陈立宇,雷鹏,师博辉,刘志林

• 1:西北大学化工学院
• 2:蒲城清洁能源化工有限责任公司

摘要(Abstract)：

对于甲烷在发烟硫酸溶液中液相部分氧化生成硫酸单甲酯的反应体系,采用密度泛函理论(DFT)进行了体系的热力学计算。在密度泛函理论B3LYP/6-31G(d)水平下结合极化连续模型(PCM),优化出了硫酸溶液中各种可能存在化合物的稳定结构,并在此基础上计算了硫酸溶液中各化合物在不同温度下的热力学性质,探讨了甲烷在发烟硫酸体系中各种可能的反应途径。计算结果表明,甲烷在发烟硫酸溶液中部分氧化生成硫酸单甲酯的反应途径是可行的,其中发烟硫酸中游离的SO3起了很重要的作用。

关键词(KeyWords)： 甲烷;部分氧化反应;硫酸单甲酯;发烟硫酸;热力学分析;密度泛函理论(DFT)

Abstract:

Keywords:

基金项目(Foundation): 陕西省科技厅重点项目(2009K10-11)

作者(Author): 陈立宇,雷鹏,师博辉,刘志林

参考文献(References)：

• [1]Periana R A,Doube J T,Gamble S,et al.Platinum catalysts for the high-yield oxidation of methane to methanol derivation[J].Science,1998,280(5363):560-564.
• [2]CHEN Li-yu(陈立宇),YANG Bo-lun(杨伯伦),ZHANG Xiu-cheng(张秀成),et al.Study of catalysis oxidation of methane tomethanol in liquid phase(甲烷液相部分氧化合成甲醇过程研究)[J].J Chem Eng of Chinese Univ(高校化学工程学报),2005,19(1):54-58.
• [3]CHEN Li-yu(陈立宇),YANG Bo-lun(杨伯伦),ZHANG Xiu-cheng(张秀成),et al.Partial oxidation of methane to methanol inliquid Phase by V2O5catalyst(V2O5催化的甲烷液相部分氧化反应)[J].Chinese Journal of Catalysis(催化学报),2005,26(11):1027-1037.
• [4]CHEN Li-yu(陈立宇),YANG Bo-lun(杨伯伦),ZHANG Xiu-cheng(张秀成),et al.Study on the partial oxidation orocess ofmethane in liquid phase catalyzed by V2O5(V2O5催化甲烷液相部分氧化工艺过程研究)[J].J Chem Eng of Chinese Univ(高校化学工程学报),2006,20(3):417-421.
• [5]ZHANG Xiu-cheng(张秀成),CAO Kai(曹凯),CHEN Li-yu(陈立宇),et al.Selective oxidation of methane to methanol catalyzedby V2O5catalyst in liquid phase(V2O5催化剂液相选择性氧化甲烷合成甲醇)[J].Petrochemical Technology(石油化工),2004,33(9):813-815.
• [6]Chen Li-yu,Yang Bo-lun,Zhang Xiu-cheng,et al.Methane partial oxidation in liquid phase using vanadium containingheteropolyacid catalysts in Oleum[J].Chinese Journal of Catalysis,2006,27(6):462-464.
• [7]Jeremy Kua,Xin Xu,Roy A Periana,et al.Stability and thermodynamics of the PtCl2 type catalyst for activating methane tomethanol:A computational study[J].Organometallics,2002,21(1):511-525.
• [8]Michalkiewicz B,Kalucki K,Sosnicki J G.Catalytic system containing metallic palladium in the process of methane partialoxidation[J].J Catal,2003,215(1):14-19.
• [9]Periana R A,Doube J T,Evitt R E,et al.A mercury-catalyzed high-yield system for the oxidation of methane to methanol[J].Science,1993,259(15):340-343.
• [10]XU Fang-nian(徐方年).Preparation of sulfuric acid dimethyl ester(硫酸二甲酯的制备)[J].Leather Chemicals(皮革化工),2000,179(3):39-40.
• [11]Xiao G,Yimin Zhu,Henning Birch,et al.Iodine as catalyst for the direct oxidation of methane to methyl sulfates in oleum[J].ApplCatal A,2004,261(1):91-98.