Novel Four-Dimensional Approach for the Structural Characterization of Neutral Nitrogen compounds in Vacuum Gas oils using UHPLC-IM-QqToF Analysis

Julie Guillemant (1) , Alexandra Berlioz-Barbier (1) , Luis P. de Oliveira (1) , Marion Lacoue-Nègre (1) , Jean-François Joly (1) , Ludovic Duponchel (2)

1 IFPEN - IFP Energies nouvelles
2 LASIRE - Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516

The molecular analysis of complex matrices such as vacuum gas oils require powerful instruments such as Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS). As this technique does not allow the separation of two isomers, ion mobility coupled to mass spectrometry (IMMS) can be used to target a structural detail. However, the resolving power of ion mobility is not sufficient to resolve isomers in such a complex mixture. In this paper, ion mobility-mass spectrometry coupled to separative methods such as Flash-HPLC and UHPLC has been used to characterize the neutral nitrogen compounds found in vacuum gas oils. One vacuum gas oil feedstock as well as different hydrotreated samples have been analyzed through a heart-cutted HPLC-UHPLC-IM-QqToF analysis to target specific compounds that have been found to be problematic within hydrotreatment context thanks to ESI(−)-FT-ICR MS analyses. The extraction of the macroscopic descriptors (mobility, full-width at half-maximum) allowed highlighting first trends about the samples. Then, the chromatographic peaks obtained for a given alkylation degree have been divided into several retention time segments and the corresponding mobilograms have been obtained. Bi-modal distributions have been obtained and the observed Collision Cross Sections and MS/MS spectra suggested the presence of compact and non-compact structures. The evolution of these structures has been followed throughout hydrotreatment to evaluate both the quantity and the reactivity of the groups of isomers. Moreover, this methodology helped giving clues whether the targeted compounds are refractory to the hydrotreatment process or reaction intermediates of the hydrotreatment process.

Domaines: Sciences de l'environnement

Julie Guillemant, Alexandra Berlioz-Barbier, Luis P. de Oliveira, Marion Lacoue-Nègre, Jean-François Joly, et al.. Novel Four-Dimensional Approach for the Structural Characterization of Neutral Nitrogen compounds in Vacuum Gas oils using UHPLC-IM-QqToF Analysis. Analytica Chimica Acta, 2021, 1169, pp.338611. ⟨10.1016/j.aca.2021.338611⟩. ⟨hal-03500291⟩