hydrolysis reactions is firmly supported by thorough characterizations with IR and Raman spectroscopy, acidity measurements with IR and 31P magi...

Heterogeneous ceria catalyst with water-tolerant Lewis acidic sites for one-pot synthesis of 1,3-diols via Prins condensation and hydrolysis reactions.

Au nanoclusters with an average size of approximately 1nm size supported on HY zeolite exhibit a superior catalytic performance for the selective oxidation of 5-hydroxymethyl-2-furfural (HMF) into 2,5-furandicarboxylic acid (FDCA). It achieved >99% yield of 2,5-furandicarboxylic acid in water under mild conditions (60 degrees C, 0.3MPa oxygen), which is much higher than that of Au supported on metal oxides/hydroxide (TiO2, CeO2, and Mg(OH)(2)) and channel-type zeolites (ZSM-5 and H-MOR). Detailed characterizations, such as X-ray diffraction, transmission electron microscopy, N-2-physisorption, and H-2-temperature-programmed reduction (TPR), revealed that the Au nanoclusters are well encapsulated in the HY zeolite supercage, which is considered to restrict and avoid further growing of the Au nanoclusters into large particles. The acidic hydroxyl groups of the supercage were proven to be responsible for the formation and stabilization of the gold nanoclusters. Moreover, the interaction between the hydroxyl groups in the supercage and the Au nanoclusters leads to electronic modification of the Au nanoparticles, which is supposed to contribute to the high efficiency in the catalytic oxidation of HMF to FDCA.

Gold Nanoclusters Confined in a Supercage of Y Zeolite for Aerobic Oxidation of HMF under Mild Conditions

The aqueous hydrogenolysis of glycerol was performed over Ni-Ce/AC catalyst. The addition of cerium showed a remarkable promoting effect on the catalytic performance compared with other metals including copper, tin, zinc, aluminum, iron and cobalt. For example, 90.4% of glycerol conversion could be achieved at 473 K under 5 MPa of H(2) with 6 h. The Ni-Ce/AC catalysts were characterized by N(2) physisorption, XRD, TEM, NH(3)-TPD and H(2)-TPR. The results showed that the addition of cerium to the Ni/AC catalyst greatly changed the reductive behavior. (C) 2010 Elsevier B.V. All rights reserved.

Qi Song

Papers

Lignin depolymerization (LDP) in alcohol over nickel-based catalysts via a fragmentation–hydrogenolysis process

Hydrogenolysis of lignosulfonate into phenols over heterogeneous nickel catalysts

Heterogeneous ceria catalyst with water-tolerant Lewis acidic sites for one-pot synthesis of 1,3-diols via Prins condensation and hydrolysis reactions.

Gold Nanoclusters Confined in a Supercage of Y Zeolite for Aerobic Oxidation of HMF under Mild Conditions

Aqueous hydrogenolysis of glycerol over Ni–Ce/AC catalyst: Promoting effect of Ce on catalytic performance