Revealing the reactivity of individual chemical entities in complex mixtures : the chemistry behind bio-oil upgrading

Bio-oils are precursors for biofuels but are highly corrosive necessitating further upgrading. Furthermore, bio-oil samples are highly complex and represent a broad range of chemistries. They are complex mixtures not simply because of the large number of poly-oxygenated compounds but because each composition can comprise many isomers with multiple functional groups. The use of hyphenated ultrahigh-resolution mass spectrometry affords the ability to separate isomeric species of complex mixtures. Here, we present for the first time, the use of this powerful analytical technique combined with chemical reactivity to gain greater insights into the reactivity of the individual isomeric species of bio-oils. A pyrolysis bio-oils and its esterified bio-oil were analyzed using gas chromatography coupled to Fourier transform ion cyclotron resonance mass spectrometry, and in-house software (KairosMS) was used for fast comparison of the hyphenated data sets. The data revealed a total of 10,368 isomers in the pyrolysis bio-oil and an increase to 18,827 isomers after esterification conditions. Furthermore, the comparison of the isomeric distribution before and after esterification provide new light on the reactivities within these complex mixtures; these reactivities would be expected to correspond with carboxylic acid, aldehyde, and ketone functional groups. Using this approach, it was possible to reveal the increased chemical complexity of bio-oils after upgrading and target detection of valuable compounds within the bio-oils. The combination of chemical reactions alongside with in-depth molecular characterization opens a new window for the understanding of the chemistry and reactivity of complex mixtures

Characterization of bio-crude components derived from pyrolysis of soft wood and its esterified product by ultrahigh resolution mass spectrometry and spectroscopic techniques

In this work, a detailed analysis of a bio-oil obtained by pyrolysis of softwoods and its esterified product is described. Information of the type of chemical function groups were obtained by 13C and 1H nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FT-IR) and compositional analysis was obtained by Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS). The results obtained indicate that aliphatic hydrogen and carbon atoms are found in higher abundance, compared with aromatic hydrogen-carbon frameworks. Furthermore, a decrease in oxygen functional groups was observed after esterification. According to the FTICR MS results, the samples contain highly oxygenated species corresponding to compound classes Ox, NOx and BOx, with a high predominance of Ox species. After esterification, the compositions shifted towards lower oxygen-content, lower number of rings and double bonds, and longer alkyl chains as a consequence of the water removal via the condensation reaction