Experimental and Modeling Investigation of <i>n</i>-Decane Pyrolysis at Supercritical Pressures

Jia, Zhenjian; Huang, Hongyan; Zhou, Weixing; Qi, Fei; Zeng, Meirong

doi:10.1021/ef5009314

Cited by 66 publications

(29 citation statements)

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“…Detail mechanisms of the pyrolysis of n-decane, n-tetradecane, and n-icosane can be found in the supplement material. These results are in agreement with experiments, [48][49][50][51] which indicate that the DP model and the dataset has strong transferability in long-chain alkanes. It is worth mentioning that long-chain alkanes are the main components of many fuels.…”

Section: Transferability Of the Dp Model/datasetsupporting

confidence: 89%

Exploring the Chemical Space of Linear Alkane Pyrolysis via Deep Potential GENerator

et al. 2020

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Reactive molecular dynamics (MD) simulation is a powerful tool to study the reaction mechanism of complex chemical systems. Central to the method is the potential energy surface (PES) that can describe the breaking and formation of chemical bonds. The development of PES of both accurate and efficent has attracted significant effort in the past two decades. Recently developed Deep Potential (DP) model has the promise to bring ab initio accuracy to large-scale reactive MD simulations. However, for complex chemical reaction processes like pyrolysis, it remains challenging to generate reliable DP models with an optimal training dataset. In this work, a dataset construction 1 scheme for such a purpose was established. The employment of a concurrent learning algorithm allows us to maximize the exploration of the chemical space while minimize the redundancy of the dataset. This greatly reduces the cost of computational resources required by ab initio calculations. Based on this method, we constructed a dataset for the pyrolysis of n-dodecane, which contains 35,496 structures. The reactive MD simulation with the DP model trained based on this dataset revealed the pyrolysis mechanism of n-dodecane in detail, and the simulation results are in good agreement with the experimental measurements. In addition, this dataset shows excellent transferability to different long-chain alkanes. These results demonstrate the advantages of the proposed method for constructing training datasets for similar systems.

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Section: Transferability Of the Dp Model/datasetsupporting

confidence: 89%

Exploring the Chemical Space of Linear Alkane Pyrolysis via Deep Potential GENerator

et al. 2020

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“…The selected PAH include several features which contribution to the bond formation mechanism between PAH is investigated in this study, like aliphatic side chains, five membered rings, different aromatic sites and radicals. [70][71][72][73][74] Based on the above-mentioned selection criteria we generated a ReaxFF-input gas mixture. The total mole fraction of the selected PAH varies between 10 and 900 ppm of the total mole fraction of the initial gas phase when changing the temperature, equivalence ratio and fuel compositions.…”

Section: Figurementioning

confidence: 99%

A Theoretical Multiscale Approach to Study the Initial Steps Involved in the Chemical Reactivity of Soot Precursors

et al. 2019

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In the present study bond formation reactions between soot precursors and their role in the soot inception process is investigated. The soot precursors were generated in macroscopic detailed gas-phase kinetic calculations and according to certain criteria introduced in simulation boxes to model bond formation between soot precursor molecules with reactive force field molecular dynamics modeling. The impacts of temperature, fuel mixture and equivalence ratio have been investigated on the rate and structure of the newly formed molecules. The resulting structures compare well to previously reported experimental results. Furthermore, the bond formation rate between PAH is found to be linearly correlated with the temperature at which the PAH precursors are generated, while fuel and equivalence ratio do not have a direct impact on the reaction rate. The generated growth structures are lumped in: 1) directly linked, 2) aliphatically linked and 3) pericondensed polycyclic hydrocarbons. It is found that the amount of aliphatically linked PAH increases with the amount of aliphatic content of fuel mixture. Finally, a reaction scheme is presented displaying the most representative reaction pathways to form growth structures in each lumping class and their eventual interconversion. The present work -that applies a combined approach of macroscopic gas-phase kinetic calculations and atomistic reactive force field simulations -offers a good alternative to obtain structural differences of nascent soot for a broad range of thermodynamic conditions and detailed reaction mechanisms for soot inception process.

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“…For pyrolysis studies, the authors exploited 1060 K at a pressure of 760 Torr and inlet mole fraction of n-decane to be 1456 ppm. Zhou et al 50 presented an experimental and modeling investigation of n-decane pyrolysis at supercritical pressures at the temperature range from 773 to 943 K and pressures of 22 500, 30 000, and 37 500 Torr. This study exposed that n-decane was mainly consumed via hydrogen abstraction reactions followed by β-scission to form smaller C1 to C6 products.…”

Section: Introductionmentioning

confidence: 99%

Combined Experimental and Computational Study on the Unimolecular Decomposition of JP-8 Jet Fuel Surrogates. I. n-Decane (n-C₁₀H₂₂)

et al. 2017

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Exploiting a high temperature chemical reactor, we explored the pyrolysis of helium-seeded n-decane as a surrogate of the n-alkane fraction of Jet Propellant-8 (JP-8) over a temperature range of 1100-1600 K at a pressure of 600 Torr. The nascent products were identified in situ in a supersonic molecular beam via single photon vacuum ultraviolet (VUV) photoionization coupled with a mass spectroscopic analysis of the ions in a reflectron time-of-flight mass spectrometer (ReTOF). Our studies probe, for the first time, the initial reaction products formed in the decomposition of n-decane-including radicals and thermally labile closed-shell species effectively excluding mass growth processes. The present study identified 18 products: molecular hydrogen (H), C2 to C7 1-alkenes [ethylene (CH) to 1-heptene (CH)], C1-C3 radicals [methyl (CH), vinyl (CH), ethyl (CH), propargyl (CH), allyl (CH)], small C1-C3 hydrocarbons [methane (CH), acetylene (CH), allene (CH), methylacetylene (CH)], along with higher-order reaction products [1,3-butadiene (CH), 2-butene (CH)]. On the basis of electronic structure calculations, n-decane decomposes initially by C-C bond cleavage (excluding the terminal C-C bonds) producing a mixture of alkyl radicals from ethyl to octyl. These alkyl radicals are unstable under the experimental conditions and rapidly dissociate by C-C bond β-scission to split ethylene (CH) plus a 1-alkyl radical with the number of carbon atoms reduced by two and 1,4-, 1,5-, 1,6-, or 1,7-H shifts followed by C-C β-scission producing alkenes from propene to 1-octene in combination with smaller 1-alkyl radicals. The higher alkenes become increasingly unstable with rising temperature. When the C-C β-scission continues all the way to the propyl radical (CH), it dissociates producing methyl (CH) plus ethylene (CH). Also, at higher temperatures, hydrogen atoms can abstract hydrogen from CH to yield n-decyl radicals, while methyl (CH) can also abstract hydrogen or recombine with hydrogen to form methane. These n-decyl radicals can decompose via C-C-bond β-scission to C3 to C9 alkenes.

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Experimental and Modeling Investigation of n-Decane Pyrolysis at Supercritical Pressures

Cited by 66 publications

References 50 publications

Exploring the Chemical Space of Linear Alkane Pyrolysis via Deep Potential GENerator

Exploring the Chemical Space of Linear Alkane Pyrolysis via Deep Potential GENerator

A Theoretical Multiscale Approach to Study the Initial Steps Involved in the Chemical Reactivity of Soot Precursors

Combined Experimental and Computational Study on the Unimolecular Decomposition of JP-8 Jet Fuel Surrogates. I. n-Decane (n-C₁₀H₂₂)

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Experimental and Modeling Investigation of n-Decane Pyrolysis at Supercritical Pressures

Cited by 66 publications

References 50 publications

Exploring the Chemical Space of Linear Alkane Pyrolysis via Deep Potential GENerator

Exploring the Chemical Space of Linear Alkane Pyrolysis via Deep Potential GENerator

A Theoretical Multiscale Approach to Study the Initial Steps Involved in the Chemical Reactivity of Soot Precursors

Combined Experimental and Computational Study on the Unimolecular Decomposition of JP-8 Jet Fuel Surrogates. I. n-Decane (n-C10H22)

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Combined Experimental and Computational Study on the Unimolecular Decomposition of JP-8 Jet Fuel Surrogates. I. n-Decane (n-C₁₀H₂₂)