Kinetic Modelling of the Oxidation of Medium Paraffins further evidence for the importance of bifunctional intermediates

Engelmann, Eleonore; Just, G.; Pritzkow, W.; Rudolf, Matthias; Spindler, Gerald; Tien, Tieu Dung; Voerckel, V.; Wittekind, Volker

doi:10.1002/prac.19863280404

Cited by 4 publications

(2 citation statements)

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“…Stark et al, also suggests that the formation of shorter-chain-length species may occur early in the process with a breaking to the C–C bond upon formation of an aldehyde from an alkoxyl radical (hydroperoxide decomposition product). The formation of γ-lactones from n -alkanes has been suggested by Engelmann et al and is one of many reactions proposed for their decomposition. This is also supported by Stark et al, in which oxidation of the branched alkane pristane resulted in two lactones being identified, specifically 5,5-dimethyldihydrofuran-2-one and 5-methyl-5-(4-methyl-pentyl)dihydrofuran-2-one.…”

Section: Resultsmentioning

confidence: 95%

Oxidation of Neat Synthetic Paraffinic Kerosene Fuel and Fuel Surrogates: Quantitation of Dihydrofuranones

et al. 2013

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Thermal stressing experiments on a modified surrogate fuel and synthetic paraffinic kerosene (SPK) have been carried out under both static and dynamic conditions at 140 °C. In order to characterize the oxidation products, some key degradation compounds were monitored throughout the stressing experiment. Products resulting from ring closure reactions were also identified in the surrogate fuel and the SPK, with the identification of iso-benzofuranone and alkyldihydrofuranones. Furanones were quantified using gas chromatography−mass spectrometry (GC-MS) with high-performance liquid chromatography (HPLC) prefractionation. The formation of these furanones indicates that dynamic stressing promotes a reactivity that has only been reported at either higher temperatures or longer residence times.

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Section: Resultsmentioning

confidence: 95%

Oxidation of Neat Synthetic Paraffinic Kerosene Fuel and Fuel Surrogates: Quantitation of Dihydrofuranones

et al. 2013

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“…Apparently, the high activation energy required for R02* intramolecular isomerization involving secondary C-H bonds was not met at their test temperatures. Aside from ethers, other products such as alkanoic acids, methyl ketones, and 1-oxyalkanes have been identified during roalkane autoxidations by Jenson et al 27 Additionally, Engelmann et al 28 identified that acids -lactones, 2-alkan-2-ones, and esters are formed via bifunctional primary products.…”

Section: Discussionmentioning

confidence: 99%

Modified reaction mechanism of aerated n-dodecane liquid flowing over heated metal tubes

Reddy¹,

Cernansky²,

Cohen³

1988

Energy Fuels

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Detailed thermal degradation mechanisms for in use distillate fuels are not available, since fuel composition is very complex and the resulting degradation products are many. This makes the study of multicomponent fuel degradation and associated reaction mechanism elucidation a very complex task. A basic approach for studying the thermal degradation problem is to understand the detailed behavior of a prototypical fuel component, i.e., a n-alkane, and then extend the study to include binary and ternary fuel component combinations, dopants, etc. This approach was undertaken to study a single-component model fuel, n-dodecane, and the results are reported here. The data from the present neat n-dodecane experiments agreed with Hazlett et al.'s pioneering work, thereby verifying both sets of data. Also, new products were detected and identified, leading to a modification of the existing n-dodecane/oxygen reaction mechanism. n-Dodecane was aerated by bubbling air through the hydrocarbon and then was stressed on a modified jet fuel thermal oxidation tester facility between 200 and 400 °C. Gas chromatography and mass spectrometry analysis of the control and stressed samples yielded reaction mechanism information. The soluble products consisted mainly of C6-C10 n-alkanes and 1-alkenes, C7-C10 aldehydes, tetrahydrofuran derivatives, dodecanol and dodecanone isomers, dodecyl hydroperoxide (ROOH) decomposition products, and C24 alkane isomers. The modified n-dodecane oxidation mechanism shows that alkyl peroxyl radical reactions dominate in the autoxidation temperature regime (T < 300 °C). The dominant path is for the alkyl peroxyl radical, R02', to react bimolecularly with fuel to yield primarily alkyl hydroperoxides. R02* also undergoes self-termination and unimolecular isomerization and decomposition reactions, to yield smaller amounts of C12 alcohol plus ketone products and tetrahydrofuran derivatives, respectively. Thus, alcohol and ketone formation in this temperature regime implies that the main termination step is via R02* self-termination reactions, which refutes an earlier hypothesis that R* radical termination reactions (giving CM hydrocarbon isomers) are important. In the intermediate temperature regime (300 < T < 400 °C), the alkyl radical, R', reactions dominate the R02* reactions. The dominant reaction steps include (i) alkyl hydroperoxide (ROOH) and surface-initiated fuel pyrolysis reactions yielding

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Determination of the difunctional primary products in the Oxidates of Medium n‐Paraffins

et al. 1987

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The proportion of difunctional and monofunctional products with the original carbon skeleton was determined in the oxidates of n‐decane, n‐tridecane, n‐pentadecane, and n‐octadecane to about 0.32. This proportion does not significantly depend on the conversion of the starting paraffin. As well as mono‐ and difunctional products with the original carbon skeleton already at very low conversions of n‐tridecane, about 45% of lower oxygen‐containing compounds, for example aldehydes, alkan‐2‐ones, carboxylic acids and γ‐lactones, are also obtained. Obviously, a part of the difunctional primary products reacts very fast with scission of the carbon chain, forming lower oxygen‐containing compounds.

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Kinetic Modelling of the Oxidation of Medium Paraffins further evidence for the importance of bifunctional intermediates

Cited by 4 publications

References 3 publications

Oxidation of Neat Synthetic Paraffinic Kerosene Fuel and Fuel Surrogates: Quantitation of Dihydrofuranones

Oxidation of Neat Synthetic Paraffinic Kerosene Fuel and Fuel Surrogates: Quantitation of Dihydrofuranones

Modified reaction mechanism of aerated n-dodecane liquid flowing over heated metal tubes

Determination of the difunctional primary products in the Oxidates of Medium n‐Paraffins

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