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Hydrothermal liquefaction of lignin-rich stream from lignocellulosic ethanol production at an industrial scale was carried out in a custom-made batch test bench. Light and heavy fractions of the HTL biocrude were collected following an ad-hoc developed two-steps solvent extraction method. A full factorial design of experiment was performed, investigating the influence of temperature, time and biomass-to-water mass ratio (B/W) on product yields, biocrude elemental composition, molecular weight and carbon balance. Total biocrude yields ranged from 39.8% to 65.7% w/w. The Temperature was the main influencing parameter as regards the distribution between the light and heavy fractions of the produced biocrude: the highest amount of heavy biocrude was recovered at 300 °C, while at 350 and 370 °C the yield of the light fraction increased, reaching 41.7% w/w at 370 °C. Instead, the B/W ratio did not have a significant effect on light and heavy biocrude yields. Feedstock carbon content was mainly recovered in the biocrude (up to 77.6% w/w). The distribution between the light and heavy fractions followed the same trend as the yields. The typical aromatic structure of the lignin-rich stream was also observed in the biocrudes, indicating that mainly hydrolysis depolymerization occurred. The weight-average molecular weight of the total biocrude was strictly related to the process temperature, decreasing from 1146 at 300 °C to 565 g mol−1 at 370 °C.

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Finding a proper way to manage the enormous amount of waste plastic that is globally produced, is one of the main environmental challenges of our times. Among the different types of chemical recycling, Hydrothermal Liquefaction (HTL) appears as a potential method for the treatment of plastic waste mixes, for sustainable production of biocrude or chemicals with high added value. In this work hydrothermal liquefaction reactions were carried out on a polymeric residue, obtained from an industrial plastic waste collection and recycling process. The residue has a heterogeneous composition consisting not only of polymers but also paper and metals. Two batch experiments were performed in a stainless-steel Parr autoclave at 340 °C, investigating a residence times of 5 hours and the use of an alkaline catalyst (NaOH). The oils obtained from the reactions, as well as the aqueous phases, have been analysed by different analytical techniques such as: FT-IR spectroscopy, GC-MS, GC-FID, IC. The operating conditions used in this work, allowed the degradation of cellulose and polymers with reactive sites for hydrolysis such as PET, nylon and PVAc, while polyolefins (PE, PP) were not attacked. The use of a basic catalyst favoured a greater hydrolysis rate.

Hydrothermal depolymerization of lignin-rich streams (LRS) from lignocellulosic ethanol was successfully carried out in a lab-scale batch reactors unit. A partial depolymerization into oligomers and monomers was achieved using subcritical water as reaction medium. The influence of temperature (300–350–370 °C) and time (5–10 minutes) was investigated to identify the optimal condition on the monomers yields in the lighter biocrude (BC1) and aqueous phase (AP) fractions, focusing on specific phenolic classes as well as carboxylic acids and alcohols. The effect of base catalyzed reactions (2–4 wt. % of KOH) was compared to the control tests as well as to acid-catalyzed reactions obtained with a biphasic medium of supercritical carbon dioxide (sCO2) and subcritical water. KOH addition resulted in enhanced overall depolymerization without showing a strong influence on the phenolic generation, whereas sCO2 demonstrated higher phenolic selectivity even though no effect was observed on the overall products mass yields. In conclusion, a comparison between two different biocrude collection procedures was carried out in order to understand how the selected chemical extraction mode influences the distribution of compounds between BC1 and AP.