Levulinic acid (LA) is one of the top bio-based platform molecules that can be converted into many valuable chemicals. It can be produced by acid catalysis from renewable resources, such as sugars, lignocellulosic biomass and waste materials, attractive candidates due to their abundance and environmentally benign nature. The LA transition from niche product to mass-produced chemical, however, requires its production from sustainable biomass feedstocks at low costs, adopting environment-friendly techniques. This review is an up-to-date discussion of the literature on the several catalytic systems that have been developed to produce LA from the different substrates. Special attention has been paid to the recent advancements on starting materials, moving from simple sugars to raw and waste biomasses. This aspect is of paramount importance from a sustainability point of view, transforming wastes needing to be disposed into starting materials for value-added products. This review also discusses the strategies to exploit the solid residues always obtained in the LA production processes, in order to attain a circular economy approach.

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5-hydroxymethylfurfural (HMF) is one of the most important renewable platform-chemicals, a very valuable precursor for the synthesis of bio-fuels and bio-products. In this work, the hydrogenation of HMF to two furan diols, 2,5-bis(hydroxymethyl)furan (BHMF) and 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF), both promising renewable monomers, was investigated. Three commercial catalysts, Ru/C, Pd/C and Pt/C, were tested in the hydrogenation of aqueous HMF solutions (2-3 wt%), using a metal loading of 1 wt% respect to HMF content. By appropriate tuning of the process conditions, either BHMF or BHMTHF were obtained in good yields, and Ru/ C resulted the best catalyst for this purpose, allowing us to obtain BHMF or BHMTHF yields up to 93.0 and 95.3 mol%, respectively. This catalyst was also tested for in the hydrogenation of a crude HMF-rich hydrolyzate, obtained by one-pot the dehydration of fructose. The influence of each component of this hydrolyzate on the hydrogenation efficiency was investigated, including unconverted fructose, rehydration acids and humins, in order to improve the yields towards each furan diol. Moreover, ICP-OES and TEM analysis showed that the catalyst was not subjected to important leaching and sintering phenomena, as further confirmed by catalyst recycling study.

Abstract:The hydrothermal conversion of giant reed (Arundo donax L.) to furfural (FA) and levulinic acid (LA) was investigated in the presence of dilute hydrochloric acid. FA and LA yields were improved by univariate optimization of the main reaction parameters: concentration of the acid catalyst, solid/liquid ratio of the reaction mixture, hydrolysis temperature, and reaction time. The catalytic performances were investigated adopting the efficient microwave (MW) irradiation, allowing significant energy and time savings. The best FA and LA yields were further confirmed using a traditionally heated autoclave reactor, giving very high results, when compared with the literature. Hydrolysis temperature and time were the main reaction variables to be carefully optimized: FA formation needed milder reaction conditions, while LA more severe ones. The effect of the crop management (e.g., harvest time) on FA/LA production was discussed, revealing that harvest time was not a discriminating parameter for the further optimization of both FA and LA production, due to the very high productivity of the giant reed throughout the year. The promising results demonstrate that giant reed represents a very interesting candidate for a very high contemporary production of FA and LA of up to about 70% and 90% of the theoretical yields, respectively.

A cascade strategy for the catalytic valorization of aqueous solutions of levulinic acid as well as of γ-valerolactone to 2-methyltetrahydrofuran or to monoalcohols, 2-butanol and 2-pentanol, has been studied and optimized. Only commercial catalytic systems have been employed, adopting sustainable reaction conditions. For the first time, the combined use of ruthenium and rhenium catalysts supported on carbon, with niobium phosphate as acid co-catalyst, has been claimed for the hydrogenation of γ-valerolactone and levulinic acid, addressing the selectivity to 2-methyltetrahydrofuran. On the other hand, the use of zeolite HY with commercial Ru/C catalyst favors the selective production of 2-butanol, starting again from γ-valerolactone and levulinic acid, with selectivities up to 80 and 70 mol %, respectively. Both levulinic acid and γ-valerolactone hydrogenation reactions have been optimized, investigating the effect of the main reaction parameters, to properly tune the catalytic performances towards the desired products. The proper choice of both the catalytic system and the reaction conditions can smartly switch the process towards the selective production of 2-methyltetrahydrofuran or monoalcohols. The catalytic system [Ru/C + zeolite HY] at 200 • C and 3 MPa H 2 is able to completely convert both γ-valerolactone and levulinic acid, with overall yields to monoalcohols of 100 mol % and 88.8 mol %, respectively.