| Summary: | The catalytic potential of Na and LiNa fly ash (FA) obtained through a simple solid-state synthesis was investigated for the pyrolysis of <i>Isochrysis</i> sp. microalgae using a fixed bed reactor at 500 °C. While both LiNa-FA and Na-FA catalysts reduced the bio-oil yield and increased char and gas production, LiNa-FA was found to enhance the quality of the resulting bio-oil by decreasing its oxygen content (−25 wt.%), increasing paraffins and olefins and decreasing its acidity. The deoxygenation activity of LiNa-FA was attributed to the presence of weak and mild base sites, which enabled dehydration, decarboxylation, ketonisation, and cracking to form olefins. The bio-oil generated with LiNa-FA contained higher amounts of alkanes, alkenes, and carbonated esters, indicating its capacity to chemisorb and partially desorb CO<sub>2</sub> under the studied conditions. These findings suggest that LiNa-FA catalysts could be a cost-effective alternative to acidic zeolites for in situ deoxygenation of microalgae to biofuels.
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