The direct carboxylation of crude glycerol, obtained as a by-product of bio-diesel synthesis, with CO 2 has been investigated over lanthanum oxide as a heterogeneous catalyst for the irst time. Adiponitrile is employed as a dehydrating agent in order to shift the reaction equilibrium to the product side. The selectivity of the reaction towards glycerol carbonate when using crude glycerol is signiicantly reduced as compared to employing reined glycerol: 2.3% cf. 17% respectively. Glycerol conversion, however remains approximately constant: 54% cf. 58%. In order to understand the role of the impurities present in crude glycerol, model systems consisting of reined glycerol and one or more of water, methanol, methyl palmitate (as a model fatty acid methyl ester), and sodium methoxide have been prepared and used as reaction media to systematically evaluate their efect. All of these impurities are seen to reduce the selectivity towards glycerol carbonate, instead favouring the formation of 4-(hydroxymethyl)oxazolidin-2-one, with the exception of methanol where no detrimental efect is observed and the measured selectivity increases slightly to ca. 22%. This efect is ascribed, in part, to improved mass transfer as a consequence of an increased solubility of carbon dioxide in the liquid media when methanol is present. Additionally, adiponitrile is observed to play a crucial role in the reaction mechanism beyond its simple role as a dehydrating agent. These results provide insights into the required puriication steps for crude glycerol, and suggest the possibility of employing crude glycerol directly, and its use as a chemical feedstock; in both cases by minimising costly separation and puriication steps.

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Improved yields of, and selectivities to, value-added products synthesised from glycerol are shown to be achieved through the judicious selection of dehydrating agents and through the development of improved catalysts. The direct carboxylation of glycerol with CO2 over lanthanum-based catalysts can yield glycerol carbonate in the presence of basic species, or acetins in the presence of acidic molecules. The formation of glycerol carbonate is thermodynamically limited; removal of produced water shifts the chemical equilibrium to the product side. Acetonitrile, benzonitrile and adiponitrile have been investigated as basic dehydrating agents to promote glycerol carbonate synthesis. In parallel, acetic anhydride has been studied as an acidic dehydrating agent to promote acetin formation. Alongside this, the influence of the catalyst synthesis method has been investigated allowing links between the physicochemical properties of the catalyst and catalytic performance to be determined. The use of acetonitrile and La catalysts allows the results for the novel dehydrating agents to be benchmarked against literature data. Notably, adiponitrile exhibits significantly enhanced performance over other dehydrating agents, e.g., achieving a 5-fold increase in glycerol carbonate yield with respect to acetonitrile. This is in part ascribed to the fact that each molecule of adiponitrile has two nitrile functionalities to promote the reactive removal of water. In addition, mechanistic insights show that adiponitrile results in reduced by-product formation. Considering by-product formation, 4-hydroxymethyl(oxazolidin)-2-one (4-HMO) has, for the first time, been observed in all reaction systems using cyanated species. Studies investigating the influence of the catalyst synthesis route show a complex relationship between surface basicity, surface area, crystallite phase and reactivity. These results suggest alternative strategies to maximise the yield of desirable products from glycerol through tailoring the reaction chemistry and by-product formation via an appropriate choice of dehydrating agents and co-reagents.

The impact of the chemical and physical composition of biochar catalysts is demonstrated in the carboxylation of glycerol with carbon dioxide for the first time, using acetonitrile as a dehydrating agent. Biochars are an important emerging class of catalytic material that can readily be produced from low-value biomass residues; however, the impact of feedstock choice is often overlooked. The ash content of biochar from three different feedstocks is shown to be catalytically active for the production of glycerol carbonate and triacetin, whilst low-ash catalysts such as soft wood biochar and commercial activated charcoal are inactive. Following treatment with hydrochloric acid, yields of glycerol carbonate over ash were reduced by over 94%, and triacetin was no longer produced. This has been attributed to the loss of potassium content. Carbon content was shown to be catalytically active for the synthesis of diacetin, and graphitic carbon may be beneficial. Through the development of structure–performance relationships, biomass feedstocks with the most suitable properties can therefore be selected to produce biochars for specific catalytic applications. This would expand the range of reactions which can be effectively catalysed by these materials and enhance the development of a more circular and sustainable chemicals industry.