Journal
NANOSCALE
Volume 7, Issue 42, Pages 17664-17671Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5nr04404a
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Funding
- US DoD Centers of Research Excellence in Science and Technology (ARO) [W911NF-11-1-0218]
- Institute for Functional Nanomaterials (NSF) [1002410]
- PR NASA EPSCoR (NASA) [NNX13AB22A]
- UPR Center for Renewable Energy and Sustainability
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We report a comprehensive quantitative study of the production of refined bio-crudes via a controlled hydrothermal liquefaction (HTL) process using Ulva fasciata macroalgae (UFMA) as biomass and ultrananocrystalline Fe3O4 (UNCFO) as catalyst. X-ray diffraction and electron microscopy were applied to elucidate the formation of the high-quality nanocatalysts. Gas chromatographymass spectroscopy (GC-MS) and CHNS analyses showed that the bio-crude yield and carbon/oxygen ratios increase as the amount of UNCFO increases, reaching a peak value of 32% at 1.25 wt% (a 9% increase when compared to the catalyst-free yield). The biocrude is mainly composed of fatty acids, alcohols, ketones, phenol and benzene derivatives, and hydrocarbons. Their relative abundance changes as a function of catalyst concentration. FTIR spectroscopy and vibrating sample magnetometry revealed that the asproduced bio-crudes are free of iron species, which accumulate in the generated bio-chars. Our findings also indicate that the energy recovery values via the HTL process are sensitive to the catalyst loading, with a threshold loading of 1.25 wt%. GC-MS studies show that the UNCFO not only influences the chemical nature of the resulting bio-crudes and bio-chars, but also the amount of fixed carbons in the solid residues. The detailed molecular characterization of the bio-crudes and bio-chars catalyzed by UNCFO represents the first systematic study reported using UFMA. This study brings forth new avenues to advance the highly-pure bio-crude production employing active, heterogeneous catalyst materials that are recoverable and recyclable for continuous thermochemical reactions.
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