We
propose to assess the selectivity of hydrotreatment catalysts by two
complementary analytical methods: (1) high-resolution mass spectrometry
(MS), called “petroleomic” analysis, by Fourier transform
ion cyclotron resonance (FT ICR, 9.4T) MS for species heavier than m/z of about 200 Da and (2) quantitative
GC*GC (heart-cutting)/MS-flame ionization detector (FID) analysis
of lighter species. The methodology is illustrated on methanol-soluble
bio-oils produced by lignin pyrolysis and hydrotreated by iron-based
catalysts. GC*GC analysis is calibrated by a combination of internal
standard and prediction of response factors on the FID. Laser desorption
ionization (LDI) and electro spray ionization (ESI) in negative-ion
mode are combined for the petroleomic analysis. The selectivity of
hydrotreatment (catalytic fixed bed, 1 atm, 400 °C) is assessed
as a function of catalyst loads and iron support (silica and activated
carbon). Hundreds of species are analyzed by GC*GC and petroleomic
and mapped in Van Krevelen diagrams. The high selectivity of reduced
iron for the hydrodeoxygenation of lignin pyrolysis vapors is demonstrated.
The effect of the catalytic treatment on oxygen content and unsaturation
is studied for a broad range of species: from C2 to C14 by GC analysis and from C8 to C37 by
petroleomic. Many heavy lignin oligomers produced by the pyrolysis
are trapped by the catalytic bed, highlighting the need of new catalytic
systems to convert them into valuable fuels or chemicals.
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