Hydrothermal liquefaction (HTL) is an emerging technology for bio-crude production but faces challenges in determining the optimal temperature for feedstocks depending on the process mode. In this study, three feedstocks—wood, microalgae spirulina (Algae Sp.), and hydrolysis lignin were tested for sub-supercritical HTL at 350 and 400 °C through six batch-scale experiments. An alkali catalyst (K₂CO₃) was used with wood and hydrolysis lignin, while e (Algae Sp.) was liquefied without catalyst. Further, two experiments were conducted on wood in a Continuous Stirred Tank Reactor (CSTR) at 350 and 400 °C which provided a batch versus continuous comparison. Results showed Algae Sp. had higher bio-crude yields, followed by wood and lignin. The subcritical temperature of 350 °C yielded more biocrude from all feedstocks than the supercritical range. At 400 °C, a significant change occurred in lignin, with the maximum percentage of solids. Additionally, the supercritical state gave higher values for Higher Heating Values (HHVs) and a greater amount of volatile matter in bio-crude. Gas Chromatography and Mass Spectrometry (GCMS) analysis revealed that phenols dominated the composition of bio-crude derived from wood and hydrolysis lignin, whereas Algae Sp. bio-crude exhibited higher percentages of N-heterocycles and amides. The aqueous phase analysis showed a Total Organic Carbon (TOC) range from 7 to 22 g/L, with Algae Sp. displaying a higher Total Nitrogen (TN) content, ranging from 11 to 13 g/L. The pH levels of all samples were consistently within the alkaline range, except for Wood Cont. 350. In a broader perspective, the subcritical temperature range proved to be advantageous for enhancing bio-crude yield, while the supercritical state improved the quality of the bio-crude.

This study primarily addresses the development of dynamic, selective and economical metal–acid (bifunctional) catalysts for one-pot menthol production by citral hydrogenation. Specifically, various metals such as Pd, Pt, Ni, Cs and Sn were doped over alumina support. Additionally, bifunctional composite catalysts were also prepared with the impregnation of heteropoly acids and Pd precursors over alumina support. Analytical techniques (e.g., BET, PXRD, FT-IR, pyridine adsorption and amine titration methods) were applied for characterization of the most efficient and selective catalysts (e.g., Al₂O₃ and PTA-Cat-I). Similarly, most of the essential operational variables (e.g., loading rate of metal precursor, type of heteropoly acid, temperature, gas pressure and reaction time) were examined during this study. The experimental data shows that the bifunctional catalyst (PTA-Cat-I) produced 45% menthol at full citral substrate conversion (r = 0.038 mmoles.min⁻¹) in liquid-phase citral hydrogenation (at optimized operating conditions: 70 °C, 0.5 MPa and 8 h). However, the heteropoly acid-supported bifunctional catalysts (e.g., PTA-Cat-I, PMA-Cat-I, SMA-Cat-I and STA-Cat-I) resulted in cracking and the dehydration of isopulegol/menthol by the generation of side products (e.g., 4-isopropyl-1-methyl, cyclohex-1-ane/ene); therefore, menthol yield was extensively diminished. On the other hand, non-acidic catalysts (e.g., Cat-I, Cat-II, Cat-III, Cat-IV and Cat-V) readily promoted hydrogenation reactions. The optimum menthol yield occurred due to the presence of strong Lewis and weak Bronsted acid sites. Mass transfer and reaction rate were substantially diminished due to acidity strength, heteropoly acid type and blockage of pores by the applied bifunctional catalysts.