引用本文:牟川淋,蒲韵霜,余洋,邓淇铮,唐子钰,王林元,等. 甲烷在钯基催化剂上脱氢的分子模拟[J]. 石油与天然气化工, 2020, 49(3): 39-47.
【打印本页】   【HTML】   【下载PDF全文】   查看/发表评论  【EndNote】   【RefMan】   【BibTex】
←前一篇|后一篇→ 过刊浏览    高级检索
本文已被:浏览 158次   下载 123 本文二维码信息
码上扫一扫!
分享到: 微信 更多
甲烷在钯基催化剂上脱氢的分子模拟
牟川淋1,蒲韵霜1,余洋2,邓淇铮1,唐子钰1,王林元1,邓洪波1
1.西南石油大学化学化工学院;2.中国石油西南油气田公司成都天然气化工总厂
摘要:
为探明甲烷在钯基二聚体催化剂上脱氢反应过程的微观机理,对甲烷燃烧催化剂的设计与使用提供指导。在M06L/6-311++G(d,p)+SDD//M06L/6-311G(d,p)+LANL2DZ基组水平上,采用密度泛函理论(DFT)对甲烷在钯基二聚体催化剂(Pd2、PdPt和PdNi)上的脱氢过程进行了研究。对比了甲烷在催化剂Pd2、PdPt和PdNi上反应的能垒(Eb)、活化能(Ea)及反应速率常数(k),结果表明:CH2→CH是甲烷在二聚体Pd2反应的速率控制步骤(RDS),而CH3→CH2是催化剂PdPt和PdNi反应的RDS;钯基二聚体催化剂对甲烷脱氢的催化活性顺序为PdPt>Pd2>PdNi;抗积炭性能顺序为PdNi>Pd2>PdPt。PdPt适用于要求催化效率较高的项目,而抗积炭性能较好的PdNi催化剂可用于大型工业催化。 
关键词:  甲烷脱氢  密度泛函理论  钯基催化剂  二聚体催化剂
DOI:10.3969/j.issn.1007-3426.2020.03.007
分类号:
基金项目:
Molecular simulation of methane dehydrogenation on Pd-based catalysts
Mou Chuanlin1, Pu Yunshuang1, Yu Yang2, Deng Qizheng1, Tang Ziyu1, Wang Linyuan1, Deng Hongbo1
1. School of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu, Sichuan, China;2. Chengdu Natural Gas Chemical Plant General, PetroChina Southwest Oil & Gasfield Company, Chengdu, Sichuan, China
Abstract:
The study of the mechanism of methane dehydrogenation on Pd-based dimer catalyst can provide a guidance for the design and selection of catalyst on methane combustion. The processes of methane dehydrogenation on three Pd-based dimer catalysts (Pd2, PdPt and PdNi) are investigated using the density functional theory (DFT) calculation under the M06L/6-311++G(d,p)+SDD//M06L/6-311G(d,p)+LANL2DZ level. The energy barrier (Eb), activation energy (Ea), and reaction rate constant (k) of methane dehydrogenation on Pd2, PdPt and PdNi are compared. The results indicate that CH2→CH is the rate-determining step (RDS) for methane dehydrogenation on dimer Pd2, while CH3→CH2 is the RDS on PdPt and PdNi; the catalytic activity for methane dehydrogenation on Pd-based dimer catalyst follows the order of PdPt > Pd2 > PdNi; the anti-carbon performance follows the order of PdNi > Pd2 > PdPt. PdPt is suitable for those cases requiring higher catalytic efficiency, while PdNi catalyst is suitable for large-scale industrial production due to the good anti-carbon property.
Key words:  methane dehydrogenation  density functional theory  Pd-based catalyst  dimer catalyst