Analytics Driving Kinetics: Advanced Mass Spectrometric Characterization of Petroleum Products

The current state-of-the-art analysis techniques for petroleum fractions has progressed substantially during the past decade. This has helped to further improve the lumping procedures and modeling approaches of these complex systems. Recent advances in gas chromatography (GC), GC-field ionization mass spectrometry (GC-FIMS), and comprehensive gas chromatography (GCxGC) have made it possible to determine the compositions of fractions with up to 45 carbon atoms and in some cases up to C80. The combination of MS techniques with other selective detectors and reversed-phase column combinations has made it possible to quantify even traces of heteroatomic compounds in these complex hydrocarbon matrices. Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), in some cases combined with GCxGC for the lighter part, has pushed the characterization of larger macromolecules in particular asphaltenes. Matrix-assisted laser desorption/ionization (MALDI) is also used widely for this purpose but has the disadvantage that quantification is not obvious. The development of more detailed characterization techniques has not remained unnoticed in the petrochemical society and more recently in the petrochemical kinetic modeling society. More detailed characterization of petrochemical fractions has made the implementation of detailed kinetic models for simulation and optimization possible including more and more molecular detail. Additionally, advances in photoionization mass spectrometry (PI-MS) have allowed the detection of reactive intermediates and direct kinetic measurements in time-resolved experiments. It can only be expected that this trend will continue and that the application field will move from now primarily petrochemistry (from catalytic cracking, over hydrotreating, and hydrocracking to pyrolysis, combustion, and steam cracking) to larger-scale chemical recycling and biomass conversion processes.