Strategic use of CO2 in the catalytic thermolysis of bio-heavy oil over Co/SiO2 for the enhanced production of syngas

•Bio-heavy oil (BHO) valorization through CO2-assisted pyrolysis was conducted.•Carbon redistribution from CO2 and fatty acids into CO was achieved.•Synergistic effect of CO2 and Co catalysts expedited CO/H2 formation from BHO. Bio-heavy oil (BHO), a mixture of remaining free fatty acids and glyceri...

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Bibliographic Details
Published in:Energy conversion and management 2020-10, Vol.222, p.113195, Article 113195
Main Authors: Cho, Seong-Heon, Jung, Sungyup, Lin, Kun-Yi Andrew, Kwon, Eilhann E.
Format: Article
Language:English
Subjects:
Bio-heavy oil
Biodiesel fuels
Biofuels
Carbon dioxide
Catalysts
Catalytic pyrolysis
CO2-to-fuel
Dehydrogenation
Fatty acids
Glycerides
Greenhouse effect
Greenhouse gases
Hydrogen
Impurities
Pretreatment
Pyrolysis
Silicon dioxide
Synthesis gas
Vapor phases
Waste materials
Waste valorization
Waste-to-energy
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Summary:•Bio-heavy oil (BHO) valorization through CO2-assisted pyrolysis was conducted.•Carbon redistribution from CO2 and fatty acids into CO was achieved.•Synergistic effect of CO2 and Co catalysts expedited CO/H2 formation from BHO. Bio-heavy oil (BHO), a mixture of remaining free fatty acids and glycerides is released as waste materials from biodiesel synthesis process. However, the complexity and impurities in BHO are drawbacks for its valorization due to essential requirement of multiple pretreatment processes. In this study, a direct valorization of BHO into value-added gaseous products was investigated using pyrolysis under CO2 condition. CO2 was used to achieve two goals: (1) establishment of environmentally benign platform using a greenhouse gas, and (2) carbon redistribution between CO2 and BHO to produce more value-added products. Pyrolysis under both CO2 and N2 showed the conversion BHO into syngas and CH4. However, CO2-mediated pyrolysis had additional CO generation with decrease of the volatile matters from BHO pyrolysis. These resulted from gas phase reaction (GPR) of CO2 with volatile matters. To further activate the thermal cracking of BHO and GPRs, multi-stage pyrolysis and catalytic pyrolysis was performed with Co catalysts. CO2-mediated catalytic pyrolysis resulted in both significant formations of CO and H2 from GPRs and dehydrogenation. Therefore, the proposed technical platform could be considered a viable environmentally benign way for waste valorization.
ISSN:0196-8904
1879-2227
DOI:10.1016/j.enconman.2020.113195