Pyrolysis of macroalgae: Insight into product yields and biochar morphology and stability

Pyrolysis of biomass residues into biochar is seen as a feasible way to mitigate climate change by biological carbon storage (carbon dioxide removal, CDR) and to substitute fossil fuel with sustainable biofuel. This study applies a combination of flash and ramp heating pyrolysis, and organic petrography to investigate the hydrocarbon (biofuel) potential and biochar stability and morphotypes of eight brown, red, and green macroalgal species of different tissue complexity. The carbon stability of biochar derived from macroalgae has not previously been assessed using organic petrography (reflectance measurements) and evaluated in the context of the geological carbon cycle. The biochar, hydrocarbon, and CO + CO₂ yields vary due to different chemical composition of the macroalgal species, but the product yield variations are not related to the brown, red, or green macroalgal groups. The total biofuel yield shows an inverse trend with biochar yield. A slower heating rate produces more biochar and higher CO + CO₂ and lower biofuel yields than the combined flash pyrolysis and faster heating rate. The morphotype composition of the biochar was qualitatively examined by reflected light microscopy while carbon stability was assessed by random reflectance (R_o) measurements. The diverse morphotype compositions observed in biochar formed under similar pyrolysis conditions likely stem from variations in the original algal composition. While some biochar samples show morphologies resembling the original macroalgal structure, porous morphotypes predominantly characterize the biochar samples overall. Despite a maximum pyrolysis production temperature (PT) of 650 °C, the highest mean R_o value among all biochar samples is 2.91%, corresponding to a carbonization temperature (CT) of 526 °C. This observation is tentatively related to the less lignocellulosic structure of the macroalgae compared to terrigenous biomass. Four biochar samples have their entire R_o distribution range above the inertinite benchmark (IBR_o2%) of R_o = 2% indicating high carbon stability. Conversely, the remaining four biochar samples exhibit R_o distributions extending below IBR_o2%, indicating the presence of a carbon fraction with lower long-term stability in soil. The statistically significant inverse relationship observed between the mean R_o values and the peak hydrocarbon generation temperature (T_max) can be attributed to the behavior of residual macromolecules within the biochar. When these macromolecules reach peak biofuel generation at a lower temperature, they undergo carbonization over a more extended time interval during pyrolysis. Consequently, this prolonged exposure to the pyrolysis process leads to higher degrees of carbonization, as reflected by higher R_o values. In conclusion, the findings from pyrolysis and organic petrography reveal: (1) Macroalgae demonstrate potential for biofuel production, although biofuel yields contingent upon both the species of macroalgal and the heating rate employed, and (2) This study documents for the first time that flash+ramp pyrolysis of macroalgae yields biochar suitable for long-term carbon storage. However, both the carbon stability inferred from R_o frequency distributions and biochar yields show variations across different macroalgal species and heating rate.