Abstract

Microalgal lipid extraction, particularly the subsequent solvent recovery phase, constitutes the primary energy bottleneck in algal-based biodiesel biorefineries. Recently, switchable polarity solvents (SPS), such as the tertiary amine N,N-dimethylcyclohexylamine (DMCHA), have emerged as promising ‘green’ alternatives capable of extracting lipids directly from wet biomass, theoretically bypassing energy-intensive drying and solvent recovery distillation stages. This study presents a rigorous techno-energetic and thermodynamic evaluation combined with supporting experiments for qualitative conclusions to scrutinize the actual viability of DMCHA-mediated extraction against conventional hexane benchmarks, across three process configurations using different biomass types: algal liquor, wet paste, and dried biomass. Contrary to widespread assumptions in the literature, fundamental thermodynamic calculations reveal that the energy required for amine regeneration via protonation/deprotonation mechanisms equals or exceeds that of conventional distillation. Furthermore, mitigating biomass drying inadvertently escalates overall downstream energy and economic penalties due to the excessive solvent volumes demanded by dilute aqueous matrices. Direct extraction from algal liquor displays a cost and energy consumption countably higher than the other scenario; precisely, a cost of 232 €/kg of lipids and energy consumption of 454 kWh/kg of lipids. Extraction from wet paste exhibits, indeed, a slightly lower energy consumption compared to the hexane process (respectively 51 kWh/h versus 72 kWh/kg), but, due to the CO2 requirements, the cost is double (19 €/kg of lipids versus 8 €/kg of lipids). Ultimately, while switchable polarity chemistry offers a marginal reduction in process water footprints, it introduces substantial operational complexity, elevated carbon dioxide payloads, and severe solvent degradation risks, challenging its current readiness for industrial upscaling.

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