A comprehensive analysis on the synthesis of value-added chemicals via slow pyrolysis: Valorisation of rapeseed residue, whitewood, and seaweed (Laminaria digitata)

Pyrolysis has emerged as a crucial thermochemical conversion technology in the field of biomass processing. Maximising the valorisation of biomass is an essential area of investigation, as it plays a pivotal role in understanding the economic viability and practical application of these advanced technologies. The novelty of this research is to investigate how slow pyrolysis and process interdependencies influence the synthesis of valueadded products (bio-oil and biogas formation alongside biochar) from distinctly different UK-based biomass feedstocks: rapeseed residue, whitewood, and seaweed (Laminaria digitata). This research also analysed the chemical composition of these products to provide a holistic understanding of the reaction mechanisms involved in their formation. The maximum yield of bio-oil from lignocellulose-rich whitewood was due to the higher selectivity of several endothermic reactions including conversions of 5-hydroxymethylfurfural into cyclic C5 ketones and alkoxyphenols into cresols and aliphatic hydrocarbons, minimizing the biochar formation. The improvement of bio-oil yield from protein-rich seaweed and lipid-rich rapeseed residue was enabled by the formation of N-heterocyclics (e.g., via the Maillard reaction, Dieckmann cyclization, and Buchwald-Hartwig amination) and aliphatic hydrocarbons (e.g., via deamination of fatty amides and nitriles and decarboxylation of fatty acids), respectively. Meanwhile, the dealkylation and demethoxylation of alkoxyphenols and alkylphenols were responsible for the increased content of hydrocarbons in biogas. The findings provide valuable insights into the maximum valorisation of different types of UK-based biomass resources in slow pyrolysis for the production of biochars and lighter bio-oils to make pyrolysis a key process in biorefineries.