Investigation on primary decomposition of ethylcyclohexane at atmospheric pressure

Wang, Zhandong; Bian, Huiting; Wang, Yu; Zhang, Youmin; Li, Yuyang; Zhang, Feng; Qi, Fei

doi:10.1016/j.proci.2014.05.119

Cited by 47 publications

(12 citation statements)

References 23 publications

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“…In a previous study [16], species mole fractions measured with GC and photoionization mass spectrometry (PIMS) showed very good agreement with each other, demonstrating the feasibility of the GC technique in similar pyrolysis studies. The detailed description of the experimental apparatus was given elsewhere [17]. In brief, the apparatus consists of a pyrolysis chamber, the sampling system and a GC (Bruker 450-GC) system.…”

Section: Flow Reactor Pyrolysismentioning

confidence: 99%

An experimental and kinetic modeling study on dimethyl carbonate (DMC) pyrolysis and combustion

Sun

Yang

Hansen

et al. 2016

Combustion and Flame

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Dimethyl carbonate (DMC) is a promising oxygenated additive or substitute for hydrocarbon fuels, because of the absence of C-C bonds and the large oxygen content in its molecular structure. To better understand its chemical oxidation and combustion kinetics, flow reactor pyrolysis at different pressures (40, 200 and 1040 mbar) and low-pressure laminar premixed flames with different equivalence ratios (1.0 and 1.5) were investigated. Mole fraction profiles of many reaction intermediates and products were obtained within estimated experimental uncertainties. From theoretical calculations and estimations, a detailed kinetic model for DMC pyrolysis and high-temperature combustion consisting of 257 species and 1563 reactions was developed. The performance of the kinetic model was then analyzed using detailed chemical composition information, primarily from the present measurements. In addition, it was examined against the chemical structure of an opposed-flow diffusion flame, relying on global combustion properties such as the ignition delay times and laminar burning velocities. These extended comparisons yielded overall satisfactory agreement, demonstrating the applicability of the present model over a wide range of high-temperature conditions. . Introduction Oxygenated hydrocarbon fuels derived from biomass are attracting considerable attention either as replacements of, or additives to, conventional hydrocarbon fuels in internal combustion engines. They offer potential benefits as renewable fuels, with a long-term zero CO 2 debt, and the tendency to reduce soot formation [1][2][3]. Dimethyl carbonate [CH 3 OC(=O)OCH 3 , DMC], being non-toxic and highly miscible with diesel fuels, is one of such promising clean fuels. Carbon-carbon bonds are absent in the DMC molecular structure which contains three oxygen atoms. In a diesel engine study, Miyamoto et al. [2] found that the extent of soot reduction mainly depended on the amount of oxygen present in the fuel. Furthermore, when the oxygen content of the fuel was above 25% by mass, soot emission fell beyond detection. Although the fuel's structure and the particular combustion conditions are of non-negligible influence on the emissions, it is worthwhile to consider the high oxygen content (53% by mass) of DMC: it suggests that DMC addition in small amounts could achieve significant soot reduction. From laboratory experiments [4,5] to practical engine operations [6-9], extensive studies have been conducted on the effects of adding DMC to hydrocarbon fuels. Specifically, Rubino and Thomson [4] used a counter-flow propane/air diffusion flame to study the inhibition of soot precursor formation by adding oxygenated compounds including DMC. They observed a remarkable reduction of soot precursors such as acetylene (C 2 H 2 ) and benzene (C 6 H 6 ), as well as a linear relationship between the C 2 H 2 concentration and the additive's oxygen and C-C bond content. Furthermore, Chen et al. [5] found that concentrations of most C 1 -C 5 hydrocarbon intermediates decreased in low-p...

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Section: Flow Reactor Pyrolysismentioning

confidence: 99%

An experimental and kinetic modeling study on dimethyl carbonate (DMC) pyrolysis and combustion

Sun

Yang

Hansen

et al. 2016

Combustion and Flame

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“…Online GC sampling system as developed by Comandini et al . (left) and modified online GC sampling system configured for acquisition of samples at higher pressures (right)…”

Section: Experimental Apparatusmentioning

confidence: 99%

“…The mechanism is an extension of Wang et al. cyclohexane mechanism, which added a methylcyclohexane submechanism composed of reactions and their rate constants calculated by the authors or borrowed from JetSurf2.0 and Wang et al.’s ethylcyclohexane work, in addition to a submechanism for cC7H13 radicals, and two cyclohexyl reactions. The reaction rates for the cC7H13 radicals and the two cyclohexyl reactions were calculated by the authors.…”

Section: Chemical Kinetic Modeling Of Experimental Datamentioning

confidence: 99%

“…The first mechanism considered is the methylcyclohexane mechanism developed by Wang et al 17 This mechanism was chosen because it is a recently developed, fairly compact mechanism with a total of 249 species and 1570 reactions, that the authors have validated against three sets of their plug flow reactor data at pressures of 30, 150, and 760 Torr in addition to also validating it against a set of their premixed flame data. The mechanism is an extension of Wang et al cyclohexane mechanism, 16 which added a methylcyclohexane submechanism composed of reactions and their rate constants calculated by the authors or borrowed from JetSurf2.0 and Wang et al's ethylcyclohexane work, 31 in addition to a submechanism for cC7H13 radicals, and two cyclohexyl reactions. The reaction rates for the cC7H13 radicals and the two cyclohexyl reactions were calculated by the authors.…”

Section: Wang Mechanismmentioning

confidence: 99%

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Variable high‐pressure and concentration study of cyclohexane pyrolysis at high temperatures

Liszka

Brezinsky

2018

Int J of Chemical Kinetics

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A high‐pressure and temperature cyclohexane pyrolysis shock tube study was completed with the goal of extending the experimental cyclohexane pyrolysis data to pressures relevant to current and future combustors and to investigate whether ring contraction products observed in high‐pressure, supercritical phase cyclohexane and cycloalkane pyrolysis experiments can form at matching, and higher, pressures in the gas phase. The experiments in the current work were completed over a range of 950–1650 K and at nominal pressures of 40, 100, and 200 bar. No alkylcyclopentanes, possible ring contraction products, were observed to form under the conditions of the current study. The production of methylenecyclopentane and 1,3‐cyclopentadiene, and the other three cyclic species quantified: cyclohexene, benzene, and toluene, increased significantly with a substantial increase in the initial fuel concentration. Two sets of experimental data obtained at 200 bar were compared with a literature and laboratory‐generated model. Both models had difficulty capturing the propadiene and propyne profiles, and the literature model significantly overestimated the benzene observed in the set of experiments completed with the more dilute fuel mixture. The literature model was able to better predict propadiene, propyne, and benzene product profiles in the 200 bar set of experiments, which used a higher concentration of fuel in the test gas. These results suggest that despite both cyclohexane and benzene being well‐studied and important species in combustion chemistry, their reaction pathways and reaction rates would benefit from further refinement.

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“…The DEC pyrolysis experiments were performed with the same apparatus as used in our previous study of DMC [6]. The detailed description of the apparatus and the schematic diagram could be referred to previous works [6,11]. Briefly, the apparatus is comprised of a pyrolysis chamber, a sampling system, a GC system and a linking transfer line.…”

Section: Flow Reactor Pyrolysismentioning

confidence: 99%

Exploring the high-temperature kinetics of diethyl carbonate (DEC) under pyrolysis and flame conditions

Sun

Huang

Tao

et al. 2017

Combustion and Flame

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To pursue insights into the high-temperature kinetics of diethyl carbonate (DEC), a potential clean oxygenated additive for diesel fuels, a systematical kinetic investigation was carried out in this work. Species mole fraction variations were recorded by a gas chromatography (GC) system during the pyrolysis of DEC in a flow reactor under three different pressures (30, 150 and 780 Torr). And quantitative measurements were conducted for over thirty species in a fuel-rich (ϕ=1.5) premixed DEC/O 2 /argon flame using synchrotron vacuum ultraviolet photoionization mass spectrometry. Pressure-dependent rate coefficients for DEC unimolecular decompositions were obtained with RRKM/master equation calculations. A kinetic model for DEC high-temperature pyrolysis and combustion was developed employing the calculated kinetic parameters, which could well predict all available measurements. Model analysis revealed that a two-step molecular elimination pathway exclusively led to the fuel decomposition under pyrolysis conditions, while in the premixed flame the fuel was consumed mainly by hydrogen abstractions from the secondary carbon atoms. The pyrolysis and combustion behaviors of DEC were compared with those of dimethyl carbonate (DMC), a simpler homologue of DEC, under similar conditions. It was found that DEC was of less thermal stability during the pyrolysis and that C 2 intermediates were of much higher concentrations in the DEC flame. Furthermore, it was found that DEC shared combustion characteristics with some other oxygenated fuels possessing specific common structural features.

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Investigation on primary decomposition of ethylcyclohexane at atmospheric pressure

Cited by 47 publications

References 23 publications

An experimental and kinetic modeling study on dimethyl carbonate (DMC) pyrolysis and combustion

An experimental and kinetic modeling study on dimethyl carbonate (DMC) pyrolysis and combustion

Variable high‐pressure and concentration study of cyclohexane pyrolysis at high temperatures

Exploring the high-temperature kinetics of diethyl carbonate (DEC) under pyrolysis and flame conditions

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