Hydrothermal liquefaction (HTL) of biomass is establishing itself as one of the leading technologies for the conversion of virtually any type of biomass feedstock into drop-in biofuels and renewable materials. Several catalysis strategies have been proposed for this process to increase the yields of the product (biocrude) and/or to obtain a product with better properties in light of the final use. A number of different studies are available in the literature nowadays, where different catalysts are utilized within HTL including both homogeneous and heterogeneous approaches. Additionally, catalysis plays a major role in the upgrading of HTL biocrude into final products, in which field significant developments have been observed in recent times. This review has the ambition to summarize the different available information to draw an updated overall picture of catalysis applied to HTL. The different catalysis strategies are reviewed, highlighting the specific effect of each kind of catalyst on the yields and properties of the HTL products, by comparing them with the non-catalyzed case. This allows for drawing quantitative conclusions on the actual effectiveness of each catalyst, in relation to the different biomass processed. Additionally, the pros and cons of each different catalysis approach are discussed critically, identifying new challenges and future directions of research.
Hydrothermal liquefaction (HTL) technology has garnered immense research interest due to its potential to convert wet biomass into petroleum-like biocrude. Understanding the reaction mechanism and kinetics of HTL is crucial for understanding the process better, estimating the yields, and scaling up. On the other hand, reaction mechanisms and kinetics largely depend upon the feedstock composition and reaction parameters of HTL. However, the literature lacks an in-depth analysis of the reaction mechanism and kinetics concerning biocrude yield and product distribution for a single to multi-feedstock scenario. This review focuses on the reaction mechanisms of various biomolecular components of lignocellulosic biomass, proteins, and lipids in the HTL process under sub- and supercritical conditions. Furthermore, the HTL reaction kinetics, effect of reaction conditions on reaction mechanisms, and product distribution are explored. The findings agree that reaction temperature and retention time follow inverse relations for high biocrude yield. A high heating rate is recommended for higher biocrude yield to avoid cracking and recombination processes. A high solvent/feedstock ratio, depending on feedstock composition, was favored for optimum biocrude yield. In addition, catalysts and reaction solvents, especially organic solvents, effectively contribute towards high biocrude yield, even up to 70%. Heterogeneous catalysts are favored due to reusability and improved biocrude quality. Also, hydrothermal co-liquefaction (multi-feedstock) use for improving biocrude yield was debated. A detailed discussion on the reaction kinetics of various biomolecular components in the HTL process revealed that reactions in HTL normally follow the first-order rate law. Finally, the authors outline the pointers for future research in HTL for industrial upscaling.
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.
In this study, hydrothermal co-liquefaction of restaurant waste for biocrude production was conducted. The feedstock was resembled using the organic fraction of restaurant waste and low-density polyethylene, polypropylene, polystyrene, and polyethylene terephthalate, four plastic types commonly present in municipal solid waste. Using design of experiment and a face-centered central composite design, three factors (feedstock plastic fraction, temperature, time) were varied at three levels each: feedstock plastic fraction (0, 0.25, 0.5), temperature (290 °C, 330 °C, 370 °C), and reaction time (0 min, 30 min, 60 min). The literature reports positive synergistic interactions in hydrothermal co-liquefaction of biomass and plastics; however, in this work, only negative synergistic interactions could be observed. A reason could be the high thermal stability of produced fatty acids that give little room for interactions with plastics. At the same time, mass might transfer to other product phases.
The valorization of waste biomass into tailored adsorbents presents a sustainable strategy for combating industrial water pollution. This study highlights the critical role of precursor morphology in determining the textural properties and function of bio-adsorbents derived from wheat straw (WS) and the organic fraction of municipal solid waste known as biopulp (BP). Through carbonization and KOH activation, the fibrous WS was transformed into a microporous, high-surface-area activated wheat straw (AWS) bio-adsorbent, while the compact BP yielded a mesoporous network in activated biopulp (ABP). This structural difference affects adsorption performance: AWS demonstrated superior efficacy in batch removal of phenols (93.2%) and total organic carbon (85%) from the complex hydrothermal liquefaction aqueous phase (HTL-AP), whereas ABP excelled in treating produced water (PW), achieving >95% removal of organic pollutants. Continuous fixed-bed column studies confirmed the scalability of AWS for HTL-AP treatment, revealing distinct breakthrough dynamics between bulk parameters and specific contaminants. This work provides evidence supporting precursor-dependent tailoring of pore structure for targeted wastewater treatment, providing a possibility for a circular and sustainable solution for the treatment of complex industrial wastewaters.