Insight into the Mechanisms of Middle Distillate Fuel Oxidative Degradation. Part 2: On the Relationship between Jet Fuel Thermal Oxidative Deposit, Soluble Macromolecular Oxidatively Reactive Species, and Smoke Point

Aksoy, Parvana; Gül, Ömer; Cetiner, Ruveyda; Fonseca, Dania A.; Sobkowiak, Maria; Falcone-Miller, Sharon; Miller, Bruce G.; Beaver, Bruce

doi:10.1021/ef8007008

Cited by 23 publications

(15 citation statements)

References 17 publications

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“…They specified that this similarity only applies to the gross mechanistic details: autoxidation, followed by coupling reactions forming soluble macromolecular oxidatively reactive species (SMORS), followed by further coupling to form oxidative deposits. This model, first described by Hardy and Wechter, , is coherent with later literature on the mechanisms of middle distillate fuel oxidative degradation. − …”

Section: Mechanisms and Kinetic Aspectssupporting

confidence: 82%

Gum Formation in Gasoline and Its Blends: A Review

Pradelle¹,

Braga²,

Martins³

et al. 2015

Energy Fuels

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Gasoline is a volatile mixture of hydrocarbons that is used in spark-ignition (SI) engines. It is a complex mixture composed of olefinic, paraffinic, naphthenic, and aromatic hydrocarbons (C 4 −C 12 ), among other substances in a smaller concentration. In several countries, such as Brazil, ethanol is used pure as a renewable fuel for SI engines, especially in flex fuel engines, and/or an additive to improve the octane number of gasoline. During storage, some classes of hydrocarbons in gasoline blends, particularly olefins and diolefins, are able to slowly react, at ambient temperatures, with the oxygen in the air. The formed oxidation products are responsible for the formation of an insoluble solid, commonly called deposits or gums, which sticks to the metal surfaces along the vehicle-fuel system, from the tank to the combustion chamber. Accumulation of these products can cause engine wear and can have adverse effects on engine efficiency, performance, emission, and durability. Consequently, it is necessary to predict gasoline blend behavior and prevent gum formation, improving gasoline quality and using additives. Even if the number of publications dedicated to gum formation in gasoline blends is reduced, results available in the literature for other fuels can be applied to the gasoline issue. This review intends to define more precise fuel stability concepts and what is considered a gum. It also aims to present the oxidation mechanism involved in gum formation, determine the main parameters influencing gum deposition in gasoline blends, and describe the experimental tools available to measure gum content.

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Section: Mechanisms and Kinetic Aspectssupporting

confidence: 82%

Gum Formation in Gasoline and Its Blends: A Review

Pradelle¹,

Braga²,

Martins³

et al. 2015

Energy Fuels

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show abstract

“…Negative ion electrospray has also been used to determine phenols in the same fuels [51]. Phenols are a critical component in low temperature oxidation mechanisms for deposit formation in turbine engines [52]. It has also been shown that fuel additives, especially a corrosion inhibitor/lubricity improver can be determined by LC-MS and ESI ionization in negative ion mode [53].…”

Section: Liquid Chromatography-mass Spectrometrymentioning

confidence: 99%

Applications of Mass Spectrometric Techniques to the Analysis of Fuels and Lubricants

Johnson¹

2017

Mass Spectrometry

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The application of mass spectrometric techniques for the analysis of the complex mixtures inherent in fuel and lubricant samples will be examined. These samples because they are naturally complex mixtures, typically requires either very high resolution mass spectrometry or one of the hyphenated techniques gas chromatography-mass spectrometry(GC-MS) or liquid chromatography-mass spectrometry (LC-MS). Some fuel problems that can be addressed through mass spectrometry are associated with the changes in composition and degradation of fuels as they age, including the analysis of both major hydrocarbon components non-polar components and minor polar components will be described. The properties and composition of natural and major classes of synthetic lubricants, the presence of additives and the problems that develop as the lubricant is used such as additive depletion, thermal and oxidative degradation and lubricant contamination have also been examined using mass spectrometric techniques.

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“…This mechanism occurs at temperatures higher than the storage temperaturetypically those encountered in the engineand is known as thermal oxidative degradation. Such mechanisms have been studied for years in jet fuels and diesel oil. − These phenols are oxidized into quinones, which then undergo oxidative coupling reactions, which increase the molecular weight.…”

Section: Introductionmentioning

confidence: 99%

Modeling of Unwashed and Washed Gum Content in Brazilian Gasoline–Ethanol Blends during Prolonged Storage: Application of a Doehlert Matrix

et al. 2016

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Gasoline is a volatile mixture of hydrocarbons that is used in spark ignition engines. It is a complex mixture composed of inflammable olefinic, paraffinic, naphthenic, and aromatic hydrocarbons (C 4 −C 12 ). It presents low contents of oxygenates and traces of sulfur, nitrogen, and metals, which introduce instability to the mixture. In several countries, such as Brazil, ethanol is used purely as a renewable fuel or as an octane improver in blends with gasoline, especially in flex fuel engines. Nevertheless, some compounds in the fuel react slowly, at room temperature, with atmospheric oxygen, and with each other. The process is observed throughout the entire fuel production and use process and increases fuel density. These high-molar-mass insoluble oxidation products are commonly called gums and form deposits throughout the vehicle fuel system. Their accumulation has adverse effects on engine efficiency, performance, and durability, in the form of incomplete combustion, engine wear, and higher pollutant emissions. Consequently, it is necessary to prevent gum formation by improving gasoline quality and using additives. A prediction of gasoline blends behavior is also an important tool to assess critical conditions. This work studied the influence of aging period, temperature, and addition of anhydrous ethanol concentration on unwashed and washed gum content of Brazilian gasoline−ethanol blends. The effect of an additive was also evaluated, by comparing the results of regular and additivated gasolines. This study also defined predictive mathematic models for the studied properties through a Doehlert matrix with three factors, from which robustness was assessed.

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Insight into the Mechanisms of Middle Distillate Fuel Oxidative Degradation. Part 2: On the Relationship between Jet Fuel Thermal Oxidative Deposit, Soluble Macromolecular Oxidatively Reactive Species, and Smoke Point

Cited by 23 publications

References 17 publications

Gum Formation in Gasoline and Its Blends: A Review

Gum Formation in Gasoline and Its Blends: A Review

Applications of Mass Spectrometric Techniques to the Analysis of Fuels and Lubricants

Modeling of Unwashed and Washed Gum Content in Brazilian Gasoline–Ethanol Blends during Prolonged Storage: Application of a Doehlert Matrix

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