镍基上羟基活化催化CH_4-CO_2重整的理论计算  

A study of the methane's hydroxyl-activate-reforming with carbon dioxide over nickel

作　　者：徐文媛[1] 胡林[1] 龙威[1] 杜瑞焕[1] 陈丽萍[1] 

机构地区：[1]华东交通大学化学化工系,江西南昌330013

出　　处：《浙江大学学报（理学版）》2013年第2期177-181,共5页Journal of Zhejiang University（Science Edition）

基　　金：国家自然科学基金资助项目(No.21163005;31160187);江西省自然科学基金资助项目(No.2008GQ0060)

摘　　要：采用DFT(B3LYP)结合二级微扰MP2/6-311+G(2d,p)方法计算镍基催化剂上羟基活化催化CH4-CO2重整制合成气的反应机理,比较并探究了重整反应机理中的各种通道.计算结果表明,重整反应包含22步,关键反应式1-1,2,3,4-1,4-2,6-4的正反应活化能分别为44.718,201.353,265.713,104.603,61.739和99.331kJ.mol-1.重整的速控步是式3表示的羟基的产生过程,甲烷的分解以脱1个H为主,基团CH3Ni具有较高的活性,可以通过2种方式与羟基反应,生成CH2OH基团继而裂解成甲醛.The mechanism of methane＇s hydroxyl-activate-reforming with carbon dioxide on nickel has been investiga- ted by DFT, MP2/6-31 lq-G（2d, p） method, Comparison of the reforming reaction mechanism and explore the vari- ous channels. The results have showed that the reforming reaction divided into 22 steps, the activation enthalpy of important five steps were： 44. 718,201. 353,265. 713,104. 603,61. 739 and 99. 331 kJ·mo1^-1. The rate-controlling step was the generation of hydroxyl process, and the most decomposition of methane was took off one hydrogen at- om, CH3 Ni has more high activity. There are two ways in the reaction between hydroxyl and CH^Ni. The product is CHz OH ,which could cleaved into formaldehyde.

关 键 词：CH4-CO2重整 过渡态 羟基活化 理论计算 

分 类 号：TE665.3[石油与天然气工程—油气加工工程]