HRMS-informed development of chemically explicit bio-oil surrogate compounds

While bio-oils are a promising source of renewable carbon for fuels and other chemicals, their valorization has been incredibly difficult. While corrosivity and coke formation hinder direct process research, the complex heterogeneous nature hinders more precise chemical characterization or simulation. The present work attempts to contribute to this area using a tandem experimental and petroleomic approach. Toward this end, we propose a novel liquid chromatography (LC) separation of fractionated bio-oil, allowing clearer analysis via HRMS, NMR, and FTIR. This experimental analysis is performed in combination with lignomic methods to develop a database of putative structures to explicitly represent and simulate each bio-oil fraction. Chromatography of bio-oil’s DCM-soluble fraction effectively separated lipids and hydrocarbons from lignin, while similar separation of DCM-insoluble bio-oil yielded degraded lignin of successively higher molecular weights. Cellulose and lignin fragmentation models proposed by Terrell et al provided good coverage ( >75%) for compounds in water-soluble and DCM-insoluble bio-oil fractions, but performed poorly for the assignment of structures to the DCM-soluble fraction. While the mechanist models used provide reasonable structures for specific compounds, we conclude they do not provide the volume of structures required for a more complete petroleomic representation.