Influence of the double bond position on the oxidation of decene isomers at high pressures and temperatures

Fridlyand, Aleksandr; Goldsborough, S. Scott; Brezinsky, Kenneth; Merchant, Shamel S.; Green, William

doi:10.1016/j.proci.2014.06.020

Cited by 29 publications

(69 citation statements)

References 30 publications

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“…This observation is in agreement with the shock tube study of decene isomers by Fridlyand et al 48 who found an increasing yield of benzene (an important precursor to particulate formation) in the speciation of reaction intermediates by gas chromatography with movement of the decene double bond from position 1 to positions 2 and 5.…”

Section: Particulate Mattersupporting

confidence: 92%

“…46,49 Hellier et al 44 suggested that the initial increase in the duration of ignition delay ( Figure 4) in engine tests of octene isomers can be similarly explained by the decreasing length of the residual saturated alkyl chain but that, in moving the double bond from position 2 to position 3, the longer saturated chain lengths relative to hexane and heptane isomers resulted in a net increase in the low-temperature reactivity. Kinetic modelling undertaken by Fridlyand et al 48 suggested that decene isomers undergo significantly different reaction pathways dependent on the double-bond position and, in a further study investigating methyl trans-2-nonenoate, methyl trans-3-nonenoate and the analogous alkenes, 1-octene and trans-2-octene, found a dissimilar influence of double-bond movement within the alkyl chain in the FAMEs relative to the alkenes. 50 Figure 4 also shows a reduced duration of ignition delay of cis-3-octene relative to that of trans-3-octene, and this was suggested to have been due to the requirement for alkenyl and alkenyl peroxy radicals to be in the cis arrangement prior to internal isomerisation across the double bond during low-temperature branching reactions.…”

Section: Alkyl Chain Length and Branchingmentioning

confidence: 98%

“…Fridlyand et al 48 investigated the relative reactivities (using speciation of stable intermediates by gas chromatography) of 1-decene, cis-2-decene, cis-5-decene and trans-5-decene in a shock tube at conditions (40-66 bar and 850-1500 K) relevant to compression ignition engines. Contrary to studies of shorter-chain alkene isomers, [44][45][46] reactivity was found to increase with the movement of the double bond towards the centre of the molecule.…”

Section: Alkyl Chain Length and Branchingmentioning

confidence: 99%

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An overview of the effects of fuel molecular structure on the combustion and emissions characteristics of compression ignition engines

Hellier

Talibi

Eveleigh

et al. 2017

Proceedings of the Institution of Mechanical Engineers, Part D:

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Future fuels for compression ignition engines will be required both to reduce the anthropogenic carbon dioxide emissions from fossil sources and to contribute to the reductions in the exhaust levels of pollutants, such as nitrogen oxides and particulate matter. Via various processes of biological, chemical and physical conversion, feedstocks such as lignocellulosic biomass and photosynthetic micro-organisms will yield a wide variety of potential fuel molecules. Furthermore, modification of the production processes may allow the targeted manufacture of fuels of specific molecular structure. This paper therefore presents an overview of the effects of fuel molecular structure on the combustion and emissions characteristics of compression ignition engines, highlighting in particular the submolecular features common to a variety of potential fuels. An increase in the straight-chain length of the alkyl moiety reduces the duration of ignition delay, and the introduction of double bonds or branching to an alkyl moiety both increase ignition delay. The movement of a double bond towards the centre of an alkyl chain, or the addition of oxygen to a molecule, can both increase and decrease the duration of ignition delay dependent on the overall fuel structure. Nitrogen oxide emissions are primarily influenced by the duration of fuel ignition delay, but in the case of hydrogen and methane pilot-ignited premixed combustion arise only at flame temperatures sufficiently high for thermal production. An increase in aromatic ring number and physical properties such as the fuel boiling point increase particulate matter emissions at constant combustion phasing.

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Section: Particulate Mattersupporting

confidence: 92%

Section: Alkyl Chain Length and Branchingmentioning

confidence: 98%

Section: Alkyl Chain Length and Branchingmentioning

confidence: 99%

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An overview of the effects of fuel molecular structure on the combustion and emissions characteristics of compression ignition engines

Hellier

Talibi

Eveleigh

et al. 2017

Proceedings of the Institution of Mechanical Engineers, Part D:

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“…The presence and position of a C=C double bond in hydrocarbons and its effect on combustion characteristics has been investigated previously [17][18][19]. The C-H bond of the carbon atom in the α-position to the C=C bond and the C-C bond between the carbon atoms in α and β-positions are weak as scission leads to resonantly stabilized radicals [17].…”

Section: Introductionmentioning

confidence: 99%

“…The C-H bond of the carbon atom in the α-position to the C=C bond and the C-C bond between the carbon atoms in α and β-positions are weak as scission leads to resonantly stabilized radicals [17]. The resonance stabilization in these radicals is lost upon addition of molecular oxygen, important for autoignition and chain branching at low temperatures, and redissociation of the adduct to the initial reactants is therefore a major reaction channel [20].…”

Section: Introductionmentioning

confidence: 99%

Understanding the reactivity of unsaturated alcohols: Experimental and kinetic modeling study of the pyrolysis and oxidation of 3-methyl-2-butenol and 3-methyl-3-butenol

Bruycker

Herbinet

Carstensen

et al. 2016

Combustion and Flame

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. Understanding the reactivity of unsaturated alcohols: Experimental and kinetic modeling study of the pyrolysis and oxidation of 3-methyl-2-butenol and 3-methyl-3-butenol. Combustion and Flame, Elsevier, 2016, 171, pp.237-251. 1 Understanding the reactivity of unsaturated alcohols: Experimental and kinetic modeling study of the pyrolysis and oxidation of 3-methyl-2-butenol and 3-methyl-3-butenol AbstractThe reactivity of unsaturated alcohols with a C=C double bond in the β-and γ-positions to the hydroxyl group is not well established. The pyrolysis and oxidation of two such unsaturated alcohols have been studied, i.e. 3-methyl-2-butenol (prenol) and 3-methyl-3-butenol (isoprenol). Experiments at three equivalence ratios, i.e. φ = 0.5, φ = 1.0 and φ = ∞ (pyrolysis), were performed using an isothermal jet-stirred quartz reactor at temperatures ranging from 500 to 1100 K, a pressure of 0.107 MPa and a residence time of 2 s. The reactant and product concentrations were quantified using gas chromatography. A kinetic model has been developed using the automatic network generation tool "Genesys". Several important rate coefficients are obtained from new quantum chemical calculations. Overall, there is a good agreement between model calculated mole fraction profiles and experimental data. Reaction path analysis reveals that isoprenol consumption is dominated by a unimolecular reaction to formaldehyde and isobutene. At the applied operating conditions, the equivalence ratio has no effect on the isoprenol conversion profile. Pyrolysis and oxidation of prenol is dominated by radical chemistry, with hydrogen abstractions from prenol forming resonantly stabilized radicals as dominating conversion path. Oxidation and decomposition of the resulting radicals are predicted to form 3-methyl-2-butenal and 2-methyl-1,3-butadiene, which have been detected as important products in the reactor effluent.

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Microkinetic model for the pyrolysis of methyl esters: From model compound to industrial biodiesel

et al. 2015

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A tool for the generation of decomposition schemes of large molecules has been developed. These decomposition schemes contain radicals which can be eliminated from the model equations if both the μ‐hypothesis and the pseudosteady‐state approximation are valid. The reaction rate coefficients and thermodynamic parameters have been calculated by incorporating a comprehensive group additive framework. A microkinetic model for the pyrolysis of methyl esters with a carbon number of up to 19 has been generated using this tool. It is validated by comparing calculated and experimental yields of the pyrolysis of methyl decanoate and novel rapeseed methyl ester pyrolysis data in the temperature range from 800 to 1100 K and methyl ester partial pressure range from 1 × 10−3 to 1 × 10−2 MPa. This modeling frame work allows to not only assess the use of methyl ester mixtures as potential feedstock for olefin production but also their effect as blend‐in or trace impurity. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4309–4322, 2015

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Influence of the double bond position on the oxidation of decene isomers at high pressures and temperatures

Cited by 29 publications

References 30 publications

An overview of the effects of fuel molecular structure on the combustion and emissions characteristics of compression ignition engines

An overview of the effects of fuel molecular structure on the combustion and emissions characteristics of compression ignition engines

Understanding the reactivity of unsaturated alcohols: Experimental and kinetic modeling study of the pyrolysis and oxidation of 3-methyl-2-butenol and 3-methyl-3-butenol

Microkinetic model for the pyrolysis of methyl esters: From model compound to industrial biodiesel

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