Wood to chemicals is the subject of this short critical review, that outlines the chemical and economic aspects of several short-term and long-term perspectives for the valorisation of lignin to aromatics, polymers and materials.
We present a simple method for solubilising lignin using liquid ammonia. Unlike water, which requires harsh conditions, ammonia can solubilise technical lignins, in particular kraft lignin. A commercial pine wood Kraft lignin (Indulin AT) was solubilized instantaneously at room temperature and 7-11 bars autogeneous pressure, while a commercial mixed wheat straw/Sarkanda grass soda lignin (Protobind™ 1000) was solubilized within 3 h at ambient temperature, and 30 min at. 85°C. Hydroxide salts were not required. Wheat straw, poplar and spruce organosolv lignins, as well as elephant grass native lignin (MWL) were also solubilized, albeit at lower values. Different sequences of solubilisation and extraction were tested on the Protobind™ 1000 lignin. The remaining lignin residues were characterized by FTIR, size exclusion chromatography (SEC), elemental analysis (ICP), 2D-NMR and 31 P NMR. Liquid ammonia is not an innocent solvent, as some nitrogen was incorporated in the residual lignin which then rearranged to higher molecular weight fractions. Nevertheless, the mild solubilisation conditions make liquid ammonia an attractive candidate as a solvent for lignin in future biorefinery processes. † Electronic supplementary information (ESI) available. See
Copper on γ-alumina and on mixed magnesia-alumina, Cu/MgO-Al 2 O 3 , catalyse the hydrodeoxygenation (HDO) of β-O-4 lignin-type dimers, giving valuable aromatics. The typical selectivity to phenol is as high as 20%. By changing the support's acidity we can modify the dispersion of copper. Interestingly, more HDO occurs with larger copper agglomerates than with finely dispersed particles. The presence of copper also increases the selectivity of the HDO cleavage. Three different pathways are hypothesized for the reaction on the catalyst surface. Thus, copper activates ketones more and especially more selective towards cleavage than their corresponding alcohols. DFT calculations of bond dissociation energies correlate well with this experimental observation. Excitingly, ethylbenzene is formed in proportional amounts to phenol, showing that these catalysts can reduce the oxygen content of lignin-type product streams. Considering its low price and ready availability, we conclude that copper on alumina is a promising alternative catalyst for lignin depolymerization. † Electronic supplementary information (ESI) available: 1 H NMR spectra of 1 and 2, and surface area measurements (BET) of both catalysts. See
A number of new N-heterocyclic carbene (NHC) ligands were synthesized via a multicomponent reaction, wherein an aldehyde or ketone, a primary amine and an α-acidic isocyanide were reacted, giving the corresponding 2H-2-imidazolines. These were easily alkylated with an alkyl halide at position N-3, yielding the final NHC precursors, that were then complexed with Ru in situ. The resulting complexes are shown to be active and selective catalysts for the transfer hydrogenation of furfural to furfurol, using isopropanol as the hydrogen source. Importantly, the carbene ligand remains coordinated to the ruthenium center throughout the reaction.
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