Molecular Characterization of Heavy Petroleum by Mass Spectrometry and Related Techniques

Abstract

The rapid advances in mass spectrometry and related technologies in the last two decades have revolutionized our understanding of heavy petroleum composition and greatly accelerated research and development within the oil and gas industry. Petroleum is a highly complex mixture of hydrocarbons and heteroatom-containing (S, N, O, metals, and more) hydrocarbons. Molecular composition has a significant impact on the properties of crude oils and the way they need to be handled in refining processes. In this review, the current state is highlighted, as well as progress in key areas of the molecular characterization of heavy petroleum, including separation approaches, ionization methods, high-resolution mass spectrometry, dissociation technology, and multidimensional separation mass spectrometry, including GC soft ionization mass spectrometry and ion mobility-mass spectrometry.

The Next Frontier of Environmental Unknowns: Substances of Unknown or Variable Composition, Complex Reaction Products, or Biological Materials (UVCBs)

“…Additionally, certain UVCBs such as petroleum substances that contain mostly hydrocarbons may be less challenging to characterize compared to UVCBs containing multiple chemical classes such as essential oils. Overall, petroleum substances appear to be the most extensively characterized UVCBs: constituent identification commonly by gas chromatography–mass spectrometry (GC–MS) and ion mobility spectrometry–mass spectrometry, and relative quantification by GC­(xGC) flame ionization detection. − Essential-oil UVCBs were characterized using low resolution GC–MS aided by available library spectra and reference standards of constituents. − Among high resolution mass spectrometry methods, one example used five different techniques to characterize a polyhalogenated flame retardant UVCB, concluding that it is “dominated by C 18 carbon chain lengths, substituted with 3–7 chlorine atoms and 1–3 bromine atoms on an alkane chain” . Unambiguous structural identification is often not feasible for many UVCBs such as these, as “no individual or mixed standards for [polyhalogenated (bromo-chloro) n -alkanes] exist” .…”

2021 Pioneers in Energy Research: Alan Marshall

“…Qian from ExxonMobil provided a broad (horizontal) overview of MS and various techniques employed in petroleum science. The author highlighted the unparalleled high mass resolution power of MS and the need to work with various techniques, including separations, different ionization methods, ion dissociation/multidimensional MS, and hyphened separation techniques.…”

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

“…The development of coupled soft ionization sources has expanded the capability to ionize nonvolatile molecules . With its ultrahigh mass resolution and accuracy in identifying the molecular formula, HR MS is extensively applied for petroleomics studies, particularly for heavy petroleum. , Direct-injection HR MS analysis assisted by Ag + complexation of unsaturated bonds or lone pair , has proven to offer compositional insight into various nonpolar compounds present in petroleum. , Roussis et al investigated the distribution of aromatic hydrocarbons’ molecular composition in heavy oil using a silver nitrate solution under electrospray ionization source (ESI) HR MS. Sherrod et al used silver nanoparticles as selective ionization probes to characterize olefin in carrot juice with laser desorption/ionization MS. Our group coupled Ag + complexation with ESI Orbitrap MS and applied this method to analyze coker diesel, coal tar liquid, and Fischer–Tropsch wax . Through HR MS analysis, we successfully detected heavy olefins with a carbon number up to C 40 .…”