文献类型：期刊文献

英文题名：Hydrogen abstraction of alkyl radicals from polycyclic aromatic hydrocarbons and heterocyclic aromatic hydrocarbons

作者：Wang, Yu-Hui[1];Wang, Li-Tao[2];Yao, Zhi-Zhen[1];Yin, Jun-Jian[1];Huang, Zi-Bin[1];Yuan, Pei-Qing[1];Yuan, Wei-Kang[1]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]Petrochina Petrochem Res Inst, Beijing 102249, Peoples R China

年份：2021

卷号：232

外文期刊名：CHEMICAL ENGINEERING SCIENCE

收录：;EI(收录号：20205109655807);WOS:【SCI-EXPANDED(收录号:WOS:000608126300003)】；

基金：The authors acknowledge the financial supports from NSFC (21676084), SINOPEC (ST18011-3-2) and CNPC (PRIKY19022).

语种：英文

外文关键词：Hydrogen abstraction; Polycyclic aromatic hydrocarbons; Heterocyclic aromatic hydrocarbons; Alkyl radicals; Density functional theory

摘要：To understand the condensation during heavy oil thermal processing, the formation of aromatic carbon radicals by H-abstraction of methyl radicals ((CH3)-C-center dot) or ethyl radicals ((C2H5)-C-center dot) from polycyclic aromatic hydrocarbons (PAHs) or heterocyclic aromatic hydrocarbons (hetero-PAHs) was studied by density functional calculation. The H-abstraction from different PAHs all has a positive standard state Gibbs free energy change, while increasing reaction temperature or radical concentration promotes the reaction to proceed spontaneously. (CH3)-C-center dot mainly contributes to the formation of aromatic carbon radicals on PAHs, and the activation entropy of H-abstraction determines the difference in reaction rate constants. The particularity of H-abstraction from hetero-PAHs is reflected at the alpha-site of heterocycles. The H abstraction from N-containing hetero-PAHs occurs preferentially at the alpha-site of heterocycles, and both (CH3)-C-center dot and (C2H5)-C-center dot could participate in abstracting the alpha-H. The H-abstraction from S-containing hetero-PAHs occurs preferentially on coupled aromatic rings, showing reaction behavior similar to the H-abstraction on PAHs. (C) 2020 Elsevier Ltd. All rights reserved.