Sulfur compounds characterization using FT-ICR MS: Towards a better comprehension of vacuum gas oils hydrodesulfurization process

Guillemant, Julie; Berlioz‐Barbier, Alexandra; Chainet, Fabien; Oliveira, Luís Pereira de; Lacoue-Nègre, Marion; Joly, Jean‐François; Duponchel, Ludovic

doi:10.1016/j.fuproc.2020.106529

Cited by 11 publications

(4 citation statements)

References 27 publications

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“…Hence, ultrahigh-resolution mass spectrometry without prior gas chromatographic separation can be used to unravel the detailed composition of the heavy tail of pyrolysis oils, including polyaromatics, as no volatilization in the chromatographic columns is required. , Especially Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has proven efficient as it provides exceptionally high resolutions to determine the detailed molecular composition of the species present in complex mixtures . The ultrahigh resolving power enabled by FT-ICR MS has its benefits for the analysis of high molecular weight compounds such as proteins and ultracomplex samples like heavy crude oils, − asphaltenes, and bitumen. − For the analysis of pyrolysis oils, the use of FT-ICR-MS has been increasing over the past years, with a limited number of studies published to this day for plastic pyrolysis oils. ,− The main focus of these studies was mixed plastic waste or polyolefin mixtures, but also a polyethylene terephthalate oil has been studied . Ware et al analyzed a mixed plastic pyrolysis oil and compared its composition to those from biomass and landfill waste pyrolysis oils to understand the role of the starting material in the composition of the pyrolysis products .…”

Section: Introductionmentioning

confidence: 99%

Characterization of PP and PE Waste Pyrolysis Oils by Ultrahigh-Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Ureel,

Chacón-Patiño,

Kusenberg

et al. 2024

Energy Fuels

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Increasing recycling rates of plastic waste is necessary to achieve a sustainable and climate-neutral chemical industry. For polyolefin waste, corresponding to 60% of plastic waste, chemical recycling via thermal pyrolysis is the most promising process. However, the hydrocarbon composition of these pyrolysis oils differs from conventional fossil-based feedstocks as they are heavier and more unsaturated. GC × GC-FID is the most prevalent characterization method for the analysis of these complex hydrocarbon mixtures but fails to discern heavy unsaturated, aromatic compounds. An up-and-coming technique to fully characterize those analytically challenging heavy fractions is ultrahigh-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) coupled with soft ionization techniques, such as atmospheric pressure photoionization and atmospheric pressure chemical ionization. In this work, FT-ICR MS has been employed to analyze both real PE and PP postconsumer waste pyrolysis oils, which allowed to provide additional insights into the pyrolysis reaction pathways of both polyolefin types. FT-ICR MS identifies heavy hydrocarbons, up to C85, and discerns a wide range of complex polycyclic aromatic hydrocarbons with up to seven aromatic rings. These hepta-aromatics were not found in PP, which only revealed penta-aromatics; this complies with the reaction mechanism proposed in the literature. Moreover, the polypropylene (PP) pyrolysis oil displayed clear signs of depolymerization reactions occurring during pyrolysis, both for the formation of olefins and diolefins. Here, FT-ICR MS identified heavier, unsaturated, and highly aromatic hydrocarbons, whereas GC × GC-FID quantified saturated and less complex unsaturated components. These observations highlight the added benefit of combining GC × GC-FID and FT-ICR MS data to completely characterize plastic pyrolysis oils and understand pyrolysis reaction pathways.

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Section: Introductionmentioning

confidence: 99%

Characterization of PP and PE Waste Pyrolysis Oils by Ultrahigh-Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Ureel,

Chacón-Patiño,

Kusenberg

et al. 2024

Energy Fuels

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“…Sulfur compounds were ionized directly by the APPI source, − while the derivatization with methyl iodide ,, or silver cation , was necessary for the ESI source. The transformations of sulfur compounds during hydroprocessings were studied for the coal tar, shale oils, VGO, , atmospheric residues, − and asphaltenes − by FT-ICR MS. Moreover, the combinations of gel permeation chromatography (GPC), high-performance liquid chromatography (HPLC), , thermogravimetry (TG), − and ion mobility (IM) − with high-resolution mass spectrometry were also applied to obtain more information about the structures of sulfur compounds in heavy oils.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2022

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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.

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“…Therefore, the sulfur content in oil should be minimized, and the residues must be subjected to hydrodesulfurization to enhance the efficiency and quality of the refinement process. Many studies have reported on the molecular transformation caused by the hydrodesulfurization process. − Moreover, results obtained using FT-ICR MS and IM–MS have been presented . However, considering the complexity and difficulty of crude oil analysis, it is advisible to employ novel techniques, such as cIM–MS, to obtain the molecular-level information.…”

Section: Introductionmentioning

confidence: 99%

“…29−32 Moreover, results obtained using FT-ICR MS and IM−MS have been presented. 33 However, considering the complexity and difficulty of crude oil analysis, it is advisible to employ novel techniques, such as cIM−MS, to obtain the molecular-level information.…”

Section: ■ Introductionmentioning

confidence: 99%

Molecular-Level Structural Analysis of Hydrotreated and Untreated Atmospheric Residue Oils via Atmospheric Pressure Photoionization Cyclic Ion Mobility Mass Spectrometry and Ultrahigh-Resolution Mass Spectrometry

Cho

Rakhmat

et al. 2021

Energy Fuels

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Changes in the structure of oil compounds subjected to hydrodesulfurization were investigated using ultrahigh-resolution mass spectrometry (UHR-MS) and cyclic ion mobility mass spectrometry (cIM–MS) techniques. The isolation of ions with a separation of less than 0.1 Da followed by collision-induced dissociation helped clarify the structure. The class and double bond equivalence (DBE) distributions of the HC class observed by UHR-MS indicated that sulfur-containing compounds were transformed to HC compounds, in accordance with the previously reported mechanisms. The transformation was further observed by examining the tandem mass spectra of HC class compounds with the DBE values. The fragility of the molecules to collision-induced dissociation increased after hydrodesulfurization as a result of the increased abundance of naphthenic rings in the processed oils. The structural change was influenced by the DBE, and the most significant structural changes corresponded to HC compounds with DBE of 7. It was considered that compounds with naphthalene in the core structure were dominant in the untreated oils; however, the number of compounds with multiple naphthenic rings increased after the treatment. Moreover, the abundance of HC compounds with short alkyl chains likely increased. The results indicate that UHR-MS and cIM–MS are effective tools to clarify molecular-level changes in processed oils.

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Sulfur compounds characterization using FT-ICR MS: Towards a better comprehension of vacuum gas oils hydrodesulfurization process

Cited by 11 publications

References 27 publications

Characterization of PP and PE Waste Pyrolysis Oils by Ultrahigh-Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Characterization of PP and PE Waste Pyrolysis Oils by Ultrahigh-Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

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

Molecular-Level Structural Analysis of Hydrotreated and Untreated Atmospheric Residue Oils via Atmospheric Pressure Photoionization Cyclic Ion Mobility Mass Spectrometry and Ultrahigh-Resolution Mass Spectrometry

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