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Formate-Assisted Pyrolysis of Defatted Microalgae for In Situ Heteroatom Removal and Carbon Retention in Bio-Oil
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DOI：10.1021/acssuschemeng.6c02328.png)
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Abstract
En 中文
Defatted microalgae serve as promising pyrolysis feedstocks for producing high-value biofuels and chemicals. However, upgrading the resulting nitrogen-rich bio-oil remains an economic challenge due to the need of costly external hydrogen in the conventional hydrotreatment for cracking of heavy components, effective deoxygenation (DeO), denitrogenation (DeN), and maximizing carbon retention. To address this, this study employed low-cost formate salts (calcium formate: CF and nickel formate: NF) as in situ hydrogen donors in the fast pyrolysis. The addition of CF resulted in higher organic and carbon yields (38.5 and 64.4 wt %, respectively) than non-additive pyrolysis, along with moderate DeO (23.2%) and DeN (8.1%). In contrast, NF was a superior hydrogen donor, achieving substantially higher DeO values of 48.9% and DeN values of 12.1%. The strong synergy between Ni and hydrogen radicals in NF lowered amide and nitrile yields by enhancing decomposition. NF and CF increased N-heterocycle yields by hydrocracking multiring structures via hydrogen radical attack and boosted olefin hydrogenation due to hydrogen from formate salt decomposition, forming hydrocarbons. These results establish the viability of using formate salts as a hydrogen donor for N-rich heavy bio-oil upgrading at ambient pressure, facilitating heteroatom removal while maintaining promising carbon retention.
Keywords:
Biofuels
Hydrocarbons
Hydrogen
Pyrolysis
formate
defatted microalgae
deoxygenation
denitrogenation
hydrogen
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