Molecular Structures of Refractory Sulfur Compounds in Heavy Oil Hydrodesulfurization Characterized by Collision-Induced Dissociation Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Abstract

Hydrodesulfurization (HDS) is a widely used technology to reduce the sulfur content of heavy oils, and the HDS reactivities of sulfur compounds are closely related to their structures. In this work, the tandem mass spectra of sulfur-containing model compounds were measured by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) coupled with collision-induced dissociation. The influences of naphthenic rings, size of aromatic rings, number of heteroatoms, and number of alkyl side chains to the fragmentation behaviors of sulfur-containing model compounds were studied. Finally, the structure differences of sulfur compounds in heavy oils before and after hydrogenation were compared by tandem mass spectra of FT-ICR MS. The most refractory sulfur compounds in the heavy oil were those with fully conjugated aromatic rings attached with fewer and longer side chains. These results would be helpful for the development of a HDS catalyst/process for heavy oils. For example, developing a new HDS catalyst with high alkyl side-chain cracking activity may be conducive to HDS of heavy oils.

PetroPhase2021 Virtual Special Issue

“…Wang characterized the refractory S using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and showed that the most refractory sulfur compounds in heavy oils during hydrodesulfurization (HDS) contained fewer but longer alkyl side chains, and the ring structures were almost fully conjugated. 8 Moncayo-Riascos and co-authors contributed two papers. In the first paper, they used petroleomics and molecular dynamics simulations to reconstruct a synthetic crude oil to understand the asphaltene aggregation behavior.…”

“…Six research articles are included on asphaltene science. Wang characterized the refractory S using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and showed that the most refractory sulfur compounds in heavy oils during hydrodesulfurization (HDS) contained fewer but longer alkyl side chains, and the ring structures were almost fully conjugated . Moncayo-Riascos and co-authors contributed two papers.…”

Analysis of Distribution and Structures of Heteroatom Compounds in Asphaltene of Medium/Low Temperature Coal Tar by Negative Anion Mode ESI FT-ICR MS

“…Aggregation are likely driven by polar heteroatom interactions, resulting in the instability of the M/LTCT processing system. Moreover, these heteroatom compounds will cause serious deactivation of the catalyst during the hydrogenation, and the remaining trace heteroatom compounds will reduce the stability of the products [8,9]. Therefore, the problem caused by asphaltenes in the hydrogenation of M/LTCT has attracted the attention of many researchers, who hope to reveal the structure and properties of asphaltenes through various characterization methods.…”

Characterization of Sulfides in Atmospheric Residue Fractions Using Selective Oxidation Followed by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

“…Liu et al [25] used a selective oxidation method combined with ESI FT-ICR MS to detect sulfur compounds in diesel fractions and oil sand bitumen saturates, which provided a new idea for high resolution mass spectrometry analysis of sulfur compounds. Cai et al [26] studied the structure differences of sulfur compounds in heavy oils by tandem mass spectra of FT-ICR MS coupled with collision-induced dissociation. Chen et al [27] introduced a novel method for direct sulfur compounds characterization in petroleum samples by ESI FT-ICR MS using fluoroboric acid as a new ionization promoter.…”