This critical review provides a survey illustrated by recent references of different strategies to achieve a sustainable conversion of biomass to bioproducts. Because of the huge number of chemical products that can be potentially manufactured, a selection of starting materials and targeted chemicals has been done. Also, thermochemical conversion processes such as biomass pyrolysis or gasification as well as the synthesis of biofuels were not considered. The synthesis of chemicals by conversion of platform molecules obtained by depolymerisation and fermentation of biopolymers is presently the most widely envisioned approach. Successful catalytic conversion of these building blocks into intermediates, specialties and fine chemicals will be examined. However, the platform molecule value chain is in competition with well-optimised, cost-effective synthesis routes from fossil resources to produce chemicals that have already a market. The literature covering alternative value chains whereby biopolymers are converted in one or few steps to functional materials will be analysed. This approach which does not require the use of isolated, pure chemicals is well adapted to produce high tonnage products, such as paper additives, paints, resins, foams, surfactants, lubricants, and plasticisers. Another objective of the review was to examine critically the green character of conversion processes because using renewables as raw materials does not exempt from abiding by green chemistry principles (368 references).

Conversion of biomass to selected chemical products

This review gives a survey on the latest most representative developments and progress concerning ionic liquids, from their fundamental properties to their applications in catalytic processes. It also highlights their emerging use for biomass treatment and transformation.

Ionic liquids and catalysis: Recent progress from knowledge to applications

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

Conversion of Biomass into Chemicals over Metal Catalysts

Recent Advances in Polyoxometalate-Catalyzed Reactions

Liquid organic hydrogen carrier (LOHC) systems offer a very attractive method for the decentralized storage of renewable excess energy. In this contribution, industrially well-established heat-transfer oils (typically sold under trade names, e.g., Marlotherm) are proposed as a new class of LOHC systems. It is demonstrated that the liquid mixture of isomeric dibenzyltoluenes (m.p. −39 to −34 °C, b.p. 390 °C) can be readily hydrogenated to the corresponding mixture of perhydrogenated analogues by binding 6.2 wt % of H2. The liquid H2-rich form can be stored and transported similarly to diesel fuel. It readily undergoes catalytic dehydrogenation at temperatures above 260 °C, which proves its applicability as a reversible H2 carrier. The presented LOHC systems are further characterized by their excellent technical availability at comparably low prices, full registration of the H2-lean forms, and excellent thermal stabilities.

Evaluation of Industrially Applied Heat‐Transfer Fluids as Liquid Organic Hydrogen Carrier Systems

Beech lignin was oxidatively cleaved in ionic liquids to give phenols, unsaturated propylaromatics, and aromatic aldehydes. A multiparallel batch reactor system was used to screen different ionic liquids and metal catalysts. Mn(NO(3))(2) in 1-ethyl-3-methylimidazolium trifluoromethanesulfonate [EMIM][CF(3)SO(3)] proved to be the most effective reaction system. A larger scale batch reaction with this system in a 300 mL autoclave (11 g lignin starting material) resulted in a maximum conversion of 66.3 % (24 h at 100 degrees C, 84x10(5) Pa air). By adjusting the reaction conditions and catalyst loading, the selectivity of the process could be shifted from syringaldehyde as the predominant product to 2,6-dimethoxy-1,4-benzoquinone (DMBQ). Surprisingly, the latter could be isolated as a pure substance in 11.5 wt % overall yield by a simple extraction/crystallization process.

Oxidative Depolymerization of Lignin in Ionic Liquids

Selective catalytic conversion of biobased carbohydrates to formic acid using molecular oxygen

Liquid Organic Hydrogen Carrier (LOHC) systems offer a very attractive way to store and transport hydrogen, a technical feature that is highly desirable to link unsteady energy production from renewables with the vision of a sustainable, CO2-free, hydrogen-based energy system. LOHCs can be charged and discharged with considerable amounts of hydrogen in cyclic, catalytic hydrogenation and dehydrogenation processes. As their physico-chemical properties are very similar to diesel, today's infrastructure for liquid fuels can be used for their handling thus greatly facilitating the step-wise transition from today's fossil system to a CO2 emission free energy supply for both, stationary and mobile applications. However, for a broader application of these liquids it is mandatory to study in addition to their technical performance also their potential impact on the environment and human health. This paper presents the first account on the toxicological profile of some potential LOHC structures. Moreover, it documents the importance of an early integration of hazard assessment in technology development and reveals for the specific case of LOHC structures the need for additional research in order to overcome some challenges in the hazard assessment for these liquids.

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Environmental and health impact assessment of Liquid Organic Hydrogen Carrier (LOHC) systems – challenges and preliminary results

The oxidation of complex, water-insoluble biomass to formic acid is reported using a Keggin-type polyoxometalate (H5PV2Mo10O40) as the homogeneous catalyst, oxygen as the oxidant, water as the solvent and p-toluenesulfonic acid as the best additive. The reaction proceeds at 90 °C and 30 bar O2 and transforms feedstock like wood, waste paper, or even cyanobacteria to formic acid and CO2 as the sole products. The reaction obtains up to 53% yield in formic acid for xylan as the feedstock within 24 h. Besides the role of the additive as a reaction promoter, the formic acid isolation and the recycling of catalyst and additive are demonstrated.

Andreas Bösmann

Papers

Evaluation of Industrially Applied Heat‐Transfer Fluids as Liquid Organic Hydrogen Carrier Systems

Oxidative Depolymerization of Lignin in Ionic Liquids

Selective catalytic conversion of biobased carbohydrates to formic acid using molecular oxygen

Environmental and health impact assessment of Liquid Organic Hydrogen Carrier (LOHC) systems – challenges and preliminary results

Selective oxidation of complex, water-insoluble biomass to formic acid using additives as reaction accelerators