Role of sulfur compounds in fuel instability: a model study of the formation of sulfonic acids from hexyl sulfide and hexyl disulfide

Mushrush, George W.; Hazlett, Robert N.; Pellenbarg, Robert E.; Hardy, Dennis R.

doi:10.1021/ef00026a006

Cited by 19 publications

(20 citation statements)

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“…Depending on the reaction conditions and the nature of organosulfur compounds, several main pathways of oxidation reaction are possible. 14,15,32 As shown in Figures 1 and 2, the final oxidation products of thiols or disulfides are sulfonic acids (Figure 1), whereas the oxidation of sulfides yields sulfones ( Figure 2). …”

Section: Main Pathways Of Oxidation Of Organosulfurmentioning

confidence: 99%

Process Control and Investigation of Oxidation Kinetics of Postoxidative Effluents Using Gas Chromatography with Pulsed Flame Photometric Detection (GC-PFPD)

Boczkaj

Kamiński

Przyjazny

2010

Ind. Eng. Chem. Res.

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This article presents the results of investigations on the use of headspace analysis and gas chromatography with pulsed flame photometric detection (HSA-GC-PFPD) to evaluate the effectiveness of oxidation of postoxidative effluents from the production of bitumens. Samples of effluents from the bitumen oxidation unit were used in the experiments. In addition, the kinetics of effluent oxidation was also investigated. The content of volatile sulfur compounds (VSCs) was determined using HSA-GC-PFPD. The results were correlated with chemical oxygen demand (COD). The changes in concentration of individual volatile sulfur compounds in the course of effluent oxidation were measured, which enabled the determination of the order of the oxidation reactions. The usefulness of the determination of VSCs in the headspace as a reliable technique for evaluating the reduction in emissions of volatile malodorous compounds was demonstrated. The developed method is also useful for process control of the oxidation of postoxidative effluents. The procedure ensures an objective evaluation of the effectiveness of the removal of volatile sulfur compounds from postoxidative effluents. The experimental results revealed that the effectiveness of the oxidation of organosulfur compounds was much higher than that of other classes of organic compounds. Furthermore, the order of oxidation reactions along with the rate constants of thiophenol, p-thiocresol, and hydrogen sulfide were determined. An advantage of the developed procedure is that it can be automated.

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Section: Main Pathways Of Oxidation Of Organosulfurmentioning

confidence: 99%

Process Control and Investigation of Oxidation Kinetics of Postoxidative Effluents Using Gas Chromatography with Pulsed Flame Photometric Detection (GC-PFPD)

Boczkaj

Kamiński

Przyjazny

2010

Ind. Eng. Chem. Res.

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“…The product slate is similar, but lower in yield. In other studies from our laboratory, sulfonic acids have been found to be the most deleterious organo-sulfur compound to storage stability Mushrush et al, 1991). This observation has implications for organo-disulfides and the decrease in storage stability that has been observed for many years in the presence of either sulfur acids or the disulfide species .…”

Section: Reprintsmentioning

confidence: 55%

“…Our laboratory has found, in past work, that sulfonic acids are the most deleterious compounds in determining fuel stability Mushrush et al, 1991). The disulfone product (reaction step l, compound lV) ultimately leads to a low, but important concentration of a product that contains the sulfonic acid functional group.…”

Section: Reprintsmentioning

confidence: 99%

Fuel Instability Studies: The Chemical Validation of Astm Method D5304

Mushrush

Beal

Hardy

et al. 2001

Petroleum Science and Technology

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The current ASTM (D5304) procedure for determining storage stability involves rather drastic conditions, namely, 16 hours at 90 C and under 100 psig of oxygen. These mandated test conditions give rise to the question, ''Does the reaction conditions induce chemical instability, or is it an accurate measure of the true instability process?'' Several organo-sulfur functional groups are known to be present in petroleum derived fuels. Thiophenes, benzothiophenes, sulfides, disulfides, and trace amounts of thiols are the organosulfur compounds most prevalent. The reaction of organosulfur compounds under the ASTM reaction conditions have not been investigated. The purpose of the present research is to determine if the ASTM reaction conditions induce a reaction in an otherwise stable fuel matrix.

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“…Scheme shows a sulfur oxidation path to produce acidic sulfur compounds (such as sulfenic, sulfinic, and sulfonic acids) from sulfides and disulfides via reaction with hydroperoxides and/or peroxy radicals Scheme shows that fuel sulfides react readily with hydroperoxides (produced during autoxidation) to yield a sulfoxide and an alcohol. , The sulfoxide can rearrange through the sulfoxide ylide form via an internal elimination process to produce a reactive sulfenic acid and an olefin . The reaction of sulfides and disulfides with hydroperoxides and peroxy radicals to produce oxidized sulfur species (e.g., sulfoxides, sulfones, thiosulfinates, sulfinyl sulfones, and disulfones) is well documented. , Less well understood are the reactions in nonpolar solvents for production of sulfur acids from these oxidized sulfur intermediates, but some reaction pathways have been proposed…”

Section: Discussionmentioning

confidence: 99%

Studies of the Role of Heteroatomic Species in Jet Fuel Thermal Stability: Model Fuel Mixtures and Real Fuels

et al. 2019

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Oxygen consumption and deposition measurements of model fuel mixtures and real fuels are used to explore the roles that heteroatomic fuel species and their interactions play during fuel autoxidation. A range of temperatures, oxygen consumption regimes, and flow environments are employed to provide results applicable over a wide range of fuel autoxidative conditions. The quartz crystal microbalance (QCM) provides a low temperature (140 °C) batch reactor environment for long reaction times (minutes to hours) with oxygen consumption and sensitive, in situ deposition measurements. The JFTOT system provides a flowing environment at higher temperatures (260 to 300 °C) and short residence times (seconds) which is modified with both an outlet oxygen sensor and with quantitative deposition measurements via ellipsometry. These techniques are used to study model systems (Exxsol D80 with added heteroatom species) and real jet fuels to determine the role of heteroatomic species in jet fuel autoxidation and deposition. The QCM results demonstrate that nitrogen and sulfur species (e.g., indoles/anilines and sulfides) interact during jet fuel autoxidation to encourage deposit formation. The further addition of phenol species, which occur naturally in most petroleum-derived jet fuels, facilitates even greater deposit production. This behavior is confirmed in the JFTOT via addition of nitrogen and sulfur-containing species to medium and low sulfur jet fuels. These results, along with gas chromatographic (GC) analysis of samples collected during autoxidation in the QCM, show rapid sulfur autoxidation followed by a slower reaction of the nitrogen species to form deposit precursors, implying a stepwise reaction of sulfur oxidation products with nitrogen species to form deposit precursors. These results have important implications for fuel production strategies and mitigation of thermal stability degradation during fuel pipeline transport, storage, and use.

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Role of sulfur compounds in fuel instability: a model study of the formation of sulfonic acids from hexyl sulfide and hexyl disulfide

Cited by 19 publications

References 0 publications

Process Control and Investigation of Oxidation Kinetics of Postoxidative Effluents Using Gas Chromatography with Pulsed Flame Photometric Detection (GC-PFPD)

Process Control and Investigation of Oxidation Kinetics of Postoxidative Effluents Using Gas Chromatography with Pulsed Flame Photometric Detection (GC-PFPD)

Fuel Instability Studies: The Chemical Validation of Astm Method D5304

Studies of the Role of Heteroatomic Species in Jet Fuel Thermal Stability: Model Fuel Mixtures and Real Fuels

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