Analytics Driving Kinetics: Advanced Mass Spectrometric Characterization of Petroleum Products

Abstract

The current state-of-the-art in analysis techniques for petroleum fractions has progressed substantially during the last 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 (GC × GC) 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 GC × GC 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 photo-ionization 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.

Machine Learning for Physicochemical Property Prediction of Complex Hydrocarbon Mixtures

“…The new approach is well suited for these process simulators because it can predict properties from the composition, whereas predictions are now made in the other way to yield a detailed composition. The software can also be applied for feeds with higher carbon numbers, when data is available, since two-dimensional gas chromatography is a powerful tool for analyzing heavy feedstocks. ,,− When considering heavier feedstocks, it is needed to represent lumps by model compounds since the number of isomers becomes astronomically large and because current analytical techniques cannot characterize heavy feeds to such a level of detail . When data is provided of feeds with higher carbon numbers, such as diesel or vacuum gas oil, the neural networks can be retrained to extend the application range.…”

“…39,65,79−81 When considering heavier feedstocks, it is needed to represent lumps by model compounds since the number of isomers becomes astronomically large and because current analytical techniques cannot characterize heavy feeds to such a level of detail. 82 When data is provided of feeds with higher carbon numbers, such as diesel or vacuum gas oil, the neural networks can be retrained to extend the application range. The main limitation is the lack of large data sets in this field.…”

Virtual Special Issue of Recent Advances in Analysis of Fuels and Products by Advanced Mass Spectrometry

“…Three review articles are included. Bojkovic et al 1 present a comprehensive review on the development of advanced mass spectrometry for characterization of petroleum products. The advantages and disadvantages of the most important techniques used in the characterization of fuels and chemical products are summarized in detail, and the value of advanced mass spectrometry to kinetic model development for petroleum processes is discussed.…”

Molecular Characterization of Heavy Olefins in Slurry-Phase Hydrocracking Products Using High-Resolution Mass Spectrometry

“…The hydrocarbon molecular composition in detail is generally characterized by gas chromatography–mass spectrometry (GC–MS) . More recently, comprehensive two-dimensional gas chromatography (GC × GC) has emerged as a powerful technique that enhances the separation capability and improves the identification of molecules. − However, differentiating between olefins and cycloalkanes is challenging, as they possess the same molecular formula and similar polarity. Therefore, it is still necessary to separate the alkanes and olefins by a Ag + -loaded solid phase extraction column before advanced measurement. , Additionally, the molecular composition analysis of high boiling point olefins cannot be conducted using gas chromatography methods due to the limitation of their volatility.…”