Hydrotreatment of bio-oil distillates produced from pyrolysis and hydrothermal liquefaction of duckweed: A comparison study

Highlights: • HTL of duckweed produces a higher crude bio-oil yield than pyrolysis at 350 °C. • Total yield of distillates below 400 °C of HTL oil is larger than pyrolysis oil. • HTL oils and their distillates show much difference in properties from pyrolysis. • N removal of distillates from pyrolysis oil is easier than from HTL oil. • Aromatics and alkanes constitute a large proportion in most of upgraded bio-oils. A comprehensive comparison of hydrothermal liquefaction (HTL) to the pyrolysis of duckweed was conducted to determine the yields and components of the crude bio-oils and their distillates. The upgrading behaviors of the distillates were thoroughly investigated with the use of used engine oil as a solvent. With all other variables fixed, HTL produced crude bio-oil with a lower H/C ratio (1.28 ± 0.03) than pyrolysis did (1.45 ± 0.04). However, its distillates had a higher H/C ratio (1.60 ± 0.05) and total yield (66.1 ± 2.0 wt%) than pyrolysis (1.46 ± 0.04 and 47.2 ± 1.4 wt%, respectively). Phenolics and nitrogenous heterocycles constituted relatively major proportions of the two crude bio-oils and most of their distillates. Obvious differences in molecular composition between the two crude bio-oils and their distillates were ascribed to the distinct impacts of HTL and pyrolysis and were affected by the distillate temperature. Co-hydrotreating with used engine oil (UEO) provided the upgraded bio-oils much higher H/C ratios (~1.78 ± 0.05) and higher heating values (~45.5 ± 1.4 MJ·kg⁻¹), as well as much lower contents of N, O and S compared to their initial distillates. Aromatics and alkanes constituted a large proportion in most of upgraded bio-oils. N removal from the pyrolysis distillates was easier than from the HTL distillates. Distinct differences in yields and molecular compositions for the upgraded bio-oils were also attributed to the different influences associated with the two conversion routes.