Refuse-derived fuels (RDF) are rich in resources that make them an attractive feedstock for the production of energy and biofuels. Hydrothermal liquefaction (HTL) is a promising thermochemical conversion technology to handle wet feedstocks and convert them to valuable bio-crude, bio-char and aqueous products. This study highlights the advantages of using glycerol as the co-solvent along with water in different proportions to produce bio-crude from RDF via HTL. The ratio of water:glycerol (vol.%:vol.%) was varied for each experiment (100:0, 90:10, 80:20, 70:30, 60:40, 50:50), and the product yields and their quality were studied. The results demonstrate that increasing the proportion of glycerol until 50 vol.% in the solvent enhances the bio-crude yield (36.2 wt.%) and its higher heating value (HHV) (30.9 MJ kg
−1
). Deoxygenation achieved in the bio-crude was 42%. The production of bio-char was minimum (9.5 wt.%) at 50 vol.% glycerol with HHV of 31.9 MJ kg
−1
. The selectivity to phenolic compounds in the bio-crude increased, while that of cyclic oxygenates decreased when the glycerol content was more than 20 vol.%. The gas-phase analysis revealed that the major deoxygenation pathway was decarboxylation. The yield of aqueous products drastically increased with the addition of glycerol. The minimum amount of glycerol in the co-solvent that favours an energetically feasible process with low carbon footprint is 30 vol.%. Using 50 vol.% glycerol resulted in the highest energy recovery in the bio-crude and bio-char (80%), the lowest energy consumption ratio (0.43) and lowest environmental factor (0.1). The mass-based process mass intensity factor, calculated based on only bio-crude and bio-char as the valuable products, decreased with an increase in addition of glycerol, while it was close to unity when the aqueous phase is also considered as a valuable product.
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