物理化学学报2021，Vol.37Issue(11)：107-113,7.DOI:10.3866/PKU.WHXB202011012
基于ReaxFF的甲烷无氧转化气相机理研究
Gas-Phase Mechanism Study of Methane Nonoxidative Conversion by ReaxFF Method
摘要
Abstract
With the rapid consumption of petrochemical resources and massive exploitation of shale gas,the use of natural gas instead of petroleum to produce chemical raw materials has attracted significant attention.While converting methane to chemicals,it has long seemed impossible to avoid its oxidation into O-containing species,followed by de-oxygenation.A breakthrough in the nonoxidative conversion of methane was reported by Guo et al.(Science 2014,344,616),who found that Fe?SiO2 catalysts exhibited an outstanding performance in the conversion of methane to ethylene and aromatics.However,the reaction mechanism is still not clear owing to the complex experimental reaction conditions.One view of the reaction mechanism is that methane molecules are first activated on the Fe?SiC2 active center to form methyl radicals,which then desorb into the gas phase to form the ethylene and aromatics.In this study,ReaxFF methods are applied to five model systems to study the gas-phase reaction mechanism under near-experimental conditions.For the pure gas-phase methyl radical system,the main simulation product is ethane after 10 ns simulation,which is produced by the combination of methyl radicals.Although a small amount of ethylene produced by C2H6 dehydrogenation can be detected,it is difficult to explain the high selectivity for ethylene in the experiment.When the methyl radicals are mixed with hydrogen and methane molecules,ethane remains the main product,together with some methane produced by the collision of hydrogen with methyl radicals,while ethylene is still difficult to produce.With the addition of hydrogen radicals to the methane atmosphere,methane activation can be enhanced by hydrogen radical collisions,which produce some methyl radicals and hydrogen molecules,but the methyl radicals eventually combine with the hydrogen species to produce methane molecules again.If some hydrogen molecules and methyl radicals are added to the CH4/H· system,the activation of methane molecules by hydrogen radicals will be weakened.Hydrogen radicals are more likely to combine with themselves or with methyl radicals to form hydrogen and methane molecules,and the high selectivity for ethylene remains difficult to achieve.Thermal cracking of C10H12 at high temperature can produce hydrogen radicals and ethylene at the same time,which can partially explain the enhanced methane conversion and ethylene selectivity in the experiment of Hao et al.(ACS Catal.2019,9,9045).Overall,the selective production of ethylene by nonoxidative conversion of methane over Fe?SiO2 catalyst appears hard to achieve via a gas-phase mechanism.The catalyst surface may play a key role in the entire process of methane transformation.关键词
甲烷活化/无氧转化/气相机理/反应力场/计算模拟/热裂解反应Key words
Methane activation/Nonoxidative conversion/Gas-phase mechanism/Reactive force field/Computational simulation/Thermal cracking reaction分类
化学化工引用本文复制引用
刘源,段增晖,李隽,常春然..基于ReaxFF的甲烷无氧转化气相机理研究[J].物理化学学报,2021,37(11):107-113,7.基金项目
The project was supported by the National Natural Science Foundation of China(91645203,22078257),the China Postdoctoral Science Foundation(2018T111034,2018M630139),the Fundamental Research Funds for the Central Universities(xtr0218016,cxtd2017004),the Shaanxi Creative Talents Promotion Plan-Technological Innovation Team(2019TD-039),and the K.C.Wong Education Foundation.国家自然科学基金(91645203,22078257),中国博士后科学基金(2018T111034,2018M630139),中央高校基本科研业务费(xtr0218016,cxtd2017004),陕西省科技创新团队支持计划(2019TD-039)及王宽诚教育基金会资助项目 （91645203,22078257）
