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Humins, (side-)products of the acid-catalysed dehydration of carbohydrates, will be produced in substantial quantities with the development of industrial biorefining processes. Most structural knowledge about such humins is based on synthetic model humins prepared at lab-scale from typical carbohydrate(-derived) compounds. Here, we report the first extensive characterisation study of an industrial humin. The soluble humin was generated from pilot plant-scale methanolic cyclodehydration of D-fructose to 5-methoxymethyl-2-furfural (MMF), as part of the Avantium YXY® process to produce FDCA. Purification of the industrial humin followed by fractionation allowed isolation of a water-insoluble, high molecular weight fraction (WIPIH) and a water-soluble, low-to-middle molecular weight soluble fraction (WES). Characterisation by elemental analysis, thermogravimetry, IR and NMR spectroscopy and size exclusion chromatography provided a detailed picture of the humin structure in both fractions. Aided by a comprehensive NMR spectral library of furanic model compounds, we identified the main furanic building blocks and inter-unit linkages and propose a structure for this industrial humin sample. The WIPIH and WES fractions were found to be composed of furanic rings interconnected by short aliphatic chains containing a wide range of functionalities including alcohols, ethers, carboxylic acids, esters, aldehydes and ketones. The low level of crosslinking and high functional group content of the industrial humin differ from the more extensively studied, (highly over-)condensed synthetic model humins, towards which they can be considered intermediates. The structural and compositional insights into the nature of an actual industrial humin open up a broad spectrum of valorisation opportunities. [ABSTRACT FROM AUTHOR]

To expedite the valorisation of lignin as a sustainable component in materials applications, rapid and generally available analytical methods are essential to overcome the bottleneck of lignin characterisation. Where features of a lignin's chemical structure have previously been found to be predicted by Partial Least Squares (PLS) regression models built on Infrared (IR) data, we now show for the first time that this approach can be extended to prediction of the glass transition temperature (Tg), a key physicochemical property. This methodology is shown to be convenient and more robust for prediction of Tg than prediction through empirically derived relationships (e. g., Flory‐Fox). The chemometric analysis provided root mean squared errors of prediction (RMSEP) as low as 10.0 °C for a botanically, and a process‐diverse set of lignins, and 6.2 °C for kraft‐only samples. The PLS models could separately predict both the Tg as well as the degree of allylation (%allyl) for allylated lignin fractions, which were all derived from a single lignin source. The models performed exceptionally well, delivering RMSEP of 6.1 °C, and 5.4 %, respectively, despite the conflicting influences of increasing molecular weight and %allyl on Tg. Finally, the method provided accurate determinations of %allyl with RMSEP of 5.2 %. [ABSTRACT FROM AUTHOR]

Transition metal ions and their complexes play a crucial role in homogeneous catalysis. These catalysts are pivotal for the production of, for example, fine chemicals and pharmaceuticals. Nevertheless, because of the homogeneous nature of these catalysts, their extraction and removal from the crude reaction mixture is cumbersome. Here, we propose an alternative approach where metal‐based homogeneous catalysts are generated electrochemically from a metallic anode (Cu), followed by their use without current, and finally again electrochemically deposited on the cathode. The generated Cu ions were used as catalysts in three different reactions of lauroyl peroxide: one ligand‐free (coupling with dienes), one without ligand but with a heteroatom containing substrate (coupling with toluidine and styrene) and one in the presence of 1,10‐phen as ligand (coupling with indazole). In the first two cases, performance of the electrochemically generated catalysts was similar to those reported in literature for classically prepared homogeneous catalysts, whereas in the last case a new reaction was observed. After reaction, the homogeneous copper catalyst could be efficiently removed electrochemically: 99% of the copper could be removed for the ligand‐free reaction, 97% for the amine coupling, whereas 89% of copper could be removed for the reaction containing N‐heterocycle and 1,10‐phenanthroline. [ABSTRACT FROM AUTHOR]