In this study, a simple and green protocol to obtain hydrochar and high-added value products, mainly 5-hydroxymethylfurfural (5-HMF), furfural (FU), levulinic acid (LA) and alkyl levulinates, by using the hydrothermal carbonization (HTC) of orange peel waste (OPW) is presented. Process variables, such as reaction temperature (180–300 °C), reaction time (60–300 min), biomass:water ratio and initial pH were investigated in order to find the optimum conditions that maximize both the yields of solid hydrochar and 5-HMF and levulinates in the bio-oil. Data obtained evidence that the highest yield of hydrochar is obtained at a 210 °C reaction temperature, 180 min residence time, 6/1 w/w orange peel waste to water ratio and a 3.6 initial pH. The bio-products distribution strongly depends on the applied reaction conditions. Overall, 180 °C was found to be the best reaction temperature that maximizes the production of furfural and 5-HMF in the presence of pure water as a reaction medium.

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Limonene is a renewable cyclic monoterpene that is easily obtainable from citrus peel and it is commonly used as a nutraceutical ingredient, antibacterial, biopesticide and green extraction solvent as well as additive in healthcare, fragrance and food and beverage industries for its characteristic lemon-like smell. Indeed, the lack of toxicity makes limonene a promising bio-alternative for the development of a wide range of effective products in modern biorefineries. As a consequence, industrial demand largely exceeds supply by now. Limonene can be also used as starting substrate for the preparation of building block chemicals, including p-cymene that is an important intermediate in several industrial catalytic processes. In this contribution, after reviewing recent advances in the recovery of limonene from citrus peel and residues with particular attention to benign-by-design extractive processes, we focus on the latest results in its dehydrogenation to p-cymene via heterogeneous catalysis. Indeed, the latest reports evidence that the selective production of p-cymene still remains a scientific and technological challenge since, in order to drive the isomerization and dehydrogenation of limonene, an optimal balance between the catalyst nature/content and the reaction conditions is needed.