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.

Lignin‐rich stream from lignocellulosic ethanol production was converted into biocrude by continuous hydrothermal liquefaction (HTL) while hydrogen was produced by aqueous phase reforming (APR) of the HTL aqueous by‐product. The effects of Na₂CO₃ and NaOH were investigated both in terms of processability of the feedstock as well as yield and composition of the obtained products. A maximum biocrude yield of 27 wt% was reached in the NaOH‐catalyzed runs. A relevant amount of dissolved phenolics were detected in the co‐produced aqueous phase (AP), and removed by liquid–liquid extraction using butyl acetate or diethyl ether, preserving the APR catalyst stability and reaching an hydrogen yield up to 146 mmol H₂ L⁻¹ AP. Preliminary mass balances integrating HTL and APR showed that the hydrogen provided by APR may account for up to 46% of the hydrogen amount theoretically required for upgrading the HTL biocrude, thus significantly improving the process performance and sustainability.

The aim of the present work is to investigate the possibility of producing activated carbons from the residual lignin stream of lignocellulosic ethanol biorefineries, as this represents an optimal opportunity to exploit a residual and renewable material in the perspective of sustainable bioeconomy, increasing biorefinery incomes by producing value-added bioproducts in conjunction with biofuels. Activated carbons (ACs) were produced via chemical (KOH) and physical (CO₂) activation. Char samples were obtained by slow pyrolysis (SP) and hydrothermal carbonization (HTC). Several HTC experiments were carried out by varying residence time (0.5–3 h) and reaction temperature (200–270 °C), in order to evaluate their influence on the product yield and on the morphological characteristics of the hydrochar (specific surface area, total pore volume and pore size distribution). ACs from hydrochars were compared with those obtained from pyrochar (via physical activation) and from the raw lignin-rich stream (via chemical activation). In both cases, by increasing the HTC temperature, the specific surface of the resulting activated carbons decreased from 630 to 77 m² g⁻¹ for physical activation and from 675 to 81 m² g⁻¹ for chemical activation, indicating that an increase in the severity of the hydrothermal pretreatment is deleterious for the activated carbons quality. In addition, the HTC aqueous samples were analyzed, with GC-MS and GC-FID. The results suggest that at low temperatures the reaction mechanisms are dominated by hydrolysis, instead when the temperature is increased to 270 °C, a more complex network of reactions takes place among which decarboxylation.