文献类型：期刊文献

英文题名：Dealkylation of Aromatics in Subcritical and Supercritical Water: Involvement of Carbonium Mechanism

作者：Chen, Yi[1];Wang, Kai[1];Yang, Jing-Yi[2];Yuan, Pei-Qing[1];Cheng, Zhen-Min[1];Yuan, Wei-Kang[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Res Inst Petr Proc, Shanghai 200237, Peoples R China

年份：2016

卷号：55

期号：36

起止页码：9578

外文期刊名：INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH

收录：;EI(收录号：20163802826969);WOS:【SCI-EXPANDED(收录号:WOS:000383409700003)】；

基金：This work was supported by the Open Project of State Key Laboratory of Chemical Engineering (SKL-ChE-13C02) and the National Natural Science Foundation of China (Grant No. 21376075; Grant No. 21676084).

语种：英文

外文关键词：Ethylene - Reaction kinetics - Heavy oil production - Thermodynamic properties - Crude oil - Protonation - Pyrolysis

摘要：Under hydrothermal environments covering the subcritical and supercritical regions of water, the involvement of the carbonium mechanism in the dealkylation of aromatics and its resulting influence on the pyrolysis of heavy oil were surveyed. a-Olefin groups, as either a part of straight chain hydrocarbons or the terminal of alkyl substitutes of aromatics, are protonated spontaneously by hydronium ions into carboniums, followed by beta-scission with similar reaction kinetic characteristics. The probability of the protonation of alpha-olefins under hydrothermal environments depends on the ionic product of water, so the occurrence of the beta-scission in the carbonium mechanism is related to the thermodynamic state of water. With the aid of the carbonium mechanism at increasing water density, a recovered conversion rate and an increasing ratio of propene to ethylene in the product occur during the pyrolysis of a model a-olefin of dodecene under hydrothermal environments. Also, the dealkylation involved in the pyrolysis of maltenes is accelerated.