The effect of temperature and pressure on n-heptane thermal cracking in regenerative cooling channel

• Published in: Combustion and flame 2018-08, Vol.194, p.233-244
• Main Authors: Wu, Yong, Wang, Xiaohan, Song, Qianshi, Zhao, Luoguang, Su, Hang, Li, Haohan, Zeng, Xiaojun, Zhao, Daiqing, Xu, Jianzhong
• Format: Article
• Language: English
• Subjects: Alkanes; Alkenes; Chemical synthesis; Conversion; Cooling effects; Endothermic reactions; Ethylene; Fuels; Heptanes; Hydrocarbon fuels; Hydrocarbons; Mechanism model; N-heptane; Oxidation; Pressure; Pressure effects; Pyrolysis; Regenerative cooling; Residential density; Temperature; Temperature effects
• ISSN: 0010-2180; 1556-2921
• DOI: 10.1016/j.combustflame.2018.04.036

A thermal cracking experimental equipment of hydrocarbon fuels was built to study n-heptane pyrolysis and the effect of reaction conditions on this reaction process. The main species were measured and the change rules were analyzed on the range of temperature 873–1073 K and pressure 0.1–3.5 MPa. The total content of alkenes products was more than alkanes on this pyrolysis process. Compared to alkenes with same number carbons, the alkanes were more easy to decompose with temperature but more conducive to formation with pressure increasing. The content of ethylene is usually the most on above reaction conditions, but its descent is also the fastest with pressure increasing. A mechanism model of n-heptane pyrolysis (44 species and 166 reactions) was constructed and validated by experiments on different conditions. Compared with n-heptane oxidation detailed model of Version 3.1 from Lawrence Livermore National Laboratory (LLNL), the pyrolysis model present a better accordant with experiment results on a range of temperature and pressure. The kinetic reaction of n-heptane pyrolysis was analyzed with present pyrolysis model, and the pyrolysis reaction pathway for the main products was obtained. The formation of alkenes are mainly through CC bond dissociation reaction, especiallyβ-C dissociation, and small alkanes are formed mainly by radical metathetical or synthesis reaction, the former are endothermic reactions, but the latter are mostly exothermal reactions. The properties of some main reactions have a critical role for the change of product content with temperature and pressure, which is the main reason for the variety of products selectivity under different conditions. Pressure increased the pyrolysis residence time and mass density but it does not significantly affect the reaction energy, so its contribution to conversion rate of fuels thermal cracking is limited, although it changes the reaction pathway greatly. However, the temperature can increase obviously the reaction activation energy, even though the residence time and concentration is decreased, the conversion rate of n-heptane pyrolysis still increased.