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.

Fast pyrolysis of biomass is a well-known opportunity for sustainable alternative fuel production for transport and energy. However, bio-oils from biomass pyrolysis are viscous, acidic bio-crudes that need further steps of upgrading before being used either as fuels or chemicals. A process that is complementary to bio-oil hydrotreatment or co-processing consists of optimizing and tuning the upstream condensation steps of fast pyrolysis to separate and concentrate selected classes of compounds. This can be implemented by varying the condensation temperatures in a multi-step condensation unit. In this study, fractional condensation of fast pyrolysis vapors from pinewood has been applied to a bubbling fluidized bed reactor of 1 kg h⁻¹ feed. The reactor was operated at 500 °C and connected to a downstream interchangeable condensation unit. Tests were performed using two different condensing layouts: (1) a series of two spray condensers and a tube-in-tube water-jacketed condenser, referred to as an intensive cooler; (2) an electrostatic precipitator and the intensive cooler. Using the first configuration, which is the focus of this study, high boiling point compounds—such as sugars and lignin-derived oligomers—were condensed at higher temperatures in the first stage (100–170 °C), while water-soluble lighter compounds and most of the water was condensed at lower temperatures and thus largely removed from the bio-oil. In the first two condensing stages, the bio-oil water content remained below 7% in mass (and therefore, the oil’s high calorific content reached 22 MJ kg⁻¹) while achieving about 43% liquid yield, compared to 55% from the single-step condensation runs. Results were finally elaborated to perform a preliminary energy assessment of the whole system toward the potential upscaling of this fractional condensation approach. The proposed layout showed a significant potential for the upstream condensation step, simplifying the downstream upgrading stages for alternative fuel production from fast pyrolysis bio-oil.

Exploring the dynamic interaction of non-thermal plasma (NTP) with catalytic processes is critical to unravelling elusive catalyst structure–function relationships under NTP conditions, specifically dielectric barrier discharges (DBD). This study investigates the efficacy of operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) as a tool for characterizing intermediates created by NTP on catalyst surfaces. Leveraging insights from traditional DRIFTS in thermochemical catalysis, we explore the complexities of plasma-induced catalytic reactions, discussing both opportunities and limitations of DRIFTS to study these reaction mechanisms. By summarizing findings from literature and addressing existing knowledge gaps, this perspective highlights how different DRIFTS configurations can affect results, stressing the importance of establishing best practices for studying DBD-driven reactions with DRIFTS. The intended outcomes of this work are to provide guidance on how to effectively use DRIFTS, share fundamental insights into DBD-assisted catalysis, and emphasize the need for complementary techniques to develop catalysts suited for NTP environments.