太原理工大学学报2017，Vol.48Issue(4)：530-538,9.DOI:10.16355/j.cnki.issn1007-9432tyut.2017.04.004
煤沥青中16种多环芳烃烷基化反应的量子化学研究
Quantum Chemistry Study on Alkylation Reaction of 16 Polycyclic Aromatic Hydrocarbons in Coal Tar Pitch
摘要
Abstract
Under the catalysis of HF,the alkylation process of 16 polycyclic aromatic hydrocarbons (PAHs) in coal tar pitch (CTP) with ethylene was studied by using the first principle.The alkylation reaction mechanism of 16 PAHs with ethylene was discussed according to the adsorption enthalpy and activation energy.The reactants could go through three processes to form the six-membered-ring transition state.In any reaction process,ethylene molecules are activated by HF and the fluorine atom help to remove hydrogen from the aromatic rings.Acenaphthylene,chrysene,benzo [a] pyrene and benzo[g,h,i] perylene were selected from 16 PAHs as objects of study,and the activation energy of alkylation reaction of the four substances were calculated.The calculated activation energy locates in two discontinuous ranges.The lower energies are between 35 and 41 kJ/mol and higher energies are between 58 and 59 kJ/mol.An obvious feature of the inactive sites with higher activation energies is that the carbon is linked by two carbon atoms which have only one C-H bond.The activation energies of active sites of the rest 12 PAHs were calculated in the following calculations.The difficulty level of reactions of 16 PAHs with ethylene was achieved on the basis of the calculated activation energies.Among the 16 PAHs,the substance with lowest activation energy is benzo [a] anthracene and the substance with highest activation energy is fluorine.This paper provides guidance to select model compounds for the modification of CTP.关键词
煤沥青/多环芳烃/烷基化反应机理/活化能Key words
coal tar pitch/polycyclic aromatic hydrocarbons/alkylation reaction mechanism/activation energy分类
化学化工引用本文复制引用
代金波,刘刚,申峻,王玉高,李瑞丰,杜建奎,徐青柏..煤沥青中16种多环芳烃烷基化反应的量子化学研究[J].太原理工大学学报,2017,48(4):530-538,9.基金项目
交通运输部公路科学研究院道路结构与材料交通行业重点实验室(北京)开放基金资助项目(KF201401) （北京）
山西省科技攻关项目(20150313014-4) （20150313014-4）
山西煤基低碳联合基金资助项目(U1610223) （U1610223）
