Molecular characterization of sulfur compounds in some specieal sulfur-rich Chinese crude oils by FT-ICR MS

Lu, Hong; Shi, Quan; Ma, Qianli; Shi, Yang; Liu, Jinzhong; Sheng, Guoying; Peng, Ping’an

doi:10.1007/s11430-013-4789-9

“…9,41,42,45 Thiadiamondoids were also found in TZ83 crude oil from Tarim Basin, 46 which also has abundant adamantanes and similar geological history to ZS1C crude oil. 11,46,47 The ZS1C crude oil was buried under the conditions of high temperature (169°C), which is conditional for TSR occurrence. The high concentration of H 2 S in natural gas (8.27 vol %) is another conditional evidence for TSR.…”

Section: Energy and Fuelsmentioning

confidence: 99%

Separation and Characterization of Sulfur Compounds in Ultra-deep Formation Crude Oils from Tarim Basin

Wang

¹

,

Zhu

²

,

Ren

³

et al. 2015

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Sulfur compounds in two representative deep crude oils (Ha9, 6598−6710 m; ZS1C, 6861−6944 m) with distinct levels of maturity from Tarim Basin, China, were analyzed by positive-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The thiophenic and sulfidic compounds were selectively separated from the crude oils with high purity and recovery by the methylation/demethylation approach and further characterized in detail by gas chromatography (GC) coupled with a sulfur chemiluminescence detector (SCD) and GC−mass spectrometry (MS). The two crude oils have a large difference in sulfur compound composition, which are both unique compared to common crude oils. A homologue series of 1,1-dimethylhexahydrodibenzothiophenes, which has been found as highly resistant organic sulfur compounds in diesel hydrodesulfurization, was detected in Ha9 crude oil. This is the first time that these biomarker-like compounds have been identified in crude oil. Thiadiamondoids (1−3 cages) with more structural isomers than reported oils as well as various acyclic sulfides, which probably derived from alkyl sulfides, were identified in the sulfidic fraction of the ZS1C crude oil, which indicates that the crude oil has an unusual geological history. The selective separation technique would offer broad prospects for geochemical research on sulfur compounds in crude oils, including their compound-specific 34 S and 13 C analyses.

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“…The identified peaks ranged from classes S1-3, DBE 1-14, and C10-35. Lu et al (2014) also showed that compounds from class S1 DBE 1-3 were detected with remarkably higher relative intensities and the predominance of C20-21 compounds was attributed to the sulfurization of phytanic acids and phytols, and the overall sulfurization mechanism in Jianghan oils was hypothesized to involve carboxylic acids and fatty alcohols, which resulted in the formation of cyclic thioethers. Kohnen et al (1993) The biogeochemistry of Peace River oils has been extensively studied in our group by and Bennett et al (2013).…”

Section: Thermally Immature Vs Biodegraded Sulfur Rich Oilsmentioning

confidence: 96%

Mechanistic insights into sulfur rich oil formation, relevant to geological carbon storage routes. A study using (+) APPI FTICR-MS analysis

Silva¹,

Yim²,

Radović³

et al. 2020

Preprint

0

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Sulfur incorporation into sedimentary organic matter has a key role in carbon preservation in the geosphere. Such processes can inform strategies for human timescale carbon storage to mitigate climate change impacts and thus more detailed knowledge of sulfur incorporation into biomass species is needed. Until recently, detailed chemical characterization of sulfurized organic matter was only possible by analyzing individual building blocks obtained after desulfurization reactions. In this study, Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), with atmospheric pressure photoionization in positive ion mode, (+) APPI, was used to investigate the chemical composition of sulfur rich crude oils and to obtain mechanistic insights into the sulfur incorporation reactions happening during early diagenesis. Contrary to expectations, (+) APPI FTICR-MS data show that sulfurized lipids (with up to 6 sulfur atoms and up to m/z 1100) occur as free molecules in these oils, rather than within a macromolecular network linked by (poly)sulfide bridges. In contrast to the mature Peace River (Canada) oils, the thermally immature Rozel Point (USA) and Jianghan Basin (China) oils show a carbon number preference in sulfurized species resembling biogenic precursor molecules, which highlights the importance of S-bound molecules as geochemical proxies for early diagenetic processes. This study indicates that sulfur incorporation reactions involve the formation of S-cyclic structures in which the double bond equivalent is ≥ the number of S atoms. Collision induced dissociation (CID-) FTICR-MS experiments suggest the occurrence of intermolecular sulfur incorporation reactions, but only as a mechanism that is secondary to intramolecular sulfur addition. The CID-FTICR-MS experiments indicated that steroid sulfurization typically yields S-bearing cyclic structures and that thiol/thioether groups may be present throughout the chemical matrix but only to a minor extent. In addition, CID-FTICR-MS also confirms the occurrence of sulfurized alkenones in low maturity oils. Knowledge of organic sulfur molecule formation informs routes for carbon dioxide removal technologies that could be used to sequester carbon in the geosphere and/or hydrosphere in the form of recalcitrant organic species.

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“…Such species were considered different from those sulfur compounds found in most oils since their structures are closely related to biogeochemical precursors (Sinninghe Damsté et al, 1989). Lu et al (2014) investigated a set of Jianghan oils using (+) ESI FTICR-MS, after S-methylation reactions and detected high levels of alkylcyclothioethers within the oils. The identified peaks ranged from classes S1-3, DBE 1-14, and C10-35.…”

Section: Thermally Immature Vs Biodegraded Sulfur Rich Oilsmentioning

confidence: 99%

“…Lu et al (2013) used (+) ESI (electrospray ionization in positive-ion mode) FTICR-MS to investigate sulfur rich heavy oils from Bohai Bay Basin, reporting a wide range of sulfurized sedimentary steroids in addition to a complex distribution of sulfur and oxidized sulfur compounds. Based on a similar approach, Lu et al (2014) detected high levels of alkylcyclothioethers within Jianghan Basin oils. More recently, Liu et al (2018) reported an in-depth investigation of polar sulfur compounds in immature crude oils from the Jianghan Basin via (-) ESI and (+) ESI FTICR-MS showing that the detected S-bearing species are mostly cyclic, originating from intramolecular sulfurization of functionalized precursors during early diagenesis.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic insights into sulfur rich oil formation, relevant to geological carbon storage routes. A study using (+) APPI FTICR-MS analysis

Silva

¹

,

Yim

²

,

Radović

³

et al. 2020

Organic Geochemistry

View full text Add to dashboard Cite

Sulfur incorporation into sedimentary organic matter has a key role in carbon preservation in the geosphere. Such processes can inform strategies for human timescale carbon storage to mitigate climate change impacts and thus more detailed knowledge of sulfur incorporation into biomass species is needed. Until recently, detailed chemical characterization of sulfurized organic matter was only possible by analyzing individual building blocks obtained after desulfurization reactions. In this study, Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), with atmospheric pressure photoionization in positive ion mode, (+) APPI, was used to (CID-) FTICR-MS experiments suggest the occurrence of intermolecular sulfur incorporation reactions, but only as a mechanism that is secondary to intramolecular sulfur addition. The CID-FTICR-MS experiments indicated that steroid sulfurization typically yields S-bearing cyclic structures and that thiol/thioether groups may be present throughout the chemical matrix but only to a minor extent. In addition, CID-FTICR-MS also confirms the occurrence of sulfurized alkenones in low maturity oils. Knowledge of organic sulfur molecule formation informs routes for carbon dioxide removal technologies that could be used to sequester carbon in the geosphere and/or hydrosphere in the form of recalcitrant organic species.

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Molecular characterization of sulfur compounds in some specieal sulfur-rich Chinese crude oils by FT-ICR MS

Cited by 28 publications

References 30 publications

Separation and Characterization of Sulfur Compounds in Ultra-deep Formation Crude Oils from Tarim Basin

Separation and Characterization of Sulfur Compounds in Ultra-deep Formation Crude Oils from Tarim Basin

Mechanistic insights into sulfur rich oil formation, relevant to geological carbon storage routes. A study using (+) APPI FTICR-MS analysis

Mechanistic insights into sulfur rich oil formation, relevant to geological carbon storage routes. A study using (+) APPI FTICR-MS analysis

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